CN111378110A - High-ignition-point polyether and preparation method and application thereof - Google Patents
High-ignition-point polyether and preparation method and application thereof Download PDFInfo
- Publication number
- CN111378110A CN111378110A CN201811615217.8A CN201811615217A CN111378110A CN 111378110 A CN111378110 A CN 111378110A CN 201811615217 A CN201811615217 A CN 201811615217A CN 111378110 A CN111378110 A CN 111378110A
- Authority
- CN
- China
- Prior art keywords
- polyether
- group
- straight
- alkyl
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 93
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000012530 fluid Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 31
- -1 alkylheterocyclyl Chemical group 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 4
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000010720 hydraulic oil Substances 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 9
- 125000002619 bicyclic group Chemical group 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000002950 monocyclic group Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 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 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009970 fire resistant effect Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 230000000903 blocking effect Effects 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 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
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 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
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 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
- 238000005461 lubrication Methods 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000010452 phosphate Substances 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
- 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
- 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
- 238000012546 transfer Methods 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
- 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
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([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
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- 238000007792 addition Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000004931 azocinyl group Chemical group N1=C(C=CC=CC=C1)* 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
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 230000005540 biological transmission Effects 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
- 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 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
- 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
- 238000004090 dissolution Methods 0.000 description 1
- 125000005883 dithianyl group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 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
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- 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
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
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- 125000002757 morpholinyl group Chemical group 0.000 description 1
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- 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
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- 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
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- 239000011591 potassium Substances 0.000 description 1
- UAJUXJSXCLUTNU-UHFFFAOYSA-N pranlukast Chemical class C=1C=C(OCCCCC=2C=CC=CC=2)C=CC=1C(=O)NC(C=1)=CC=C(C(C=2)=O)C=1OC=2C=1N=NNN=1 UAJUXJSXCLUTNU-UHFFFAOYSA-N 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
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Abstract
The invention 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 invention maintains the excellent performances of high viscosity index, low volatility, low pour point, good lubricity and the like of the polyether, and simultaneously greatly improves the ignition point of the polyether. And the high melting point polyether hasThe additive is needed, and the environment is not affected. The application of the composite material in hydraulic fluid (oil) has the advantages of environmental protection, high safety performance and long service life.
Description
Technical Field
The invention belongs to the technical field of high-ignition-point polyether, and particularly relates to high-ignition-point polyether and a preparation method and application thereof.
Background
The polyether is a polymer prepared by polymerization reaction of ethylene oxide, propylene oxide, butylene oxide and the like serving as raw materials 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 in energy transfer, system lubrication, corrosion prevention, rust prevention, cooling and the like in a hydraulic system. The polyether is applied to water-glycol flame-retardant hydraulic fluid as a thickening agent of flame-retardant hydraulic fluid, and plays a decisive role in the performances of viscosity, viscosity-temperature characteristics, reverse melting point, defoaming property and the like of the hydraulic fluid. Polyethers can also be used as the main component of fire-resistant hydraulic fluids in full-oil formulations.
The fire-resistant hydraulic fluid is mainly applied to hydraulic systems which are easy to approach high-temperature open fire in the industries of metallurgy, mining, power plants, machining and the like, and when a high-pressure hydraulic pipeline leaks or breaks, oil is atomized and can be sprayed far away. In this case, an open flame, or a very hot surface, may cause a fire. The spreading of fire and the danger are increased due to the flowing and diffusing property of the oil. The fire-resistant hydraulic fluid can avoid the occurrence of fire accidents caused by the leakage of the traditional mineral oil type hydraulic fluid. In addition, some hydraulic systems of aviation, aerospace and naval vessels which require high safety factors must also use flame-resistant hydraulic oil. Currently, the main types of fire-resistant hydraulic oils include: phosphoric ester type, fatty acid ester type, synthetic type, water-glycol type, emulsion, high water base liquid, etc.
