CN111378110B - Polyether with high ignition point and preparation method and application thereof - Google Patents
Polyether with high ignition point and preparation method and application thereof Download PDFInfo
- Publication number
- CN111378110B CN111378110B CN201811615217.8A CN201811615217A CN111378110B CN 111378110 B CN111378110 B CN 111378110B CN 201811615217 A CN201811615217 A CN 201811615217A CN 111378110 B CN111378110 B CN 111378110B
- Authority
- CN
- China
- Prior art keywords
- polyether
- substituted
- butanol
- straight
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000570 polyether Polymers 0.000 title claims abstract description 80
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000010720 hydraulic oil Substances 0.000 abstract description 13
- 239000003921 oil Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 231100000989 no adverse effect Toxicity 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 88
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 40
- -1 phosphate ester Chemical class 0.000 description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 12
- 125000002619 bicyclic group Chemical group 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 7
- 125000002950 monocyclic group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- 125000006714 (C3-C10) heterocyclyl group Chemical group 0.000 description 2
- 125000006708 (C5-C14) heteroaryl group Chemical group 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- MZNDIOURMFYZLE-UHFFFAOYSA-N butan-1-ol Chemical compound CCCCO.CCCCO MZNDIOURMFYZLE-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005959 diazepanyl group Chemical group 0.000 description 1
- 125000005045 dihydroisoquinolinyl group Chemical group C1(NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
- 125000005883 dithianyl group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000005844 heterocyclyloxy group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005556 thienylene group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000005455 trithianyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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Abstract
The application belongs to the technical field of polyether synthesis, and particularly relates to high-ignition-point polyether shown in the following formula (I) and a preparation method and application thereof.The polyether obtained by the application has the advantages of high viscosity index, low volatility, low pour point, good lubricity and other excellent performances, and meanwhile, the ignition point of the polyether is greatly improved. And the high-melting polyether does not need to use additives, and has no adverse effect on the environment. The hydraulic oil has the advantages of environmental protection, high safety performance and long service life when being applied to hydraulic fluid (oil).
Description
Technical Field
The application belongs to the technical field of high ignition point polyethers, and particularly relates to a high ignition point polyether, a preparation method and application thereof.
Background
The polyether is a polymer prepared by taking ethylene oxide, propylene oxide, butylene oxide and the like as raw materials and carrying out polymerization reaction with different initiators under the action of a catalyst.
The hydraulic technology is a key technology for realizing modern transmission and control, and hydraulic oil (liquid) is an important component of the hydraulic technology and plays roles of energy transmission, system lubrication, corrosion prevention, rust prevention, cooling and the like in a hydraulic system. The polyether is applied to the water-glycol flame-resistant hydraulic fluid as a thickener of the flame-resistant hydraulic fluid, and plays a decisive role in performances such as viscosity, viscosity-temperature characteristic, inverse melting point, defoaming property and the like of the hydraulic fluid. The polyether can also be used as the main component of the flame-retardant hydraulic fluid to be applied to the whole oil formula.
The flame-resistant hydraulic fluid is mainly applied to hydraulic systems which are easy to access high-temperature open fire in industries such as metallurgy, mining, power plants, machining and the like, and when a high-pressure hydraulic pipeline is leaked or broken, oil is atomized and can be sprayed far. In this case, an open flame, or a very hot surface, may cause a fire. Because of the flowing and diffusing property of the oil, the fire is increased, and the danger is increased. The fire-resistant hydraulic fluid can avoid fire accidents caused by leakage of hydraulic oil using traditional mineral oil. In addition, some hydraulic systems requiring high safety factors for aviation, aerospace and naval vessels must also use fire-resistant hydraulic oil. Currently, the main types of fire-resistant hydraulic oils include: phosphate ester type, fatty acid ester type, synthetic type, water-glycol type, emulsion, high water-based liquid, and the like.
The phosphate flame-retardant hydraulic oil is suitable for a high-pressure hydraulic system with the temperature range of-20-150 ℃ and the pressure of less than 40 MPa. The phosphate has the most outstanding flame resistance, and the self-ignition point is up to 550 ℃ or more. The flame does not spread even if it catches fire at high temperature. The hydraulic system is suitable for a hydraulic system with high temperature and open fire nearby. Its disadvantages are toxicity to humans and the price of it is much higher than other classes of fire-resistant hydraulic oil.
