CN105778105A - Synthesis of siloxane containing nitrile group and vinyl group at same time and preparation method of room-temperature addition type nitrile silicone rubber - Google Patents
Synthesis of siloxane containing nitrile group and vinyl group at same time and preparation method of room-temperature addition type nitrile silicone rubber Download PDFInfo
- Publication number
- CN105778105A CN105778105A CN201610173479.8A CN201610173479A CN105778105A CN 105778105 A CN105778105 A CN 105778105A CN 201610173479 A CN201610173479 A CN 201610173479A CN 105778105 A CN105778105 A CN 105778105A
- Authority
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- China
- Prior art keywords
- siloxanes
- vinyl
- group
- silicone rubber
- nitrile
- Prior art date
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- Granted
Links
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 67
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 65
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 64
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 63
- 125000002560 nitrile group Chemical group 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 14
- -1 siloxanes Chemical class 0.000 claims description 97
- 229920002554 vinyl polymer Polymers 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 9
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001343 alkyl silanes Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 241000487918 Acacia argyrodendron Species 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000011222 chang cao shi Nutrition 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 16
- 230000000903 blocking effect Effects 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VJKZYNWRXKAUJF-UHFFFAOYSA-N NCCC[Si](OCC)(OCC)C=CC Chemical compound NCCC[Si](OCC)(OCC)C=CC VJKZYNWRXKAUJF-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 210000003953 foreskin Anatomy 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000002939 oilproofing Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to synthesis of siloxane containing nitrile group and vinyl group at same time and a preparation method of room-temperature addition type nitrile silicone rubber. The siloxane containing the nitrile group and the vinyl group is prepared from the siloxane containing amino group and the vinyl group at the same time, and a vinyl-group-containing compound with unsaturated bonds through an addition reaction of the amino group and the double bonds; the synthesized siloxane containing the nitrile group and the vinyl group at same time is used for preparing the room-temperature addition type nitrile silicone rubber. The synthesis method is simple and controllable, and high in synthesis efficiency. The synthesized siloxane containing the nitrile group and the vinyl group at same time contains the vinyl group so that the polarity and the dissolvability parameters of the siloxane are improved; the room-temperature addition type nitrile silicone rubber prepared from the siloxane containing the nitrile group has a property of resisting solvent oil and can be widely applied to various oil-resisting and low-temperature-resisting fields.
Description
Technical field
The preparation method of the synthesis of the siloxanes of nitrile group-containing and vinyl and room temperature add-on type nitrile silicone rubber while of the present invention relates to a kind of, belongs to organosilicon macromolecule synthesis field.
Background technology
Organosilicon macromolecule material has many superior functions, such as high-low temperature resistant, weather-proof, ageing-resistant, electric insulation etc., it is widely used in the aspects such as Aero-Space, electric, light industry, weaving, machinery, building, agricultural and transportation, in close relations with daily life, it has also become macromolecular material important in national economy.Silicone rubber is important organosilicon macromolecule material, its application products mainly include pressing (as various offset plates, packing ring, pad, thin film, rubber roll, electronic apparatus button, for the various die rubber goods etc. of extraordinary occasion), squeeze (pressure) and go out goods (such as various sebific ducts, glue rope, section bar, electric wire foreskin, adhesive tape etc.), spread goods (as sealing gasket, diaphragm, from sticking cloth, isolation cloth etc.).The main chain of silicone rubber is polydimethylsiloxane, introducing hetero-atoms or specific groups in its main chain, it is possible to give the performance that silicone rubber is special, expands its application further.Such as being introduced by itrile group in silicone rubber main chain, prepared new type silicone rubber has good oil resistance, cold-resistant and satisfied physical and mechanical properties, and market is called for short nitrile silicone rubber.
Novel nitrile silicone rubber is a kind of heat-resisting and oil resistant rubber, and conventional oil, fuel and solvent are had good stability, can use in-70 DEG C to+260 DEG C temperature ranges.Containing nitrile alkyl in nitrile silicone rubber molecule, mainly γ-nitrile propyl group, gained rubber low temperature resistance performance is close to phenyl siloxane rubber；Oil resistivity increases with the increase of γ-nitrile propyl group content, and when content is 33-50%, oil resistivity is similar to NBR-26 rubber；Nitrile alkyl can also be β-nitrile ethyl, and gained rubber heat-resistant stability is good, resistant to 250 DEG C of long term thermal air agings.
