CN116751343A - VPR/NBR nanoparticle latex with core-shell structure and preparation method and application thereof - Google Patents
VPR/NBR nanoparticle latex with core-shell structure and preparation method and application thereof Download PDFInfo
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- CN116751343A CN116751343A CN202310742369.9A CN202310742369A CN116751343A CN 116751343 A CN116751343 A CN 116751343A CN 202310742369 A CN202310742369 A CN 202310742369A CN 116751343 A CN116751343 A CN 116751343A
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- latex
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- butadiene
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- 229920000126 latex Polymers 0.000 title claims abstract description 160
- 239000004816 latex Substances 0.000 title claims abstract description 157
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- 239000011258 core-shell material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 139
- 239000004094 surface-active agent Substances 0.000 claims abstract description 97
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 39
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 33
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 32
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 83
- 238000003756 stirring Methods 0.000 claims description 37
- -1 fatty alcohol sulfate Chemical class 0.000 claims description 34
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000007872 degassing Methods 0.000 claims description 30
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- NVJCKICOBXMJIJ-UHFFFAOYSA-M potassium;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [K+].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O NVJCKICOBXMJIJ-UHFFFAOYSA-M 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 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 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011874 heated mixture Substances 0.000 claims description 9
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 claims description 7
- 239000011995 wilkinson's catalyst Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 229940096992 potassium oleate Drugs 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 229940114930 potassium stearate Drugs 0.000 claims description 6
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 6
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 6
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 6
- 229940080350 sodium stearate Drugs 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 241001391944 Commicarpus scandens Species 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 18
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 18
- 229940051841 polyoxyethylene ether Drugs 0.000 description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 description 18
- 239000013068 control sample Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000693 micelle Substances 0.000 description 7
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical compound CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a VPR/NBR nanoparticle latex with a core-shell structure, a preparation method and application thereof. The invention is composed of an inner core and an outer shell, wherein the inner core comprises butadiene-acrylonitrile latex, the outer shell comprises butadiene-acrylonitrile latex, and the butadiene-acrylonitrile latex is formed by copolymerizing butadiene and acrylonitrile; the preparation method comprises the following raw materials: 100-200 parts of deionized water, 50-100 parts of butadiene-pyridine latex, 3-10 parts of surfactant, 30-50 parts of acrylonitrile, 50-70 parts of butadiene, 0.02-0.10 part of initiator and 0.2-1.0 part of chain transfer agent. The invention also provides a preparation method of the nanoparticle latex and application of the nanoparticle latex in preparation of hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation. The VPR/NBR nanoparticle latex with the core-shell structure has stable performance, small particle size distribution range, good hydrogenation effect and high hydrogenation degree, and is not easy to break emulsion.
Description
Technical Field
The invention belongs to the technical field of rubber polymers, and particularly relates to a VPR/NBR nanoparticle latex with a core-shell structure, and a preparation method and application thereof.
Background
Hydrogenated nitrile rubber (Hydrogenated nitrile rubber), abbreviated as HNBR or HSN, is the product of the hydrogenation saturation of carbon-carbon double bonds on the molecular chain in nitrile rubber, also known as highly saturated nitrile rubber. The hydrogenated nitrile latex (HNBR) has good oil resistance and good resistance to fuel oil, lubricating oil and aromatic solvents; in addition, due to the highly saturated structure, the material also has good heat resistance and excellent chemical corrosion resistance, and has good resistance to freon, acid and alkali; meanwhile, hydrogenated nitrile rubber (HNBR) also has high strength, high tear properties, excellent abrasion resistance and the like, and is one of rubbers excellent in combination properties.
Currently, there are three main processes for the preparation of hydrogenated nitrile rubber (HNBR): an ethylene-acrylonitrile copolymerization process, a nitrile rubber (NBR) solution hydrogenation process, and a nitrile rubber (NBR) emulsion hydrogenation process. When preparing HNBR by ethylene-acrylonitrile copolymerization, r is because of large difference of reaction rate of each monomer in copolymerization process Acrylonitrile (Acrylonitrile) ＝0.04，r Ethylene =0.8, relatively difficult to control, the resulting product has high molecular chain branching, and poor randomness, and poor polymer properties. When HNBR is prepared by NBR solution hydrogenation, noble metals palladium, ruthenium and rhodium are used as catalysts in NBR solution, hydrogen is used for hydrogenation, and the solvents used are chlorobenzene, cyclohexanone, dimethylbenzene, chloroform and the like; this method has the disadvantages of high catalyst cost and high catalyst efficiencyDifficult separation, incomplete NBR hydrogenation reaction, high reaction temperature and pressure, easy environmental pollution caused by the use of a large amount of organic reagents, and the like. When HNBR is prepared by an NBR emulsion hydrogenation method, a catalyst is directly added into NBR emulsion, and HNBR emulsion and crude rubber are prepared by hydrogen reduction reaction; the existing NBR emulsion has complex micelle structure, has various micelles with different forms, has poor size uniformity and large particle size distribution range, and influences the hydrogenation effect of NBR, thereby leading to low hydrogenation degree of the NBR latex.