Fatty acid esters are technically feasible to replace mineral oils for hydraulic systems with fire-resistant requirements, but fatty acid ester fire-resistant hydraulic fluids also have significant disadvantages: the fatty acid ester hydraulic fluid is easily hydrolyzed in the presence of water, and carboxylic acid generated by the hydrolysis causes metal corrosion, in which case oil change is necessary.
The water-glycol flame-retardant hydraulic oil has the largest application proportion at present, and is suitable for a hydraulic system with the temperature range of-30-60 ℃ and the pressure of less than 20 MPa. The disadvantage of water-glycol is the poor lubrication properties, and as hydraulic devices develop towards high temperature, high pressure and high efficiency, the lubrication properties and lifetime of the fire-resistant hydraulic oils are very important. The water-glycol has micro toxicity and general environmental protection performance.
The emulsion has low price and is suitable for hydraulic systems with the temperature range of 5-55 ℃ and the pressure of less than 14 MPa. Under the working condition of high temperature and high pressure, the emulsion has poor stability, is easy to decompose, and has serious pollution to the environment by waste oil. The high water-based HFA hydraulic fluid has the advantages of good flame resistance, high heat transfer efficiency, low price and the like, but also has the defects of poor lubricity, easy corrosion, leakage and the like.
Polyether is used as synthetic flame-resistant hydraulic fluid with many excellent properties, including good lubricating property, long service life, high flash point and viscosity index, low volatility and pour point, little effect on metal and rubber, and the oxidation products generated during high temperature use are completely dissolved in the rest liquid or completely volatilized, no deposit is left in the equipment, and especially the properties of polyether products can be flexibly adjusted by using variable factors in polyether molecules to meet various different use requirements. These characteristics of polyethers open up a wide prospect for their practical use, and polyethers have been successfully used as high temperature lubrication, flame resistant hydraulic fluids, gear oils, compressor oils, brake fluids, metal working fluids, and specialty grease base oils. Polyethers are one of the most widely used synthetic lubricants with the greatest yield. However, the existing polyether products have lower ignition points and higher potential safety hazards in use.
Disclosure of Invention
In order to ameliorate the deficiencies of the prior art, the present application provides a polyether of formula (I):
wherein n is an integer of 1 or more;selected from unsubstituted or optionally substituted one, two or more R a Substituted as follows: alkyl, cycloalkylA group, heterocyclyl, aryl, heteroaryl, alkylcycloalkyl, alkylheterocyclyl, alkylaryl, alkylheteroaryl, alkyloxyalkyl, alkyloxy;
R 1 、R 2 identical or different, independently of one another, from unsubstituted or optionally substituted by one, two or more R' s b A substituted alkylene group;
R 3 selected from unsubstituted or optionally substituted by one, two or more R c Substituted as follows: alkyl, cycloalkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkylcycloalkyl or alkylheterocyclyl;
m1 and m2 are the same or different and are each independently selected from the group consisting of numbers from 0 to 300, provided that m1 and m2 are not both 0;
the R is a 、R b 、R c The same or different, independently of one another, are selected from halogen, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.
According to an embodiment of the application, forAnd->The connection position of (2) is not particularly limited as long as the valence rule is satisfied after the connection. Those skilled in the art will appreciate that when n>1, each->Can be substituted in->On the same atom, can also be substituted in +.>On different atoms of the group. For example, the atom may be a carbon atom or a heteroatom.
According to an embodiment of the application, in formula (I), n is an integer from 1 to 6, for example 1,2. 3,4, 5 or 6;selected from C 1-10 Straight-chain or branched alkyl, C 1-10 Straight-chain or branched alkyl-O-C 1-10 Linear or branched alkyl;
R 1 、R 2 identical or different, independently of one another, from unsubstituted or optionally substituted C 1-10 C substituted by straight-chain or branched alkyl groups 2-4 An alkylene group of (a);
R 3 selected from C 1-10 Straight-chain or branched alkyl, unsubstituted or optionally substituted by 1-3C 1-10 Straight or branched alkyl, halogen substituted as follows: c (C) 5-12 Cycloalkyl, C 5-12 Aryl, C 1-10 Straight-chain or branched alkyl C 5-12 An aryl group;
m1 and m2 are the same or different and are each independently selected from the group consisting of numbers from 0 to 200, provided that m1 and m2 are not both 0.