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 ester has the most outstanding fire resistance, and the self-ignition point is as high as above 550 ℃. Even if fired at high temperature, the flame does not spread. The hydraulic system is suitable for high-temperature and nearby open fire hydraulic systems. Its disadvantages are toxicity to human beings and much higher price than other kinds of fuel-resistant hydraulic oil.
Fatty acid esters are technically feasible for use in hydraulic systems with fire resistant requirements instead of mineral oils, but fatty acid esters also have significant disadvantages: fatty acid ester hydraulic fluids are susceptible to hydrolysis in the presence of water, and carboxylic acids produced by hydrolysis cause metal corrosion, in which case oil changes must be made.
The water-glycol anti-flaming hydraulic oil is largest in application proportion at present and is suitable for a hydraulic system with the temperature range of minus 30-60 ℃ and the pressure of less than 20 MPa. The water-ethylene glycol has the disadvantage of poor lubricating performance, and as hydraulic devices develop toward high temperature, high pressure and high efficiency, the lubricating performance and the service life of the flame-retardant hydraulic oil are very important. The water-glycol has micro toxicity and general environmental protection performance.
The emulsion is low in price and is suitable for a hydraulic system 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 liquid. 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.
The polyether has many excellent properties for synthetic anti-burning hydraulic fluid, such as good lubricating property, long service life, high flash point and viscosity index, low volatility and low pour point, little effect on metal and rubber, complete dissolution or complete volatilization of oxidation products generated by using the polyether at high temperature, no deposit left in equipment, and flexible adjustment of the properties of polyether products by variable factors in polyether molecules to meet various different use requirements. These characteristics of polyethers open up a broad prospect for their practical application, and polyethers have been successfully used as high temperature lubrication, flame-retardant hydraulic fluids, gear oils, compressor oils, brake fluids, metal working fluids, and special grease base oils. Polyether is one of the most widely used synthetic lubricants with the greatest yield. However, the existing polyether product has low ignition point and high potential safety hazard in use.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides polyether shown in formula (I):
wherein n is an integer of 1 or more;
selected from unsubstituted or optionally substituted by one, two or more RaSubstituted with the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkylcycloalkyl, alkylheterocyclyl, alkylaryl, alkylheteroaryl, alkyloxyalkyl, alkyloxy;
R1、R2identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RbA substituted alkylene group;
R3selected from unsubstituted or optionally substituted by one, two or more RcSubstituted with the following groups: alkyl, cycloalkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkylcycloalkyl, or alkylheterocyclyl;
m1, m2 are identical or different and are each independently selected from a number from 0 to 300, with the proviso that m1 and m2 are not both 0 at the same time;
the R isa、Rb、RcIdentical or different, independently of one another, from the group consisting of halogen, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.
According to an embodiment of the present invention, for
And
the bonding position of (a) is not particularly limited as long as it conforms to the valence bond rule after bonding. It will be understood by those skilled in the art that when n is present>1 time, each
Can be substituted in
On the same atom as above, or may be substituted on
On different atoms. For example, the atom may be a carbon atom or a heteroatom.
According to an embodiment of the invention, in formula (I), n is an integer from 1 to 6, such as 1,2, 3,4, 5 or 6;
is selected from C1-10Straight or branched alkyl, C1-10Straight or branched alkyl-O-C1-10A linear or branched alkyl group;
R1、R2identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by C1-10Straight or branched alkyl substituted C2-4An alkylene group of (a);
R3is selected from C1-10Straight or branched chain alkyl, unsubstituted or optionally substituted by 1 to 3C1-10Straight or branched chain alkyl, halogen substituted as follows: c5-12Cycloalkyl radical, C5-12Aryl radical, C1-10Straight or branched alkyl C5-12An aryl group;
m1 and m2 are identical or different and are each independently selected from the group consisting of a number from 0 to 200, with the proviso that m1 and m2 are not both 0 at the same time.