Disclosure of Invention
The invention aims to provide a VPR/NBR nanoparticle latex with a core-shell structure, a preparation method and application thereof, and aims to solve the problem that the hydrogenation degree of NBR latex is low due to the influence of uneven particle size distribution of NBR micelle on the hydrogenation effect of NBR when HNBR is prepared by an NBR emulsion hydrogenation method in the prior art.
In order to solve the technical problems, the invention is mainly realized by the following technical scheme:
in one aspect, the VPR/NBR nanoparticle latex with a core-shell structure comprises a core and a shell, wherein the core comprises butadiene-acrylonitrile latex, the shell comprises butadiene-acrylonitrile latex, and the butadiene-acrylonitrile latex is formed by copolymerizing butadiene and acrylonitrile; the VPR/NBR nanoparticle latex with the core-shell structure comprises the following raw materials in parts by weight: 100-200 parts of deionized water, 50-100 parts of butadiene-pyridine latex, 3-10 parts of surfactant, 30-50 parts of acrylonitrile, 50-70 parts of butadiene, 0.02-0.10 part of initiator and 0.2-1.0 part of chain transfer agent.
The VPR/NBR nanoparticle latex with the core-shell structure takes the seed emulsion-butadiene-acrylonitrile latex as an inner core, and the butadiene-acrylonitrile copolymer is formed into a nitrile latex shell on the surface of the seed emulsion, so that the VPR/NBR nanoparticle latex with the core-shell structure has stable performance, good size uniformity of the nano micelle, small particle size distribution range, difficult demulsification and 40-46% of solid content; the VPR/NBR nanoparticle latex with the core-shell structure has good hydrogenation effect and high hydrogenation degree in the process of preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation.
As a preferred embodiment, the particle size of the butadiene-pyridine latex is 80-100nm, and the solid content of the butadiene-pyridine latex is 40-50%. The butadiene-pyridine latex of the invention is a binary copolymer of vinyl pyridine (alpha-methyl-5-vinyl pyridine) and butadiene, called butadiene-pyridine latex (butadiene vinyl-pyridine rubber latex). The butyl-pyridine latex (VPR) is rubber with higher tensile strength and tear strength, takes the butyl-pyridine latex as an inner core, and is polymerized on the surface to form a nitrile-butadiene latex (NBR) shell, so that the excellent heat resistance, oil resistance and wear resistance of the nitrile-butadiene latex are maintained, and the obvious mechanical property of the VPR/NBR nanoparticle latex is provided.
As a preferred embodiment, the surfactant is any one or more of alkyl sulfonate, alkylbenzenesulfonate, carboxylate salt, fatty alcohol sulfate salt, alkyl sulfate salt, phosphate salt, alkylphenol ethoxylate, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine. The invention uses the surfactant in the preparation process of the VPR/NBR nanoparticle latex with the core-shell structure, the surfactant can greatly reduce the tension of an oil/water interface, and an interface film is formed by adsorption at the interface, thereby being beneficial to improving the stability.
As a preferred embodiment, the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether. The surfactant comprises an anionic surfactant and a nonionic surfactant, the anionic surfactant has poor chemical stability to electrolyte, the particle size of the generated latex particles is small, the latex stability is good, aggregation is not easy to generate in the polymerization process, and the latex with high and stable solid content can be obtained; the nonionic surfactant has good chemical stability to electrolyte, but the polymerization reaction speed is slower, the particle size of the obtained latex particles is larger, and coagulation blocks are easy to generate in the polymerization process; the anionic surfactant and the nonionic surfactant are used in a combined way, complement each other and promote each other.
As a preferred embodiment, the surfactant is a mixture of disproportionated potassium abietate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether according to the weight ratio of 3-5:1-3:1-3. The surfactant of the invention is a composite surfactant, which is composed of anionic surfactant and nonionic surfactant, thus not only improving the physical stability of latex, but also improving the chemical stability of latex and having good comprehensive performance.
As a preferred embodiment, the initiator is any one or more of ammonium persulfate, potassium persulfate and sodium persulfate. The initiator of the invention is a polysulfide initiator, the oxidation capacity of the polysulfide initiator is strong, the reaction speed is high, and the highest concentration of the reaction can be achieved at normal temperature.
As a preferred embodiment, the chain transfer agent is any one or more of n-dodecyl mercaptan, tert-butyl mercaptan and n-butyl mercaptan. The chain transfer agent of the invention is properly selected, has good performance and can effectively reduce the molecular weight of the latex.