By way of example, in formula (I), n is an integer from 1 to 4, for example 1,2, 3 or 4;
as an example of this, the process may be performed,selected from CH 3 —、CH 3 CH 2 —、CH 3 CH 2 CH 2 —、CH 3 CH 2 CH 2 CH 2 —、—CH 2 CH 2 —、—CH 2 CH 2 CH 2 —、—CH 2 CH 2 OCH 2 CH 2 —、—CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 —、 Wherein, one end of the chemical bond is a connecting site;
by way of example, R 1 、R 2 Identical or different from each otherIndependently selected from unsubstituted or optionally C 1-3 C substituted by straight-chain or branched alkyl groups 2-4 An alkylene group of (a); for example R 1 O、R 2 O is the same or different and is selected from EO and PO units independently;
as an example, m1, m2 are the same or different and are independently selected from the numbers 0 to 100, provided that m1 and m2 are not both 0;
by way of example, R 3 Selected from C 1-6 Straight-chain or branched alkyl, unsubstituted or optionally substituted by 1-3C 1-6 Straight or branched alkyl, halogen substituted as follows: c (C) 5-12 Cycloalkyl, C 5-12 Aryl or C 1-6 Straight-chain or branched alkyl C 5-12 Aryl groups.
The application also provides a preparation method of the polyether, which comprises the following steps:
S1)reacting with an alkylene oxide to obtain a polyether represented by the following formula (II),
s2) reacting the polyether obtained in step S1) with an isocyanate R 3 -NCO reaction to give a high ignition point polyether of formula (I);
wherein ,R 1 、R 2 、R 3 m and n have the definitions as described above;
the alkylene oxide is obtained after ring opening 1 O-and/or-R 2 O-alkylene oxide.
According to an embodiment of the application, the reaction of step S1) is carried out in the presence of a catalyst selected from basic catalysts, such as one, a mixture of two or more of metallic sodium, potassium, sodium hydride, potassium hydroxide, sodium alkoxide.
According to an embodiment of the application, the catalyst is used in an amount of 0.01 to 10.0%, preferably 0.01 to 8.0%, still preferably 0.02 to 6.0%, for example 0.02 to 3.0% of the total mass of the raw materials.
According to an embodiment of the application, the temperature of the reaction in step S1) is 40 to 180 ℃, preferably 60 to 160 ℃, still preferably 90 to 130 ℃.
According to an embodiment of the present application, the amount of alkylene oxide fed in step S1) is such that the pressure of the reaction system is 0.1 to 0.6MPa, preferably 0.2 to 0.4MPa.
According to an embodiment of the present application, in step S1), the polyether represented by formula (II) may be prepared as follows: to the direction ofAdding a catalyst into an alkylene oxide system to react to prepare polyether oligomer; adding the catalyst again to continue the reaction to prepare polyether; wherein the catalyst added for the first time and the catalyst added for the second time may be the same or different.
According to an embodiment of the application, in step S2), the temperature of the reaction is 50 to 160 ℃, preferably 60 to 150 ℃, further preferably 80 to 130 ℃; the reaction time is 2 to 8 hours, preferably 3 to 7 hours, and more preferably 4 to 6 hours;
according to an embodiment of the present application, in step S2), the polyether of formula (II) is reacted with an isocyanate R 3 The molar ratio of NCO is from 1:0.01 to 6.1, for example from 1:0.5 to 1.0, 1:2.0, 1:3.0, 1:4.0, 1:5.0.
The application also provides hydraulic fluid or hydraulic oil, which comprises the polyether.
The application also provides application of the polyether in preparing hydraulic liquid or hydraulic oil.
Term interpretation and definition
Unless otherwise indicated, the numerical ranges recited in the specification and claims, when defined as "numbers", should be understood to recite both endpoints of the range, each integer within the range, and each fraction within the range. For example, a "number of 0 to 10" should be understood to describe not only each integer of 0, 1,2, 3,4, 5,6, 7, 8, 9 and 10, but also at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively. For example, a "number of 0-300" should be understood to describe not only each integer of 0, 1,2, 3,4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 … … up to 300, but also at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
The term "halogen" refers to F, cl, br and I. In other words, F, cl, br, and I may be described as "halogen" in the present specification.