As examples, in formula (I), n is an integer from 1 to 4, such as 1,2, 3 or 4;
as an example of this, the following is given,
is selected from CH3—、CH3CH2—、CH3CH2CH2—、CH3CH2CH2CH2—、—CH2CH2—、—CH2CH2CH2—、—CH2CH2OCH2CH2—、—CH2CH2CH2OCH2CH2CH2—、
Wherein, one end of the chemical bond- (R) -is a connecting site;
as an example, R1、R2Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by C1-3Straight or branched alkyl substituted C2-4An alkylene group of (a); for example R1O、R2O, equal to or different from each other, are independently selected from EO, PO units;
as an example, m1, m2, which are identical or different, are selected independently of one another from a number from 0 to 100, with the proviso that m1 and m2 are not both simultaneously 0;
as an example, R3Is selected from C1-6Straight or branched chain alkyl, unsubstituted or optionally substituted by 1 to 3C1-6Straight or branched chain alkyl, halogen substituted as follows: c5-12Cycloalkyl radical, C5-12Aryl or C1-6Straight or branched alkyl C5-12And (4) an aryl group.
The invention also provides a preparation method of the polyether, which comprises the following steps:
S1)
reacting with olefin oxide to obtain polyether shown in the following formula (II),
s2) reacting the polyether obtained in step S1) with an isocyanate R3-NCO reaction to obtain the polyether with high ignition point shown in formula (I);
wherein ,
R1、R2、R3m and n have the definitions as described above;
the alkylene oxide is ring-opened to obtain-R1O-and/or-R2Alkylene oxide of O-.
According to an embodiment of the invention, 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 alkoxides.
According to an embodiment of the present invention, the amount of the catalyst is 0.01 to 10.0% by mass, preferably 0.01 to 8.0% by mass, further preferably 0.02 to 6.0% by mass, for example 0.02 to 3.0% by mass of the total raw materials.
According to an embodiment of the present invention, the temperature of the reaction in the step S1) is 40 to 180 ℃, preferably 60 to 160 ℃, and further preferably 90 to 130 ℃.
According to an embodiment of the present invention, the amount of the alkylene oxide introduced in the step S1) is 0.1 to 0.6MPa, preferably 0.2 to 0.4MPa, based on the pressure of the reaction system.
According to an embodiment of the present invention, in step S1), the polyether represented by formula (II) may be prepared in the following manner: to the direction of
Adding a catalyst into an olefin oxide system for reaction to prepare polyether oligomer; adding the catalyst again to continue reacting to prepare polyether; wherein the first and second additions of catalyst may be the same or different.
According to an embodiment of the invention, in the step S2), the temperature of the reaction is 50-160 ℃, preferably 60-150 ℃, and more preferably 80-130 ℃; the reaction time is 2-8 hours, preferably 3-7 hours, and further preferably 4-6 hours;
according to an embodiment of the invention, in step S2), the polyether of formula (II) is reacted with an isocyanate R3The molar ratio of-NCO is 1: 0.01-6.1, such as 1: 0.5-1.0, 1:2.0, 1:3.0, 1:4.0, 1: 5.0.
The invention also provides hydraulic fluid or hydraulic oil which contains the polyether.
The invention also provides the application of the polyether in the preparation of hydraulic fluid or hydraulic oil.
Term interpretation and definition
Unless otherwise indicated, the description and claims reciting numerical ranges, when defined as "numbers," are to be understood as reciting both endpoints of the range, each integer within the range, and each decimal within the range. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2, 3,4, 5,6, 7, 8, 9, and 10, but also to recite 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. For example, a "number from 0 to 300" should be understood to not only recite 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 to recite 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 C1-10An alkyl group. "C1-10Alkyl "is understood to preferably mean 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-methylbutaneA methyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 1-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group, or a 1, 2-dimethylbutyl group, or isomers thereof. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)1-3Alkyl groups) 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 "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.