In another aspect, the invention provides a method for preparing a core-shell structured VPR/NBR nanoparticle latex, comprising the steps of: 1) Mixing deionized water, butadiene-pyridine latex and a surfactant to obtain a mixture A; 2) Taking acrylonitrile and a chain transfer agent, sequentially adding the acrylonitrile and the chain transfer agent into the mixture A obtained in the step 1), and mixing to obtain a mixture B; 3) Introducing inert gas into the mixture B obtained in the step 2), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the mixture B after the degassing treatment, mixing, and pre-emulsifying for 0.5-6h at normal temperature and a rotating speed of 150-450r/min to obtain a mixture C; 4) Heating the mixture C obtained in the step 3) to 40-80 ℃, taking an initiator, adding the initiator into the heated mixture C, and carrying out polymerization reaction for 2-5h at the stirring rotation speed of 100-500r/min to obtain the VPR/NBR nanoparticle latex with the core-shell structure.
In the preparation method of the VPR/NBR nanoparticle latex with the core-shell structure, seed emulsion, namely the butadiene-pyridine latex, is dispersed in deionized water by utilizing a surfactant, and the dispersion performance of the butadiene-pyridine latex in the deionized water is greatly improved under the action of the surfactant, so that the butadiene-pyridine latex is uniformly dispersed, and emulsion with stable performance is formed, thereby ensuring that the butadiene-pyridine latex can be uniformly mixed with acrylonitrile added subsequently; after butadiene is added, pre-emulsification reaction is carried out first to fully pre-emulsify the monomer, thereby effectively controlling the molecular weight of the polymer, controlling the particle size distribution of the latex and ensuring the good performance of the latex. The preparation method of the VPR/NBR nanoparticle latex with the core-shell structure is simple, convenient to operate and easy to realize industrialization.
As a preferred embodiment, in the step 3), the degassing treatment is performed at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min. The degassing treatment of the invention is to sufficiently remove oxygen in the reaction system, inert gases used in the degassing treatment are nitrogen, helium, argon and the like, and the degassing is carried out under the stirring condition, so that the oxygen in the reaction system can be sufficiently removed, and the degassing efficiency is high.
As a preferred embodiment, in said step 3), the time of pre-emulsification is 1 to 3 hours. The invention controls the polymerization reaction process of acrylonitrile and butadiene through pre-emulsification, and controls the molecular weight of the polymer, thereby effectively controlling the particle size distribution of the latex.
As a preferred embodiment, in the step 3), the speed of the pre-emulsification is 200-350r/min. The pre-emulsification is realized by stirring, the rotating speed in the pre-emulsification process is controlled to control the speed and uniformity of the pre-emulsification, and the pre-emulsification device is convenient to control and easy to operate.
In a further aspect, the invention relates to the use of a core-shell structured VPR/NBR nanoparticle latex for the preparation of hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation.
The VPR/NBR nanoparticle latex with the core-shell structure is used for preparing the hydrogenated butyl-pyridine/hydrogenated nitrile rubber by emulsion hydrogenation, and has stable performance, difficult demulsification, small particle size distribution range, good hydrogenation effect and high hydrogenation degree in the emulsion hydrogenation process.
As a preferred embodiment, the method comprises the steps of: a) Taking the VPR/NBR nanoparticle latex with a core-shell structure and a Wilkinson catalyst, wherein the dosage of the Wilkinson catalyst is 0.02-0.10% of the weight of the VPR/NBR nanoparticle latex with the core-shell structure, and mixing to obtain a first mixture; b) Taking a surfactant, adding the surfactant into the first mixture obtained in the step a), wherein the dosage of the surfactant is 2-8% of the weight of the VPR/NBR nanoparticle latex with a core-shell structure, and mixing to obtain a second mixture; c) And (3) introducing inert gas into the second mixture, stirring, degassing, introducing high-pressure hydrogen, wherein the pressure of the hydrogen is 5-10MPa, and carrying out hydrogenation reaction for 2-8h at 100-150 ℃ to obtain the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber.
The VPR/NBR nanoparticle latex with a core-shell structure is used for preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation, and is a post-polymerization green process; the deionized water carried in the preparation process of the VPR/NBR nanoparticle latex with the core-shell structure is a solvent in the reaction process of preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by hydrogenating the emulsion, is used for stabilizing hydrogenated unsaturated polymer particles in the emulsion, replaces an organic solvent, and is a safer, cheaper and environmentally friendly preparation method of the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber.
In a preferred embodiment, in the step b), the surfactant is any one or more of alkyl sulfonate, alkylbenzenesulfonate, carboxylate, fatty alcohol sulfate, alkyl sulfate, phosphate, alkylphenol ethoxylate, fatty acid polyoxyethylene ester, and polyoxyethylene alkylamine. The surfactant is added in the process of preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation to stabilize the VPR/NBR nanoparticle latex with a core-shell structure, so that the emulsion is not broken in the process of emulsion hydrogenation, and the hydrogenation effect is effectively improved.