The term "alkyl" is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C 1-10 An alkyl group. "C 1-10 Alkyl "is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof. In particular, the radicals have 1,2, 3,4, 5,6, carbon atoms ("C 1-6 Alkyl "), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly said groups having 1,2 or 3 carbon atoms (" C 1-3 Alkyl "), such as methyl, ethyl, n-propyl or isopropyl.
The term "cycloalkyl" is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C 3-10 Cycloalkyl groups). The term "C 3-10 Cycloalkyl "is understood to mean a saturated monovalent mono-or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The C is 3-10 Cycloalkyl may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.
The term "heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1 to 5 heteroatoms independently selected from N, O and S, preferably a "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1 to 5, preferably 1 to 3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the remainder of the molecule through any of the carbon atoms or a nitrogen atom, if present. In particular, the heterocyclic groups may include, but are not limited to: 4-membered rings such as azetidinyl, oxetanyl; a 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6 membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclyl may be benzo-fused. The heterocyclyl may be bicyclic, such as, but not limited to, a 5,5 membered ring, such as hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom-containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydro-oxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the application, the heterocyclic group is non-aromatic.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring of monovalent aromatic or partly aromatic character having 6 to 20 carbon atoms, preferably "C 6-14 Aryl group). The term "C 6-14 Aryl "is understood to mean preferably a radical having 6,7. Monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon rings of 8, 9, 10, 11, 12, 13 or 14 carbon atoms ("C) 6-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 13 Aryl "), e.g. fluorenyl, or a ring having 14 carbon atoms (" C) 14 Aryl "), such as anthracenyl.
The term "heteroaryl" is understood to include such monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: it has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and it contains 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazole, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, and the like; or an axcinyl group, an indolizinyl group, a purinyl group, etc., and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g. positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridinyl or pyridylene include pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thienyl or thienylene include thiophen-2-yl, thienylene-2-yl, thiophen-3-yl and thienylene-3-yl.
The above definition of the term "alkyl", such as "alkyl", applies equally to other terms containing "alkyl", such as the terms "alkyloxy", "alkyloxyalkyl", and the like. Likewise, the above pair of terms "C 3-20 Cycloalkyl "," C 5-20 Cycloalkenyl "," 3-20 membered heterocyclyl "," C 6-20 The definition of aryl "and" 5-20 membered heteroaryl "correspondingly applies equally to other terms containing it, such as the term" C 3-20 Cycloalkyloxy "," 3-20 membered heterocyclyl "," 3-20 membered heterocyclyloxy "," C 6-20 Aryloxy "," C 6-20 Arylalkyl "and" 5-20 membered heteroarylalkyl ", and the like.
Advantageous effects
The inventors have unexpectedly found that the use of isocyanate compounds to modify the polyether end groups results in polyethers that substantially increase their own fire point while maintaining the excellent properties of polyether, such as high viscosity index, low volatility, low pour point, good lubricity, etc. And the high-melting polyether does not need to use additives, and has no adverse effect on the environment. The hydraulic oil has the advantages of environmental protection, high safety performance and long service life when being applied to hydraulic fluid (oil).
In addition, the preparation method of the polyether is simple and can be used for large-scale industrial production.
Drawings
FIG. 1 is an infrared spectrum of the butanol polyether prepared in example 1.
FIG. 2 is an infrared spectrum of the p-toluene isocyanate-terminated butanol polyether prepared in example 1.
FIG. 3 is an infrared spectrum of the phenyl isocyanate terminated butanol polyether prepared in example 3.
FIG. 4 is an infrared spectrum of the polyether prepared in example 5.
FIG. 5 is an infrared spectrum of the phenyl-isocyanate-terminated polyether prepared in example 5.
Detailed Description
The application is further illustrated below in connection with specific examples. It is understood that these examples are provided only for illustrating the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications of the present application may be made by those skilled in the art after reading the disclosure of the present application, and such equivalents are intended to fall within the scope of the present application as defined by the appended claims.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below, unless otherwise specified, are all commercially available or may be prepared by known methods.
The average molecular weight hereinafter is the number average molecular weight.
Example 1
(1) 148g of butanol, 1.2g of solid potassium hydroxide and nitrogen replacement are added into a reaction kettle, the temperature is raised to 100 ℃, 652g of PO (propylene oxide) is continuously introduced into the reaction kettle under the pressure of 0.2MPa, and the butanol polyether oligomer is prepared after the reaction is carried out until the pressure is not reduced any more; 200g of butanol polyether oligomer is taken, 0.85g of potassium methoxide is added into the mixture, 225g of PO is continuously introduced into the mixture at 100 ℃ and 0.4MPa, and the mixture is reacted until the pressure is not reduced, thus 414.6g of butanol polyether (the average molecular weight is 850, and the polymerization degree of PO is m1=13.4); the infrared spectrum of the product is shown in figure 1.