The term "heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings 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 heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a 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-dihydrooxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic radical is non-aromatic.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring having a monovalent aromatic or partially aromatic character of 6 to 20 carbon atoms, preferably "C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), 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 comprising 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: which 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 which comprises 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, heteroaryl 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, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; 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, pyridyl or pyridinylene includes pyridin-2-yl, pyridinylene-2-yl, pyridin-3-yl, pyridinylene-3-yl, pyridin-4-yl, and pyridinylene-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl.
The above definitions of the term "alkyl", such as "alkyl", apply equally to other terms containing "alkyl", such as the terms "alkyloxy", "alkyloxyalkyl", and the like. Likewise, the above pair of terms "C3-20Cycloalkyl group "," C5-20Cycloalkenyl group "," 3-20 membered heterocyclic group "," C6-20The definitions of aryl "and" 5-to 20-membered heteroaryl "apply correspondingly equally to the other terms containing it, such as the term" C3-20Cycloalkyloxy "," 3-20 membered heterocyclyl "," 3-20 membered heterocyclyloxy "," C6-20Aryloxy group and C6-20Arylalkyl "and" 5-20 membered heteroarylalkyl "and the like.
Advantageous effects
The inventor surprisingly finds that the polyether obtained by modifying the polyether end group with the isocyanate compound has the advantages of high viscosity index, low volatility, low pour point, good lubricity and the like, and greatly improves the ignition point of the polyether. And the high-melting-point polyether does not need to use additives and has no adverse effect on the environment. The application of the composite material in hydraulic fluid (oil) has the advantages of environmental protection, high safety performance and long service life.
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 butanolpolyether prepared in example 1.
FIG. 2 is an IR spectrum of p-toluene isocyanate terminated butanol polyether prepared in example 1.
FIG. 3 is an infrared spectrum of phenyl isocyanate capped butanol polyether prepared in example 3.
FIG. 4 is an IR spectrum of the polyether prepared in example 5.
FIG. 5 is an IR spectrum of a phenyl isocyanate-terminated polyether prepared in example 5.
Detailed Description
The invention is further illustrated by the following specific examples. It should be understood that these examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available or can be prepared by known methods unless otherwise specified.
Hereinafter, the average molecular weight is the number average molecular weight.
Example 1
(1) Adding 148g of butanol and 1.2g of solid potassium hydroxide into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO (propylene oxide) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; taking 200g of butanol polyether oligomer, adding 0.85g of potassium methoxide into the butanol polyether oligomer, continuously introducing 225g of PO at 100 ℃ and 0.4MPa, and reacting until the pressure is not reduced any more to obtain 414.6g of butanol polyether (with the average molecular weight of 850, wherein the polymerization degree of PO is m 1-13.4); 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 at 70 ℃, 50g of p-toluene isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, a proper amount of acetic acid is used for neutralizing to be neutral, and the temperature is reduced to obtain 442.7g of butanol polyether blocked by the p-toluene isocyanate. The infrared test of the sample shows the detection result in fig. 2.
As can be seen from FIG. 2, at 1050cm-1The nearby absorption peak is the infrared absorption peak of polyether, and compared with the infrared spectrum before blocking (FIG. 1), at 1720--1The characteristic absorption peak of the carbamate group appears at the position of (a), which indicates that the product is the butanol polyether blocked by the p-toluene isocyanate.
Example 2
(1) Adding 148g of butanol and 1.6g of NaH into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO/EO (the weight ratio of the two is 50/50) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; 200g of butanol polyether oligomer is taken, 1.1g of sodium methoxide is added into the butanol polyether oligomer, 240g of PO/EO (50/50) is continuously introduced at 100 ℃ and 0.4MPa, the reaction is carried out until the pressure is not reduced any more, and 428.7g of butanol polyether (average molecular weight 880, wherein the polymerization degree of PO or EO is m1(PO) ═ 6.9, 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 the temperature of 100 ℃, a proper amount of acetic acid is used for neutralizing to be neutral, and the temperature is reduced to obtain 440.3g of butanol polyether blocked by p-toluene isocyanate. The product formed was confirmed by infrared spectroscopy to be p-toluene isocyanate terminated butanol polyether.