In a preferred embodiment, in the step b), the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether. The invention also uses anionic surfactant and nonionic surfactant in the process of preparing the hydrogenated butyl-pyridine/hydrogenated nitrile rubber by emulsion hydrogenation, and the two surfactants are exactly matched with the VPR/NBR nanoparticle latex system with a core-shell structure, so that the use effect is good.
In a preferred embodiment, in the step b), the surfactant is a mixture of potassium disproportionated abietic acid and sodium dodecyl sulfate in a weight ratio of 2-6:3-5. In the process of preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation, the invention uses the composite surfactant composed of the anionic surfactant-disproportionated potassium abietate and the nonionic surfactant-sodium dodecyl sulfate, and the composite surfactant mutually promotes and mutually cooperates, thereby better meeting the requirements of a VPR/NBR nanoparticle latex system with a core-shell structure and having good use effect.
As a preferred embodiment, in the step c), the degassing treatment is carried out at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min. In the process of preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation, the degassing treatment is also needed, the oxygen in the reaction system is sufficiently removed, inert gases used in the degassing treatment are nitrogen, helium, argon and the like, and the degassing is carried out under the stirring condition, so that the oxygen in the reaction system can be sufficiently removed, and the degassing efficiency is high.
Compared with the prior art, the invention has the beneficial effects that: the VPR/NBR nanoparticle latex with the core-shell structure takes the seed emulsion, namely the butadiene-acrylonitrile latex, as an inner core, and the butadiene-acrylonitrile copolymer is formed on the surface of the seed emulsion to form a nitrile latex shell, so that the VPR/NBR nanoparticle latex with the core-shell structure has stable performance, good size uniformity of the nano micelle, small particle size distribution range, difficult demulsification, simple preparation method, convenient operation and easy realization of industrialization; the VPR/NBR nanoparticle latex with the core-shell structure has good hydrogenation effect and high hydrogenation degree in the process of hydrogenating the emulsion.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with specific embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The VPR/NBR nanoparticle latex with the core-shell structure comprises a core and a shell, wherein the core comprises butadiene-acrylonitrile latex, the shell comprises butadiene-acrylonitrile latex, and the butadiene-acrylonitrile latex is formed by copolymerizing butadiene and acrylonitrile; the VPR/NBR nanoparticle latex with the core-shell structure comprises the following raw materials in parts by weight: 100-200 parts of deionized water, 50-100 parts of butadiene-pyridine latex, 3-10 parts of surfactant, 30-50 parts of acrylonitrile, 50-70 parts of butadiene, 0.02-0.10 part of initiator and 0.2-1.0 part of chain transfer agent.
Preferably, the particle size of the butadiene-pyridine latex is 80-100nm, and the solid content of the butadiene-pyridine latex is 40-50%.
Preferably, the surfactant is any one or more of alkyl sulfonate, alkylbenzenesulfonate, carboxylate, fatty alcohol sulfate, alkyl sulfate, phosphate, alkylphenol ethoxylate, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine.
Further, the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether.
Specifically, the surfactant is a mixture of disproportionated potassium abietate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether according to the weight ratio of 3-5:1-3:1-3.
Preferably, the initiator is any one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the chain transfer agent is any one or more of n-dodecyl mercaptan, tert-butyl mercaptan and n-butyl mercaptan.
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Mixing deionized water, butadiene-pyridine latex and a surfactant to obtain a mixture A;
2) Taking acrylonitrile and a chain transfer agent, sequentially adding the acrylonitrile and the chain transfer agent into the mixture A obtained in the step 1), and mixing to obtain a mixture B;
3) Introducing inert gas into the mixture B obtained in the step 2), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the mixture B after the degassing treatment, mixing, and pre-emulsifying for 0.5-6h at normal temperature and a rotating speed of 150-450r/min to obtain a mixture C;
4) Heating the mixture C obtained in the step 3) to 40-80 ℃, taking an initiator, adding the initiator into the heated mixture C, and carrying out polymerization reaction for 2-5h at the stirring rotation speed of 100-500r/min to obtain the VPR/NBR nanoparticle latex with the core-shell structure.
Preferably, in the step 3), the degassing treatment is performed at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min.
Preferably, in the step 3), the time of pre-emulsification is 1-3h.
Preferably, in the step 3), the speed of the pre-emulsification is 200-350r/min.
The invention relates to application of a VPR/NBR nanoparticle latex with a core-shell structure, which is used for preparing hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber by emulsion hydrogenation.
Preferably, the method comprises the following steps: a) Taking the VPR/NBR nanoparticle latex with a core-shell structure and a Wilkinson catalyst, wherein the dosage of the Wilkinson catalyst is 0.02-0.10% of the weight of the VPR/NBR nanoparticle latex with the core-shell structure, and mixing to obtain a first mixture; b) Taking a surfactant, adding the surfactant into the first mixture obtained in the step a), wherein the dosage of the surfactant is 2-8% of the weight of the VPR/NBR nanoparticle latex with a core-shell structure, and mixing to obtain a second mixture; c) And (3) introducing inert gas into the second mixture, stirring, degassing, introducing high-pressure hydrogen, wherein the pressure of the hydrogen is 5-10MPa, and carrying out hydrogenation reaction for 2-8h at 100-150 ℃ to obtain the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber.