Solvent resistance is relevant to the nitrile alkyl content in elastomer with tolerance to cold.Russia's bibliographical information, with the increase of nitrile group content in polymer, the oil resistant of vulcanizate, fuel-resistant performance significantly increase.The molar concentration of nitrile group from 20% increase to 50% time, vulcanizate swellbility in the isobutyltrimethylmethane. of 50 DEG C reduces 4-5 times, reduction 1-2 times in 200 DEG C of fuel oil T-1.Without significant difference between vulcanizate containing γ-nitrile propyl group and β-nitrile ethyl group.Containing fuel-resistant T-1 performance under the benzene resistance of nitrile silicon vulcanizate of 33-50 mole % nitrile alkyl molecule chain, high temperature no less than butyronitrile CKH-26 vulcanizate, heat-resisting, cold-resistant then more advantageous.Without line relationship between polymer tolerance to cold and nitrile alkyl concentration.When nitrile alkyl amount is few (7-10 mole %), owing to destroying polymer architecture regularity and tolerance to cold significantly improves.Nitrile strand continues to cause that polymer glass temperature increases when increasing, it is believed that limit caused by Chain Flexibility owing to the very strong-CN base of polarity adds intermolecular force.
The most promising purposes of nitrile silicone rubber is to be made for sleeve pipe, connector, barrier film, O, sealing gasket and packing ring on airplane frame, automobile, railway traffic, electrical equipment and oil well rig.Its specific use potentially includes and is made for obturaging of aircraft fuel tank sealing shroud, the sealing of powered pump, brake component and slip transmission.Aircraft industry will be the main user of this new material.
Nitrile silicone rubber is produced in 1958 by General Electric Co. Limited, elastomeric compound (rubber the is β-nitrile ethyl type) trade mark has NSR-X5602, X4803 and X8701 three kinds, estimate its itrile group methylsiloxane segment respectively 10,25 and 50 mole %, hardness respectively 55 ± 5 (vulcanizing 1 hour) or 60 ± 5 (vulcanizing 3 hours), 70 ± 5 and 80 ± 5 totally four kinds.It is reported, novel butyronitrile silicone rubber at jet fuel JP-4, ASTM standard fuel A (isobutyltrimethylmethane .) and in ASTM standard fuel B (isobutyltrimethylmethane. and toluene) volumetric expansion little.In dibasic acid esters liquid (MiL-L7808), ASTMNo.3 oil and A type transmission fluid at 148.8 DEG C after aging 70 hours, its volumetric expansion is only small.It is said that these rubber make sealing member at industrial departments such as aviation, automobile and oil, the said firm still further developed the nitrile silicone rubber containing phenyl, has good heat-resisting, radiation resistance, and its intensity is higher.It addition, Union Carbide Corporation also began to produce nitrile silicone rubber in nineteen fifty-nine, also there is test manufacture (trade mark is HCKT) in the Soviet Union.Domestic Jilin chemical research institute has preproduction to produce, and in its nitrile silicon-25 model, acetonitrile ethylsiloxane mole content is 22%, and in nitrile silicon-50 model, content is 40%.Its conditions of vulcanization is at 155 DEG C 25 minutes.Shore hardness is 70 ± 5, and brittleness temperature is resistant to-66 DEG C.
It has been mentioned that use nitrile silicone rubber preparation to have the silastic material of property in domestic many patent documents, such as, Chinese patent document CN104059242A mentions the autohension silicon rubber foam material adopting nitrile silicone rubber and the use heat treatment foaming technique preparation of other filler to have superperformance；Chinese patent document CN104109296A adopts fluorubber, silicone-nitrile rubber and the composite use of other filler to be prepared for a kind of elastomeric material with excellent Waterproofing/oilproofing performance；Additionally Chinese patent document CN104312169A is prepared for a kind of corrosion-resistant silicone rubber with nitrile silicone rubber for main composite use neoprene and other filler.But these patent documents domestic only reported the purposes using nitrile silicone rubber rubber, do not report the preparation process of nitrile silicone rubber rubber.