(2) 400g of butanol polyether (with average molecular weight of 850) is added into a reaction kettle, the temperature is controlled to be 70 ℃, 50g of p-toluene isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, the mixture is neutralized to be neutral by proper amount of acetic acid, and 442.7g of butanol polyether blocked by the p-toluene isocyanate is obtained after cooling. The sample was subjected to infrared test, and the detection result is shown in fig. 2.
As can be seen from FIG. 2, at 1050cm -1 The nearby absorption peak is that of polyether, and the infrared spectrum before end capping (figure 1) is compared, at 1720-1750cm -1 The characteristic absorption peak of carbamate group appears at the position of (2), which indicates that the generated product is paratoluene iso-tolueneCyanate ester-terminated butanol polyether.
Example 2
(1) 148g of butanol, 1.6g of NaH and 652g of PO/EO (weight ratio of 50/50) are continuously introduced into a reaction kettle, and the mixture is reacted until the pressure is not reduced, so that a butanol polyether oligomer is prepared; 200g of butanol polyether oligomer is taken, 1.1g of sodium methoxide is added into the mixture, 240g of PO/EO (50/50) is continuously introduced into the mixture at 100 ℃ and 0.4MPa, and the mixture is reacted until the pressure is not reduced, so that 428.7g of butanol polyether (average molecular weight 880, wherein the polymerization degree of PO or EO is m1 (PO) =6.9 and m2 (EO) =9.2) is prepared;
(2) 400g of butanol polyether (average molecular weight 880) is added into a reaction kettle, the temperature is controlled to be 70 ℃, 48g of p-toluene isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, the mixture is neutralized to be neutral by proper amount of acetic acid, and the temperature is reduced to obtain 440.3g of p-toluene isocyanate blocked butanol polyether. The product formed was confirmed by infrared spectroscopic testing to be p-toluene isocyanate-terminated butanol polyether.
Example 3
(1) 148g of butanol, 1.2g of solid potassium hydroxide and nitrogen replacement are added into a reaction kettle, the temperature is raised to 100 ℃, 652g of PO (propylene oxide) is continuously introduced into the reaction kettle under the pressure of 0.2MPa, and the butanol polyether oligomer is prepared after the reaction is carried out until the pressure is not reduced any more; 200g of butanol polyether oligomer is taken, 0.85g of potassium methoxide is added into the mixture, 225g of PO is continuously introduced into the mixture at 100 ℃ and 0.4MPa, and the mixture is reacted until the pressure is not reduced, thus 413.4g of butanol polyether (the average molecular weight is 850, and the polymerization degree of PO is m1=13.4);
(2) 400g of butanol polyether (average molecular weight 850) is added into a reaction kettle, the temperature is controlled at 70 ℃, 28g of phenyl isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, the mixture is neutralized to neutrality by proper amount of acetic acid, and 418.1g of phenyl isocyanate-terminated butanol polyether is obtained after cooling. The infrared detection result of the product is shown in figure 3.
Comparing the IR spectra before end capping, FIG. 3 shows at 1720-1750cm -1 The characteristic absorption peak of carbamate group appears at the position of the polyurethane group, and the synthesized product is proved to be butyl alcohol polyether terminated by phenyl isocyanate.
Example 4
(1) 148g of butanol, 1.6g of NaH and 652g of PO/EO (weight ratio of 50/50) are continuously introduced into a reaction kettle, and the mixture is reacted until the pressure is not reduced, so that a butanol polyether oligomer is prepared; 200g of butanol polyether oligomer is taken, 1.1g of sodium methoxide is added into the mixture, 240g of PO/EO (50/50) is continuously introduced into the mixture at 100 ℃ and 0.4MPa, and the mixture is reacted until the pressure is not reduced, so that 427.5g of butanol polyether (average molecular weight 880, wherein the polymerization degree of PO or EO is m1 (PO) =6.9 and m2 (EO) =9.2) is prepared;
(2) 400g of butanol polyether (average molecular weight is 880) is added into a reaction kettle, the temperature is controlled to be 70 ℃, 27g of phenyl isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, a proper amount of acetic acid is used for neutralization, and 419.6g of phenyl isocyanate end-capped butanol polyether is obtained after cooling. The infrared spectrum test proves that the generated product is phenyl isocyanate end-capped butanol polyether.