Preferably, in the step b), the surfactant is any one or more of alkyl sulfonate, alkylbenzenesulfonate, carboxylate salt, fatty alcohol sulfate salt, alkyl sulfate salt, phosphate salt, alkylphenol ethoxylate, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine.
Further, in the step b), the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether.
Specifically, in the step b), the surfactant is a mixture of disproportionated potassium abietate and sodium dodecyl sulfate according to the weight ratio of 2-6:3-5.
Preferably, in the step c), the degassing treatment is performed at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min.
Example 1
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Weighing the following raw materials in parts by weight: 124g of deionized water, 85g of butadiene-pyridine latex, 1.5g of surfactant sodium dodecyl sulfate, 1.5g of surfactant nonylphenol polyoxyethylene ether, 36g of acrylonitrile, 64g of butadiene, 0.04g of initiator ammonium persulfate and 0.5g of chain transfer agent tertiary dodecyl mercaptan; wherein, the particle size of the butadiene-pyridine latex is 80nm, and the solid content is 50%;
2) Taking deionized water, butadiene-pyridine latex, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the deionized water, the butadiene-pyridine latex, the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into a beaker, mixing and stirring uniformly to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and chain transfer agent tertiary dodecyl mercaptan, sequentially adding the acrylonitrile and chain transfer agent tertiary dodecyl mercaptan into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing inert gas into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 6 hours at normal temperature and a rotating speed of 150r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 40 ℃, taking an initiator ammonium persulfate, adding the initiator ammonium persulfate into the heated mixture C, and carrying out polymerization reaction for 5 hours at a stirring rotation speed of 100r/min to obtain the VPR/NBR nanoparticle latex with a core-shell structure.
Example two
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Weighing the following raw materials in parts by weight: 200g of deionized water, 100g of butadiene-pyridine latex, 5g of surfactant disproportionated potassium abietate, 2g of surfactant sodium dodecyl sulfate, 3g of surfactant nonylphenol polyoxyethylene ether, 50g of acrylonitrile, 70g of butadiene, 0.10g of initiator potassium persulfate and 1.0g of chain transfer agent terbutamol; wherein, the particle size of the butadiene-pyridine latex is 100nm, and the solid content is 40%;
2) Taking deionized water, butadiene-pyridine latex, surfactant disproportionated potassium abietate, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the deionized water, the butadiene-pyridine latex, the surfactant disproportionated potassium abietate, the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into a beaker, mixing, and stirring uniformly to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and a chain transfer agent terbutamol, sequentially adding the acrylonitrile and the chain transfer agent terbutamol into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing inert gas into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 0.5h at normal temperature and a rotating speed of 450r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 80 ℃, taking an initiator potassium persulfate, adding the initiator potassium persulfate into the heated mixture C, and carrying out polymerization reaction for 2 hours at a stirring rotation speed of 500r/min to obtain the VPR/NBR nanoparticle latex with a core-shell structure.
Example III
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Weighing the following raw materials in parts by weight: 100g of deionized water, 50g of butadiene-pyridine latex, 3g of surfactant disproportionated potassium abietate, 1g of surfactant lauryl sodium sulfate, 1g of surfactant nonylphenol polyoxyethylene ether, 30g of acrylonitrile, 50g of butadiene, 0.02g of initiator sodium persulfate and 0.2g of chain transfer agent n-butyl mercaptan; wherein, the particle size of the butadiene-pyridine latex is 86nm, and the solid content is 45%;
2) Taking deionized water, butadiene-pyridine latex, surfactant disproportionated potassium abietate, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the deionized water, the butadiene-pyridine latex, the surfactant disproportionated potassium abietate, the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into a beaker, mixing, and stirring uniformly to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and a chain transfer agent n-butyl mercaptan, sequentially adding the acrylonitrile and the chain transfer agent n-butyl mercaptan into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing inert gas into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 3 hours at normal temperature and a rotating speed of 300r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 60 ℃, adding an initiator sodium persulfate into the heated mixture C, and carrying out polymerization reaction for 4 hours at a stirring speed of 400r/min to obtain the VPR/NBR nanoparticle latex with a core-shell structure.