According to the literature, nitrile silicone rubber rubber is a kind of new polysiloxanes by acetonitrile alkyl dichlorosilane and dimethyldichlorosilane polycondensation.The reaction of this polymerization process is violent, poor controllability.And nitrile silicone rubber also exists more serious shortcoming in processing and aspect of performance, moisture absorption when being mainly mixing, and increase with the increase of itrile group unit content, the elastomeric compound after water suction is difficult to vulcanize, also have the problem such as cure time length and thermostability deficiency, thus limit its application and development.Nitrile silicone rubber cold-resistant, oil resistant, solvent resistant, corrosion-resistant etc. in there is the performance of excellence, have a extensive future, but the report recently in prepared by nitrile silicone rubber be few.
Summary of the invention
For the deficiency of nitrile silicone rubber rubber in prior art and elastomeric compound synthesis and processing aspect, the synthetic method of nitrile group-containing and vinylsiloxane while that the present invention providing a kind of, the method synthesis condition is simple, controlled, and combined coefficient is high；While the present invention uses synthesis further, the siloxanes of nitrile group-containing and vinyl is prepared for room temperature add-on type nitrile silicone rubber.
Summary of the invention
The synthetic method of nitrile group-containing and vinylsiloxane while provided by the invention, by additive reaction between double bond in the amino in the siloxane molecule containing vinyl and the unsaturated compound containing itrile group, the siloxanes of preparation nitrile group-containing and vinyl simultaneously；While prepared, the siloxanes of nitrile group-containing and vinyl can be used alone or composite use as extraordinary siloxanes, it is also possible to preparation room temperature add-on type nitrile silicone rubber and other compounded rubber further, for various oil resistants, the place such as low temperature resistant.
Detailed Description Of The Invention
Technical scheme is as follows:
The while of a kind of, the synthetic method of the siloxanes of nitrile group-containing and vinyl, comprises the following steps that
When using solvent or not using solvent, the siloxanes simultaneously containing amino and vinyl is mixed mutually with the unsaturated compound containing itrile group, when using catalyst or not using any catalyst, by the reaction occurred between the double bond in amino and unsaturated compound, itrile group is incorporated in siloxane molecule, prepares the siloxanes simultaneously containing itrile group and vinyl.
The synthesis equation of the present invention nitrile group-containing and vinylsiloxane simultaneously is:
≡ Si-R ＇-NH2+CH2=CH-R "-CN → ≡ Si-R '-NH-CH2CH2-R″-CN
Wherein, R ' and R " for various organic groups.
According to the invention it is preferred to, amino and be 25-100 DEG C containing the temperature that reacts between the double bond in the unsaturated compound of itrile group, it is preferred that 40-60 DEG C；
Preferably, the response time is 3-5 hour.
According to the invention it is preferred to, the mol ratio simultaneously containing the siloxanes of amino and vinyl and the unsaturated compound containing itrile group is 1:(1-2).
According to the present invention, preferably, the siloxanes containing amino and vinyl while described is the compound containing one or more siliconoxygen bonds, including the block compound of tri-alkoxy one alkyl silane, dialkoxydialkyl silane, an alkoxyl trialkyl silane, disiloxane, polysiloxanes, siloxanes and the graft compound of the copolymerization of other compound, siloxanes and other compound, siloxanes and other compound；
Siloxanes more preferably dialkoxy one vinyl one alkyl silane of amino and vinyl, tetramethyl one vinyl one alkyl disiloxane and polysiloxanes is contained while described；
Preferably, contain amino content in the siloxanes of amino and vinyl is 1-20% simultaneously, molar content.