Example 3
(1) Adding 148g of butanol and 1.2g of solid potassium hydroxide into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO (propylene oxide) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; taking 200g of butanol polyether oligomer, adding 0.85g of potassium methoxide into the butanol polyether oligomer, continuously introducing 225g of PO at 100 ℃ and 0.4MPa, and reacting until the pressure is not reduced any more to obtain 413.4g of butanol polyether (with the average molecular weight of 850, wherein the polymerization degree of PO is m 1-13.4);
(2) 400g of butyl 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 ℃, a proper amount of acetic acid is used for neutralization to neutrality, and the temperature is reduced to obtain 418.1g of butyl polyether blocked by phenyl isocyanate. The infrared detection result of the product is shown in fig. 3.
Comparing the infrared spectrum before blocking, at 1720 and 1750cm in FIG. 3-1The characteristic absorption peak of the carbamate group appears at the position of (A), which proves that the synthesized product is phenyl isocyanate terminated butanol polyether.
Example 4
(1) Adding 148g of butanol and 1.6g of NaH into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO/EO (the weight ratio of the two is 50/50) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; taking 200g of butanol polyether oligomer, adding 1.1g of sodium methoxide into the butanol polyether oligomer, continuously introducing 240g of PO/EO (50/50) at 100 ℃ and 0.4MPa, and reacting until the pressure is not reduced any more to obtain 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);
(2) 400g of butyl polyether (average molecular weight is 880), the temperature is controlled at 70 ℃, 27g of phenyl isocyanate is slowly added, the reaction is carried out for 4 hours at 100 ℃, an appropriate amount of acetic acid is used for neutralization to neutrality, and the temperature is reduced to obtain 419.6g of phenyl isocyanate terminated butyl polyether. The infrared spectrum test proves that the generated product is phenyl isocyanate terminated butanol polyether.
Example 5
(1) 134g of dipropylene glycol and 1.2g of solid potassium hydroxide are added into a reaction kettle, nitrogen is replaced, the temperature is increased to 120 ℃, 666g of PO (propylene oxide) is continuously introduced under 0.2MPa, and the reaction is carried out until the pressure is not reduced any more, so that 776.3g of PPG800 (average molecular weight 800, wherein the polymerization degree of PO is m 1-11.5) is prepared; the infrared characterization results are shown in fig. 4.
(2) 400g of PPG (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 the temperature of 100 ℃, a proper amount of acetic acid is used for neutralizing to be neutral, and the temperature is reduced to obtain 420.3g of PPG420 blocked by the phenyl isocyanate. The infrared characterization results are shown in fig. 5.
Comparing the infrared spectrum before blocking at 1720-1750cm-1The characteristic absorption peak of the carbamate group appears at the position of (a), which proves that the synthesized product is the phenyl isocyanate-terminated PPG 800.
Comparative example 1
Adding 148g of butanol and 1.2g of solid potassium hydroxide into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO (propylene oxide) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; 200g of butanol polyether oligomer was taken, 0.85g of potassium methoxide was added thereto, and then, 225g of PO was continuously introduced at 100 ℃ and 0.4MPa, and the mixture was reacted until the pressure was not lowered any more, and neutralized to neutrality with an appropriate amount of acetic acid, whereby 413.1g of butanol polyether (average molecular weight 850, wherein the degree of polymerization of PO was m. 13.4) was obtained.