Example IV
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Weighing the following raw materials in parts by weight: 160g of deionized water, 70g of butadiene-pyridine latex, 4g of surfactant disproportionated potassium abietate, 3g of surfactant lauryl sodium sulfate, 2g of surfactant nonylphenol polyoxyethylene ether, 40g of acrylonitrile, 60g of butadiene, 0.06g of initiator ammonium persulfate and 0.8g of chain transfer agent n-dodecyl mercaptan; wherein, the particle size of the butadiene-pyridine latex is 86nm, and the solid content is 45%;
2) Taking deionized water, butadiene-pyridine latex, surfactant disproportionated potassium abietate, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the deionized water, the butadiene-pyridine latex, the surfactant disproportionated potassium abietate, the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into a beaker, mixing, and stirring uniformly to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and a chain transfer agent n-dodecyl mercaptan, sequentially adding the acrylonitrile and the chain transfer agent n-dodecyl mercaptan into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing inert gas into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 5 hours at normal temperature and a rotating speed of 250r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 50 ℃, taking an initiator ammonium persulfate, adding the initiator ammonium persulfate into the heated mixture C, and carrying out polymerization reaction for 3 hours at the stirring rotation speed of 300r/min to obtain the VPR/NBR nanoparticle latex with the core-shell structure.
Example five
The invention relates to a preparation method of a VPR/NBR nanoparticle latex with a core-shell structure, which comprises the following steps:
1) Weighing the following raw materials in parts by weight: 180g of deionized water, 90g of butadiene-pyridine latex, 2g of surfactant disproportionated potassium abietate, 2g of surfactant sodium dodecyl sulfate, 2g of surfactant nonylphenol polyoxyethylene ether, 45g of acrylonitrile, 60g of butadiene, 0.06g of initiator ammonium persulfate and 0.8g of chain transfer agent tertiary dodecyl mercaptan; wherein, the particle size of the butadiene-pyridine latex is 86nm, and the solid content is 45%;
2) Taking deionized water, butadiene-pyridine latex, surfactant disproportionated potassium abietate, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the deionized water, the butadiene-pyridine latex, the surfactant disproportionated potassium abietate, the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into a beaker, mixing, and stirring uniformly to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and chain transfer agent tertiary dodecyl mercaptan, sequentially adding the acrylonitrile and chain transfer agent tertiary dodecyl mercaptan into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing inert gas into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 1.0h at normal temperature and a rotating speed of 350r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 70 ℃, taking an initiator ammonium persulfate, adding the initiator ammonium persulfate into the heated mixture C, and carrying out polymerization reaction for 4 hours at a stirring rotation speed of 200r/min to obtain the VPR/NBR nanoparticle latex with a core-shell structure.
Comparative example one
The procedure for the homemade NBR latex was as follows:
1) Weighing the raw materials in sequence: 180g of deionized water, 2g of surfactant disproportionated potassium abietate, 2g of surfactant sodium dodecyl sulfate, 2g of surfactant nonylphenol polyoxyethylene ether, 36g of acrylonitrile, 64g of butadiene, 0.06g of initiator ammonium persulfate and 0.8g of chain transfer agent tertiary dodecyl mercaptan;
2) Taking deionized water, surfactant disproportionated potassium abietate, surfactant sodium dodecyl sulfate and surfactant nonylphenol polyoxyethylene ether, placing the mixture in a beaker, mixing the mixture at room temperature, and uniformly stirring the mixture to obtain a mixture A;
3) Adding the mixture A obtained in the step 2) into a reaction kettle, taking acrylonitrile and chain transfer agent tertiary dodecyl mercaptan, sequentially adding the acrylonitrile and chain transfer agent tertiary dodecyl mercaptan into the reaction kettle, and mixing to obtain a mixture B;
4) Introducing nitrogen into the reaction kettle in the step 3), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the degassed mixture B, mixing, and pre-emulsifying for 1.0h at normal temperature and a rotating speed of 350r/min to obtain a mixture C;
5) Heating the mixture C obtained in the step 4) to 70 ℃, taking an initiator ammonium persulfate, adding the initiator ammonium persulfate into the heated mixture C, and carrying out polymerization reaction for 4 hours at the stirring rotation speed of 200r/min to obtain NBR latex, thus obtaining a first control sample.
Comparative example two
The commercially available NBR latex gave control II.
Comparative example three
The self-made NBR latex obtained in the first comparative example is mixed with the butadiene-pyridine latex with the particle size of 86nm and the solid content of 45% according to the mass ratio of 100:50 to form a mixture, and a third comparative sample is obtained.
Five core-shell structured VPR/NBR nanoparticle latices obtained in examples one to five of the present invention, and a first control sample, a second control sample and a third control sample were subjected to performance test, respectively, to determine the solid content, the particle size and the particle size distribution index, and the experimental results are shown in Table 1.
The method for measuring the solid content comprises the following steps: about 1g of the sample was taken, and the water content was measured on a Metrehler HX204 rapid moisture meter manufactured by Metrehler-tolidox, U.S.A., and calculated to obtain the solid content.
The particle size distribution index and the particle size are determined by: the particle size and particle size distribution index of the samples were measured at 25℃using a ZS 90 laser particle sizer manufactured by Markov instruments, inc., UK, and each sample was tested three times to obtain the median.