According to the present invention, preferably, the described compound that the unsaturated compound containing itrile group is the unsaturated bond simultaneously containing itrile group and other non-itrile group, it is preferred that, the undersaturated aliphatic compound of nitrile group-containing, the aromatic compound of nitrile group-containing, the unsaturated heterocyclic compound of nitrile group-containing, nitrile group-containing unsaturated compound；
It is furthermore preferred that the described unsaturated compound containing itrile group be acrylonitrile, butene nitrile, to cyanostyrene.
According to the invention it is preferred to, described solvent be can dissolve reactant and not with the various polarity of reactant generation chemical reaction or non-polar solven；It is preferred that, toluene, oxolane, chloroform, methanol, diphenyl ether, dimethyl sulfoxide, DMF；It is further preferred that toluene, oxolane.
According to the invention it is preferred to, described catalyst be can all kinds of materials of catalytic amino and double bond addition, it is preferred that, triethylamine, sodium acetate, pyridine, second bipyridine or tripolycyanamide；It is further preferred that triethylamine, sodium acetate or pyridine.
The preparation method of a kind of room temperature add-on type nitrile silicone rubber, comprises the following steps that
The siloxanes containing itrile group and vinyl while preparing is carried out composite with cross-linking agent, crosslinking catalyst, filler and other auxiliary agent, prepares room temperature add-on type nitrile silicone vulcanizates.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, it is preferred that reactive component weight proportion is as follows: simultaneously contain the siloxanes 100 parts of itrile group and vinyl, cross-linking agent 1-10 part, catalyst 0.01-1 part, filler 0.1-400 part, other auxiliary agent 0-200 part are used in crosslinking.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, it is preferred that reactive component weight proportion is as follows: simultaneously contain the siloxanes 100 parts of itrile group and vinyl, cross-linking agent 2-5 part, catalyst 0.01-0.5 part, filler 0.1-200 part, other auxiliary agent 0-50 part are used in crosslinking.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, it is preferred that described prepare while contain itrile group and vinyl siloxane molecule chain in contain itrile group and vinyl simultaneously, contain or do not contain other group；
Preferably, the siloxanes number-average molecular weight containing itrile group and vinyl while preparing is 3000-300000, it is preferred that 5000-30000.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, it is preferred that described cross-linking agent is under catalyst or does not use any catalyst, with the compound of siloxanes medium vinyl generation additive reaction, can single use also can composite can use；
Described cross-linking agent more preferably contains the compound of two and two or more sulfydryl；It is furthermore preferred that four (3-mercaptopropionic acid) pentaerythritol ester, 2,2 '-(1,2-second two base dioxygen generation) double; two ethyl mercaptans.
Preparation method according to the additional hot vulcanized nitrile silicone rubber of the present invention, it is preferred that described crosslinking catalyst and light trigger are the compound that can cause sulfydryl with siloxanes medium vinyl generation additive reaction, can single use also can composite use；
Described light trigger more preferably DMPA (2,2-dimethoxy-2-phenyl acetophenone), light trigger 1173,184,907,369,1490,1700；It is furthermore preferred that DMPA.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, preferably, described filler is to improve the various additives that room temperature add-on type nitrile silicone rubber performance uses, it is preferred that, fume colloidal silica, precipitated silica, black wood charcoal are black, calcium carbonate, aluminium hydroxide be or/and magnesium hydroxide and the various above-claimed cpd through special handling, more preferably the white carbon that silazane processes.The use number of filler is 0.1-400 part, it is preferred to 3-30 part.
Preparation method according to room temperature add-on type nitrile silicone rubber of the present invention, preferably, other described auxiliary agent is the various auxiliary agents not significantly reducing room temperature add-on type nitrile silicone rubber performance after adding, it is preferred that thermal oxidation stabilizer, fire retardant, conductive agent, foaming agent, deeply-curing agent, pigment or plasticizer；More preferably iron oxide red, uses number to be preferably 1-10 part.
The present invention does not elaborate, all by prior art.