Example 5
(1) 134g of dipropylene glycol, 1.2g of solid potassium hydroxide, nitrogen substitution, heating to 120 ℃, continuously introducing 666g of PO (propylene oxide) at 0.2MPa, and reacting until the pressure is not reduced, thus obtaining 776.3g of PPG800 (average molecular weight 800, wherein the polymerization degree of PO is m1=11.5); the infrared analysis results are shown in FIG. 4.
(2) 400g of PPG800 (average molecular weight 800) is added into a reaction kettle, the temperature is controlled to be 80 ℃, 29.8g of phenyl isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, the mixture is neutralized to be neutral by proper amount of acetic acid, and the mixture is cooled to obtain 420.3g of PPG capped by the phenyl isocyanate. The infrared analysis results are shown in FIG. 5.
Comparing the infrared spectrum before end capping at 1720-1750cm -1 The position of (2) shows a characteristic absorption peak of carbamate group, and the synthesized product is PPG800 capped by phenyl isocyanate.
Comparative example 1
148g of butanol, 1.2g of solid potassium hydroxide and nitrogen replacement are added into a reaction kettle, the temperature is raised to 100 ℃, 652g of PO (propylene oxide) is continuously introduced into the reaction kettle under the pressure of 0.2MPa, and the butanol polyether oligomer is prepared after the reaction is carried out until the pressure is not reduced any more; 200g of butanol polyether oligomer was taken, 0.85g of potassium methoxide was added thereto, 225g of PO was continuously introduced at 100℃and 0.4MPa and reacted until the pressure was no longer lowered, and neutralized to neutrality with an appropriate amount of acetic acid to obtain 413.1g of butanol polyether (average molecular weight: 850, wherein the polymerization degree of PO was m=13.4).
Comparative example 2
148g of butanol, 1.6g of NaH and 652g of PO/EO (weight ratio of 50/50) are continuously introduced into a reaction kettle, and the mixture is reacted until the pressure is not reduced, so that a butanol polyether oligomer is prepared; 200g of butanol polyether oligomer was taken, 1.1g of sodium methoxide was added thereto, 240g of PO/EO (50/50) was continuously introduced at 100℃and 0.4MPa and reacted until the pressure was no longer lowered, and neutralized to neutrality with an appropriate amount of acetic acid to obtain 425.7g of butanol polyether (average molecular weight: 880, wherein the polymerization degree of PO or EO was: m1 (PO) =6.9, and m2 (EO) =9.2).
Comparative example 3
134g of dipropylene glycol, 1.2g of solid potassium hydroxide, nitrogen substitution, heating to 120 ℃, continuously introducing 666g of PO (propylene oxide) under the condition of 0.2MPa, reacting until the pressure is no longer reduced, and neutralizing to neutrality by using a proper amount of acetic acid to obtain 778.1g of PPG800 (average molecular weight 800, m1=11.5);
test case
The results of testing the ignition points of the products of examples 1-5 and comparative examples 1-3 above according to the method of GB/T3536-2008 petroleum product ignition points (Cleveland open cup method) are shown in the following Table:
| product source | Initiator | EO/PO | End capping agent | Ignition point (DEG C) |
| Example 1 | Butanol (Butanol) | PO | Para-toluene isocyanate | 270 |
| Example 2 | Butanol (Butanol) | PO/EO＝50/50 | Para-toluene isocyanate | 234 |
| Example 3 | Butanol (Butanol) | PO | Phenyl isocyanate | 267 |
| Example 4 | Butanol (Butanol) | PO/EO＝50/50 | Phenyl isocyanate | 231 |
| Example 5 | Dipropylene glycol | PO | Phenyl isocyanate | 285 |
| Comparative example 1 | Butanol (Butanol) | PO | —— | 235 |
| Comparative example 2 | Butanol (Butanol) | PO/EO＝50/50 | —— | 200 |
| Comparative example 3 | Dipropylene glycol | PO | —— | 240 |
From the above results, it is clear that the high ignition point polyether prepared by the application has an ignition point significantly higher than that of a product prepared without isocyanate end capping, and can be used for improving the safety of hydraulic fluid or hydraulic oil. In addition, the high-ignition-point polyether product prepared by the application has the excellent performances of high viscosity index, low volatility, low pour point, good lubricity and the like, so the high-ignition-point polyether product has more practical value.