As can be seen from Table 1, the core-shell structured VPR/NBR nanoparticle latex of the present invention has a solids content of 40-46% which is substantially consistent with the solids content of control one, control two, and control three. However, the particle size of the VPR/NBR nanoparticle latex with core-shell structure of the invention is 110-128nm, and the particle size distribution index is 0.23-0.29, and the particle size distribution index is large, for example: 128nm, also small particle size, for example: 110nm, and the particle size distribution index is smaller than 0.3; however, the particle size of the first control sample was 89nm, and the particle size distribution index reached 0.58; the particle size of the second comparison sample is 96nm, and the particle size distribution index reaches 0.65; the particle size of the third comparison sample is 40nm, and the particle size distribution index is 1.15; therefore, the particle size distribution of the VPR/NBR nanoparticle latex nano-micelle with the core-shell structure can be kept in a small range.
TABLE 1 results of Performance test of different latices
Experiment 1
The five core-shell structured VPR/NBR nanoparticle latex obtained in the first to fifth embodiments of the present invention and the first, second and third control samples were subjected to emulsion hydrogenation application tests, respectively, comprising the following specific steps:
a) Taking 147g of the VPR/NBR nanoparticle latex with the core-shell structures of the first embodiment to the fifth embodiment, and placing the VPR/NBR nanoparticle latex, the first control sample, the second control sample or the third control sample into a reaction kettle;
b) Adding 0.025g of Wilkinson catalyst into the reaction kettle in the step a), and mixing to obtain a first mixture;
c) Taking 1.5g of surfactant disproportionated potassium abietate and 2.0g of surfactant sodium dodecyl sulfate, adding the surfactant sodium dodecyl sulfate and the surfactant nonylphenol polyoxyethylene ether into the first mixture obtained in the step a), and mixing to obtain a second mixture;
d) And (3) introducing nitrogen into the second mixture, stirring at the speed of 300r/min, degassing at normal temperature, wherein the air pressure is 1.0MPa, the time is 60min, introducing high-pressure hydrogen, the pressure of the hydrogen is 8MPa, and carrying out hydrogenation reaction for 6h at 120 ℃ to obtain the hydrogenated rubber.
The degree of hydrogenation of the hydrogenated rubber obtained during the test was calculated by an iodine value titration method (GB/T13892-2020), and the test results are shown in Table 2.
As can be seen from Table 2, the core-shell structured VPR/NBR nanoparticle latex obtained in the invention has a hydrogenation degree of 97.8-99.8% in the preparation of hydrogenated butyl-pyridine/hydrogenated nitrile (HVPR/HNBR) rubber by the emulsion hydrogenation method, however, the hydrogenation degree of the first control sample in the preparation of hydrogenated nitrile rubber by the emulsion hydrogenation method is only 92.9%, the hydrogenation degree of the second control sample in the preparation of hydrogenated nitrile rubber by the emulsion hydrogenation method is only 91.8%, and the hydrogenation degree of the third control sample in the preparation of mixed rubber of hydrogenated butyl-pyridine and hydrogenated nitrile by the emulsion hydrogenation method is only 93.2%. Therefore, the VPR/NBR nanoparticle latex with the core-shell structure has good hydrogenation effect in the emulsion hydrogenation process, and the obtained HVPR/HNBR rubber has high hydrogenation degree.
TABLE 2 results of Performance test of hydrogenated rubber obtained by hydrogenation of emulsions of different raw materials
| Raw material name | Degree of hydrogenation (%) |
| Example 1 | 97.8 |
| Example two | 98.5 |
| Example III | 98.3 |
| Example IV | 98.8 |
| Example five | 99.8 |
| Control sample one | 92.9 |
| Control sample two | 91.8 |
| Control sample three | 93.2 |
Therefore, compared with the prior art, the invention has the beneficial effects that: the VPR/NBR nanoparticle latex with the core-shell structure takes the seed emulsion, namely the butadiene-acrylonitrile latex, as an inner core, and the butadiene-acrylonitrile copolymer is formed on the surface of the seed emulsion to form a nitrile latex shell, so that the VPR/NBR nanoparticle latex with the core-shell structure has stable performance, good size uniformity of the nano micelle, small particle size distribution range, difficult demulsification, simple preparation method, convenient operation and easy realization of industrialization; the VPR/NBR nanoparticle latex with the core-shell structure has good hydrogenation effect and high hydrogenation degree in the process of hydrogenating the emulsion.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A VPR/NBR nanoparticle latex with a core-shell structure is characterized in that:
the VPR/NBR nanoparticle latex with the core-shell structure consists of a core and a shell, wherein the core comprises butadiene-acrylonitrile latex, the shell comprises butadiene-acrylonitrile latex, and the butadiene-acrylonitrile latex is formed by copolymerizing butadiene and acrylonitrile;
the VPR/NBR nanoparticle latex with the core-shell structure comprises the following raw materials in parts by weight: 100-200 parts of deionized water, 50-100 parts of butadiene-pyridine latex, 3-10 parts of surfactant, 30-50 parts of acrylonitrile, 50-70 parts of butadiene, 0.02-0.10 part of initiator and 0.2-1.0 part of chain transfer agent.