Principles of the invention and having the beneficial effect that:
The reaction scheme of the present invention has abandoned the reaction scheme using chlorosilane of prior document report, it is to avoid a large amount of hydrochloric acid that course of reaction the produces corrosion to equipment；After primary amino radical reacts with double bond in the present invention, make primary amino radical change into active less secondary amine, improve the storage stability of siloxanes, decrease the Yellowing deposited containing amino silicones or easily produce in use procedure.The present invention is based on the additive reaction of amino and double bond, and common amino just can react with the temperature that the additive reaction of double bond needs in the presence of a catalyst, experience is higher and long period.In the present invention, due to the itrile group activation to double bond, this reaction is reacted more easy than common amino and double bond and is carried out.In the present invention, if not using catalyst, it is possible to react quickly, reaction efficiency is high；If use catalyst, reaction is comparatively rapid, and reaction efficiency is greatly improved.Therefore significant effect is achieved.
The compound that unsaturated compound containing itrile group is the unsaturated bond simultaneously containing itrile group and other non-itrile group of the present invention, such material all can react in the reaction condition that the present invention relates to.When itrile group is connected with double bond, the itrile group sensitization best results to double bond, so acrylonitrile can be easier to when not using any catalyst react with amino；When double bond is not adjacent with any sensitizing group, this reaction can also carry out, and however it is necessary that use catalyst, and the response time is longer.
The additive reaction of amino involved in the present invention and double bond, it is possible to do not use any solvent to occur.The use of solvent can aid in the raising of the blended of reaction mass and reaction efficiency, considers based on aspects such as the polarity of solvent, boiling point, stability and safeties, it is preferable that toluene and oxolane.
The siloxanes containing itrile group of the present invention, owing to containing this kind of polar group of itrile group, changing polarity and the solubility parameter of siloxanes, being different from common polydimethylsiloxane, enriching the kind of siloxanes；Use room temperature add-on type nitrile silicone vulcanizates prepared by the siloxanes containing itrile group further, it is possible to there is the resistance to wet goods performance of solvent resistant.
Use involved in the present invention contains room temperature add-on type nitrile silicone vulcanizates prepared by the siloxanes of itrile group and vinyl simultaneously, its cross-linked network is built with mercapto groups addition by vinyl, and the position of vinyl and quantity directly influence the performance of the room temperature add-on type nitrile silicone vulcanizates of preparation.If contents of ethylene is high, prepared vulcanite crosslink density is big, hardness and hot strength high, but elongation at break is low；If contents of ethylene is low, crosslinking points is few, and elongation at break is high, and hardness is little.Consider via test recipe, it is preferable that the nitrile group-containing siloxanes of ethenyl blocking, the mechanical mechanics property of vulcanite prepared therefrom is preferably.
Cross-linking agent involved in the present invention adopts the compound containing two and two or more sulfydryl, carries out cross-linking reaction by mercapto alkene click-reaction under irradiation under ultraviolet ray.This crosslinking method is efficient, quick, easy, is more suitable for application and promotes.Test via inventive formulation, it is preferable that with four (3-mercaptopropionic acid) pentaerythritol ester, 2,2 '-(1,2-second two base dioxygen generation) double; two ethyl mercaptans.
Crosslinking catalyst used in the present invention and light trigger, carry out additive reaction for sulfydryl with the vinyl in polysiloxanes；Spendable light trigger has DMPA (2,2-dimethoxy-2-phenyl acetophenone), light trigger 1173,184,907,369,1490,1700 etc..Consider initiation effect, it is preferable that DMPA, owing to its efficiency of initiation is high, so it uses number more preferably 0.01-0.5 part；
Room temperature add-on type nitrile silicone vulcanizates prepared by the present invention, if being added without any filler and auxiliary agent, it is also possible to sulfidization molding, but intensity is not high.Use various filler, particularly reinforced filling, it is possible to improve the mechanical mechanics property of vulcanite preferably.Due in base glue used in the present invention containing itrile group, band polarized, therefore various inorganic fillers and polar organic filler eaten that powder is fast, the compatibility good, reinforcement efficiency high.In order to improve the high temperature resistant serviceability of nitrile silicone rubber further, the present invention is it is preferred that nitrile silicone rubber is carried out reinforcement by the white carbon processed, reduce nitrile silicone rubber sizing material mixing or deposit the structuring produced in process, slow down the generation of signs of degradation when applied at elevated temperature.