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. Use of a polyether of formula (I) for the preparation of a hydraulic or hydraulic fluid:
wherein n is an integer of 2 to 4;selected from unsubstituted or optionally substituted one, two orMore R a Substituted as follows: c (C) 2-12 Alkyl or C 2-12 Alkyloxy C 2-12 An alkyl group;
R 1 、R 2 identical or different, independently of one another, from unsubstituted or optionally substituted C 1-3 C substituted by straight-chain or branched alkyl groups 2-4 An alkylene group of (a);
R 3 to be optionally substituted by one, two or more R c Substituted as follows: alkyl, cycloalkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkylcycloalkyl or alkylheterocyclyl;
m1 and m2 are the same or different and are each independently selected from the group consisting of numbers from 0 to 300, provided that m1 and m2 are not both 0;
the R is a Is halogen;
R c is halogen, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.
2. Use according to claim 1, characterized in that in formula (I), n is an integer from 2 to 4;
selected from-CH 2 CH 2 —、—CH 2 CH 2 CH 2 —、—CH 2 CH 2 OCH 2 CH 2 —、—CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 —、Wherein, one end of the chemical bond is a connecting site;
R 1 、R 2 identical or different, independently of one another, from unsubstituted or optionally substituted C 1-3 C substituted by straight-chain or branched alkyl groups 2-4 An alkylene group of (a);
m1 and m2 are the same or different and are each independently selected from the group consisting of numbers from 0 to 100, provided that m1 and m2 are not both 0;
R 3 selected from C 1-6 Straight-chain or branched alkyl, unsubstituted or optionally substituted by 1-3C 1-6 Straight or branched alkyl, halogen substituted as follows: c (C) 5-12 Cycloalkyl, C 6-12 Aryl or C 1-6 Straight-chain or branched alkyl C 6-12 Aryl groups.
3. Use according to claim 1 or 2, characterized in that the polyether is prepared by the following method:
S1)reacting with an alkylene oxide to obtain a polyether represented by the following formula (II);
s2) reacting the polyether obtained in step S1) with an isocyanate R 3 -NCO reaction to give a high ignition point polyether of formula (I);
wherein ,R 1 、R 2 、R 3 m and n have the definitions as defined in claim 1 or 2;
the alkylene oxide is obtained after ring opening 1 O-and/or-R 2 O-alkylene oxide.
4. Use according to claim 3, characterized in that the reaction of step S1) is carried out in the presence of a catalyst selected from basic catalysts.
5. The method according to claim 4, wherein the catalyst is used in an amount of 0.01 to 10.0% by mass of the total raw material.
6. Use according to claim 3, characterized in that the temperature of the reaction of step S1) is 40-180 ℃;
in step S2), the temperature of the reaction is 50-160 ℃.
7. The process according to claim 4, wherein in step S2) the polyether of the formula (II) is reacted with an isocyanate R 3 The molar ratio of NCO is 1:0.01-6.1.
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| WO1990005172A1 (en) * | 1988-11-11 | 1990-05-17 | Asahi Glass Company Ltd. | Tetrafluoroethane composition for a regrigerator |
| CN105778013A (en) * | 2016-03-23 | 2016-07-20 | 联泓(江苏)新材料研究院有限公司 | Polycarboxylic acid water reducer, preparation method thereof and cement admixture |
| CN108084362A (en) * | 2017-12-28 | 2018-05-29 | 联泓(江苏)新材料研究院有限公司 | A kind of solid polycarboxylic acid water reducing agent and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1990005172A1 (en) * | 1988-11-11 | 1990-05-17 | Asahi Glass Company Ltd. | Tetrafluoroethane composition for a regrigerator |
| CN105778013A (en) * | 2016-03-23 | 2016-07-20 | 联泓(江苏)新材料研究院有限公司 | Polycarboxylic acid water reducer, preparation method thereof and cement admixture |
| CN108084362A (en) * | 2017-12-28 | 2018-05-29 | 联泓(江苏)新材料研究院有限公司 | A kind of solid polycarboxylic acid water reducing agent and its preparation method and application |
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