2. The core-shell structured VPR/NBR nanoparticle latex of claim 1 wherein:
the particle size of the butadiene-pyridine latex is 80-100nm, and the solid content of the butadiene-pyridine latex is 40-50%.
3. The core-shell structured VPR/NBR nanoparticle latex of claim 1 wherein:
the surfactant is any one or more of alkyl sulfonate, alkylbenzenesulfonate, carboxylate, fatty alcohol sulfate, alkyl sulfate, phosphate, alkylphenol ethoxylate, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine;
preferably, the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether;
preferably, the surfactant is a mixture of disproportionated potassium abietate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether according to the weight ratio of 3-5:1-3:1-3.
4. The core-shell structured VPR/NBR nanoparticle latex of claim 1 wherein:
the initiator is any one or more of ammonium persulfate, potassium persulfate and sodium persulfate;
preferably, the chain transfer agent is any one or more of n-dodecyl mercaptan, tert-butyl mercaptan and n-butyl mercaptan.
5. A method for preparing the VPR/NBR nanoparticle latex of core-shell structure according to any one of claims 1 to 4, comprising the steps of:
1) Mixing deionized water, butadiene-pyridine latex and a surfactant to obtain a mixture A;
2) Taking acrylonitrile and a chain transfer agent, sequentially adding the acrylonitrile and the chain transfer agent into the mixture A obtained in the step 1), and mixing to obtain a mixture B;
3) Introducing inert gas into the mixture B obtained in the step 2), stirring, carrying out degassing treatment, taking butadiene, adding the butadiene into the mixture B after the degassing treatment, mixing, and pre-emulsifying for 0.5-6h at normal temperature and a rotating speed of 150-450r/min to obtain a mixture C;
4) Heating the mixture C obtained in the step 3) to 40-80 ℃, taking an initiator, adding the initiator into the heated mixture C, and carrying out polymerization reaction for 2-5h at the stirring rotation speed of 100-500r/min to obtain the VPR/NBR nanoparticle latex with the core-shell structure.
6. The method for preparing the VPR/NBR nanoparticle latex with a core-shell structure according to claim 5, wherein the method comprises the following steps:
in the step 3), the degassing treatment is carried out at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min;
preferably, in the step 3), the time of pre-emulsification is 1-3h;
preferably, in the step 3), the speed of the pre-emulsification is 200-350r/min.
7. Use of a VPR/NBR nanoparticle latex of core-shell structure according to any one of claims 1-4, characterized in that:
the VPR/NBR nanoparticle latex with the core-shell structure is used for preparing the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber through emulsion hydrogenation.
8. The use of the core-shell structured VPR/NBR nanoparticle latex according to claim 7, comprising the steps of:
a) Taking the VPR/NBR nanoparticle latex with a core-shell structure and a Wilkinson catalyst, wherein the dosage of the Wilkinson catalyst is 0.02-0.10% of the weight of the VPR/NBR nanoparticle latex with the core-shell structure, and mixing to obtain a first mixture;
b) Taking a surfactant, adding the surfactant into the first mixture obtained in the step a), wherein the dosage of the surfactant is 2-8% of the weight of the VPR/NBR nanoparticle latex with a core-shell structure, and mixing to obtain a second mixture;
c) And (3) introducing inert gas into the second mixture, stirring, degassing, introducing high-pressure hydrogen, wherein the pressure of the hydrogen is 5-10MPa, and carrying out hydrogenation reaction for 2-8h at 100-150 ℃ to obtain the hydrogenated butadiene-acrylonitrile/hydrogenated nitrile rubber.
9. The use of the core-shell structured VPR/NBR nanoparticle latex of claim 8 wherein:
in the step b), the surfactant is any one or more of alkyl sulfonate, alkylbenzene sulfonate, carboxylate salt, fatty alcohol sulfate salt, alkyl sulfate salt, phosphate salt, alkylphenol ethoxylate, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine;
preferably, in the step b), the surfactant is any one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, potassium oleate, sodium stearate, potassium stearate, sodium dodecyl sulfate and polyoxyethylene nonylphenol ether;
preferably, in the step b), the surfactant is a mixture of disproportionated potassium abietate and sodium dodecyl sulfate according to a weight ratio of 2-6:3-5.
10. The use of the core-shell structured VPR/NBR nanoparticle latex of claim 9 wherein:
in the step c), the degassing treatment is carried out at normal temperature, the air pressure is 0.1-2.0MPa, the time is 30-100min, and the stirring speed is 100-500r/min.
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