Room temperature add-on type nitrile silicone vulcanizates prepared by the present invention, adds various auxiliary agent in its formula, it is possible to improves its performance further and expands its application, such as thermal oxidation stabilizer, fire retardant, conductive agent, foaming agent, deeply-curing agent, pigment, plasticizer etc..Some auxiliary agent can play multiple effect, and such as iron oxide red can simultaneously work as the effect of thermal oxidation stabilizer, pigment, reinforced filling.The consumption and the multiple auxiliary agent that change auxiliary agent are used in conjunction with, it is possible to prepare the nitrile silicone rubber of multiple premium properties.
The polysiloxanes containing itrile group and vinyl while the present invention can be used alone or composite use as extraordinary polysiloxanes, it is also possible to prepares into nitrile silicone rubber and other compounded rubber, for various oil resistants, low temperature resistant place, has a extensive future.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the nitrile group-containing siloxanes of the embodiment of the present invention 13 medium vinyl end-blocking.
Detailed description of the invention
Below by specific embodiment, the present invention will be further described, but is not limited to this.
Raw materials used in embodiment it be conventional commercial raw material or be synthetically derived according to list of references method.
Molecular weight described in embodiment is number-average molecular weight.
Number described in embodiment is weight portion.
" % " described in embodiment is molar content.
Embodiment 1
Aminopropyl methylvinyldiethoxysilane and acrylonitrile are carried out blended by the ratio than 1:1.5 of measuring by mol in tetrahydrofuran solution, keeping temperature is 40 DEG C, mechanical agitation 4 hours, obtains N-(β-itrile group)-γ-aminopropyl methylvinyldiethoxysilane, and reaction yield is 100%.
Embodiment 2
As described in Example 1, the difference is that aminopropyl methylvinyldiethoxysilane changes into aminopropyl vinyl tetramethyl disiloxane, reaction temperature is 40 DEG C, mechanical agitation 4 hours, obtaining N-(β-itrile group)-γ-aminopropyl vinyl tetramethyl disiloxane, reaction yield is 100%.
Embodiment 3
In tetrahydrofuran solution, by blended with acrylonitrile for mole siloxanes (molecular weight is 10000) containing aminopropyl (15%) of the metering ethenyl blocking than 1:2, keeping reaction temperature is 50 DEG C, mechanical agitation 4 hours, obtain the nitrile group-containing siloxanes of ethenyl blocking, reaction yield 100%.
The nitrile group-containing siloxanes prepared, molecular weight is 10985, and nitrile group content is 15%.
Embodiment 4
As described in Example 3, the difference is that: the link content of aminopropyl is 5%.Reaction temperature is 50 DEG C, and the response time is 4 hours, and reaction yield reaches 100%.
Embodiment 5
As described in Example 3, the difference is that the polysiloxanes containing N-(β-aminoethyl)-γ-aminopropyl (chain link content 15%) that the polysiloxanes containing aminopropyl of ethenyl blocking is changed into ethenyl blocking.Reaction temperature 60 DEG C, in 4 hours response time, reaction yield is 100%.
Embodiment 6
As described in Example 5, the difference is that changing N-(β-aminoethyl)-γ-aminopropyl chain link content of polysiloxanes into 5%.Reaction temperature 60 DEG C, in 4 hours response time, reaction yield is 100%.
Embodiment 7
As described in Example 3, the difference is that changing acrylonitrile into butene nitrile.Reaction temperature is 60 DEG C, 4 hours response time, reaction yield 95%.
Embodiment 8
In toluene solution, by blended with acrylonitrile for mole siloxanes (molecular weight is 10000) containing aminopropyl (15%) of the metering ethenyl blocking than 1:2, catalyst is pyridine, keeping reaction temperature is 60 DEG C, mechanical agitation 4 hours, obtain the nitrile group-containing siloxanes of ethenyl blocking, reaction yield 100%.
The nitrile group-containing siloxanes prepared, molecular weight is 10985, and nitrile group content is 15%.
Embodiment 9
As described in Example 8, the difference is that changing into cyanostyrene by acrylonitrile, catalyst changing sodium acetate into, reaction temperature is 60 DEG C, 4 hours response time, reaction yield 100%.
Embodiment 10
As described in Example 8, the difference is that changing acrylonitrile into butene nitrile, catalyst changing triethylamine into, reaction temperature is 60 DEG C, 4 hours response time, reaction yield 100%
Embodiment 11
The nitrile group-containing siloxanes 100 parts of ethenyl blocking that molecular weight is 10000, four (3-mercaptopropionic acid) pentaerythritol ester 3 parts, silazane process gas-phase silica 20 parts, DMPA0.15 part, titanium dioxide 8 parts, maleic acid diallyl ester 0.09 part carry out composite, preparation room temperature add-on type sulfuration nitrile silicone rubber.
Embodiment 12
The nitrile group-containing siloxanes 100 parts of ethenyl blocking that molecular weight is 20000, four (3-mercaptopropionic acid) pentaerythritol ester 5 parts, silazane process precipitated silica 20 parts, DMPA0.1 part, methyl-silicone oil 7 parts, titanium dioxide 8 parts, iron oxide red 10 parts carry out composite, preparation room temperature add-on type sulfuration nitrile silicone rubber.
Embodiment 13
The nitrile group-containing siloxanes 100 parts of ethenyl blocking that molecular weight is 30000, four (3-mercaptopropionic acid) pentaerythritol ester 5 parts, silazane process fume colloidal silica 30 parts, DMPA0.12 part, methyl-silicone oil 7 parts, titanium dioxide 8 parts, benzimidazole 0.06 part carry out composite, preparation room temperature add-on type sulfuration nitrile silicone rubber.
Test example 1
Being analyzed the nitrile group-containing siloxanes of the ethenyl blocking in embodiment 13 characterizing, its infrared spectrum is as it is shown in figure 1, infrared spectrum data are: F-IR (KBrpelletcm-1): υ=1094.59,1021.37cm-1(Si-O-Si), υ=1261.64cm-1(Si-CH3), υ=2963.65cm-1(-CH3), υ=3080.52cm-1(-CH=CH2), υ=2242.23cm-1(-CN)。
Test example 2
Room temperature add-on type sulfuration nitrile silicone rubber embodiment 11,12 and 13 prepared carries out mechanical test, and result is as shown in table 1 below.
Table 1
| Index numbering | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Hardness (continue that A) | 40 | 42 | 43 |
| Hot strength (MPa) | 2.30 | 2.56 | 2.68 |
| Elongation rate of tensile failure % | 123 | 134 | 138 |
| Tearing strength KN/m | 11.23 | 11.65 | 12.38 |
As shown in Table 1, the mechanical property of room temperature add-on type that the present invention prepares sulfuration nitrile silicone rubber is better, and along with while nitrile group-containing and the increase of vinyl polysiloxane molecular weight and increase to some extent.The use number of nitrile group-containing and the molecular weight of vinyl polysiloxane, nitrile group content and contents of ethylene and cross-linking agent, crosslinking catalyst, filler and other auxiliary agent is regulated and controled further, the nitrile silicone rubber that mechanical property is more excellent can be obtained.
Claims (10)
1. a preparation method for room temperature add-on type nitrile silicone rubber, comprises the following steps that
The siloxanes simultaneously containing itrile group and vinyl is carried out composite with cross-linking agent, crosslinking catalyst, filler and other auxiliary agent, prepares room temperature add-on type nitrile silicone vulcanizates；
The siloxanes containing itrile group and vinyl while described is when using solvent or not using solvent, the siloxanes simultaneously containing amino and vinyl is mixed mutually with the unsaturated compound containing itrile group, when using catalyst or not using any catalyst, by the reaction occurred between the double bond in amino and unsaturated compound, itrile group is incorporated in siloxane molecule, prepares；
Described cross-linking agent is many sulfhydryl compounds；
Described crosslinking catalyst is the compound that can cause sulfydryl with siloxanes medium vinyl generation additive reaction.
2. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, reactive component weight proportion is as follows: contain the siloxanes 100 parts of itrile group and vinyl simultaneously, cross-linking agent 1-10 part, catalyst 0.01-1 part is used in crosslinking, filler 0.1-400 part, other auxiliary agent 0-200 part；
Preferably, reactive component weight proportion is as follows: containing the siloxanes 100 parts of itrile group and vinyl, cross-linking agent 2-5 part, catalyst 0.01-0.5 part, filler 0.1-200 part, other auxiliary agent 0-50 part are used in crosslinking simultaneously.
3. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterised in that described many sulfhydryl compounds are the compound containing two and two or more sulfydryl；
Preferably, four (3-mercaptopropionic acid) pentaerythritol ester, 2,2 '-(1,2-second two base dioxygen generation) double; two ethyl mercaptans.
4. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterised in that described crosslinking catalyst is light trigger, it is preferred to DMPA (2,2-dimethoxy-2-phenyl acetophenone), light trigger 1173,184,907,369,1490,1700.
5. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, described filler is that fume colloidal silica, precipitated silica, black wood charcoal be black, calcium carbonate, aluminium hydroxide be or/and magnesium hydroxide and the various above-claimed cpd through special handling；
Preferably, other described auxiliary agent is thermal oxidation stabilizer, fire retardant, conductive agent, foaming agent, deeply-curing agent, pigment or plasticizer；More preferably iron oxide red.
6. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterised in that the siloxanes number-average molecular weight containing itrile group and vinyl while described is 3000-300000, it is preferable that 5000-30000；
Preferably, the siloxanes containing itrile group and vinyl while described is the siloxanes that vinyl is in polymer end positions.
7. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, contain in the preparation process of siloxanes of itrile group and vinyl while described: amino and be 25-100 DEG C containing the temperature that reacts between the double bond in the unsaturated compound of itrile group, it is preferable that 40-60 DEG C；
Preferably, the response time is 3-5 hour；
Preferably, the mol ratio simultaneously containing the siloxanes of amino and vinyl and the unsaturated compound containing itrile group is 1:(1-2).
8. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, contain while described in the preparation process of siloxanes of itrile group and vinyl: the siloxanes containing amino and vinyl while described is the compound containing one or more siliconoxygen bonds, preferred tri-alkoxy one alkyl silane, dialkoxydialkyl silane, one alkoxyl trialkyl silane, disiloxane, polysiloxanes, the copolymerization of siloxanes and other compound, the graft compound of siloxanes and other compound, the block compound of siloxanes and other compound.
9. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, contain in the preparation process of siloxanes of itrile group and vinyl while described: the described unsaturated compound containing itrile group is the compound simultaneously contain itrile group with the unsaturated bond of other non-itrile group, it is preferable that the undersaturated aliphatic compound of nitrile group-containing, the aromatic compound of nitrile group-containing, the unsaturated heterocyclic compound of nitrile group-containing, nitrile group-containing unsaturated compound；
It is furthermore preferred that the described unsaturated compound containing itrile group be acrylonitrile, butene nitrile, to cyanostyrene.
10. the preparation method of room temperature add-on type nitrile silicone rubber according to claim 1, it is characterized in that, contain in the preparation process of siloxanes of itrile group and vinyl while described: described solvent is toluene, oxolane, chloroform, methanol, diphenyl ether, dimethyl sulfoxide, DMF；
Preferably, described catalyst is triethylamine, sodium acetate, pyridine, second bipyridine or tripolycyanamide.
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| CN106810697A (en) * | 2016-12-28 | 2017-06-09 | 沈阳化工大学 | A kind of preparation method containing itrile group POSS modified organic silicon glue |
| CN112538271A (en) * | 2020-12-09 | 2021-03-23 | 山东大学 | Hydrophilic silicone rubber capable of being used as medical catheter and preparation method and application thereof |
| CN115260498A (en) * | 2021-04-30 | 2022-11-01 | 郑州中原思蓝德高科股份有限公司 | Thiol-terminated polymer and preparation method thereof |
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