Comparative example 2
Adding 148g of butanol and 1.6g of NaH into a reaction kettle, replacing with nitrogen, heating to 100 ℃, continuously introducing 652g of PO/EO (the weight ratio of the two is 50/50) under 0.2MPa, and reacting until the pressure is not reduced any more to obtain butanol polyether oligomer; 200g of butanol polyether oligomer is taken, 1.1g of sodium methoxide is added into the butanol polyether oligomer, 240g of PO/EO (50/50) is continuously introduced at 100 ℃ and 0.4MPa, the reaction is carried out until the pressure is not reduced any more, and a proper amount of acetic acid is used for neutralizing the mixture to be neutral, so that 425.7g of butanol polyether (the average molecular weight is 880, wherein the polymerization degree of PO or EO is m1(PO) ═ 6.9, and m2(EO) ═ 9.2) is prepared.
Comparative example 3
Adding 134g of dipropylene glycol and 1.2g of solid potassium hydroxide into a reaction kettle, replacing with nitrogen, heating to 120 ℃, continuously introducing 666g of PO (propylene oxide) at 0.2MPa, reacting until the pressure is not reduced, and neutralizing with a proper amount of acetic acid until the reaction is neutral to obtain 778.1g of PPG800 (average molecular weight 800, m1 is 11.5);
test example
The ignition points of the products of examples 1 to 5 and comparative examples 1 to 3 above were tested according to the method for determining the ignition point of GB/T3536-2008 petroleum products (Cleveland open cup method), and the results are shown in the following table:
| product source | Initiator | EO/PO | End-capping agents | Ignition Point (. degree.C.) |
| Example 1 | Butanol | PO | P-toluene isocyanate | 270 |
| Example 2 | Butanol | PO/EO＝50/50 | P-toluene isocyanate | 234 |
| Example 3 | Butanol | PO | Phenyl isocyanate | 267 |
| Example 4 | Butanol | PO/EO＝50/50 | Phenyl isocyanate | 231 |
| Example 5 | Dipropylene glycol | PO | Phenyl isocyanate | 285 |
| Comparative example 1 | Butanol | PO | —— | 235 |
| Comparative example 2 | Butanol | PO/EO＝50/50 | —— | 200 |
| Comparative example 3 | Dipropylene glycol | PO | —— | 240 |
From the above results, it can be seen that the high ignition point polyether prepared by the present invention has an ignition point significantly higher than that of a product prepared without using an isocyanate end-capping, and can be used for improving the safety of hydraulic fluid or hydraulic oil. In addition, the polyether product with high ignition point prepared by the method has the excellent performances of high viscosity index, low volatility, low pour point, good lubricity and the like, so the method has practical value.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A polyether of the formula (I):
wherein n is an integer of 1 or more;
selected from unsubstituted or optionally substituted by one, two or more RaSubstituted with the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkylcycloalkyl, alkylheterocyclyl, alkylaryl, alkylheteroaryl, alkyloxyalkyl, alkyloxy;
R1、R2identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RbA substituted alkylene group;
R3selected from unsubstituted or optionally substituted by one, two or more RcSubstituted with the following groups: alkyl, cycloalkyl, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkylcycloalkyl, or alkylheterocyclyl;
m1, m2 are identical or different and are each independently selected from a number from 0 to 300, with the proviso that m1 and m2 are not both 0 at the same time;
the R isa、Rb、RcIdentical or different, independently of one another, from the group consisting of halogen, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.
2. The polyether of claim 1, wherein in formula (I), n is an integer of 1 to 6;
is selected from C1-10Straight or branched chainChain alkyl radical, C1-10Straight or branched alkyl-O-C1-10A linear or branched alkyl group;
R1、R2identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by C1-10Straight or branched alkyl substituted C2-4An alkylene group of (a);
R3is selected from C1-10Straight or branched chain alkyl, unsubstituted or optionally substituted by 1 to 3C1-10Straight or branched chain alkyl, halogen substituted as follows: c5-12Cycloalkyl radical, C5-12Aryl radical, C1-10Straight or branched alkyl C5-12An aryl group;
m1 and m2 are identical or different and are each independently selected from the group consisting of a number from 0 to 200, with the proviso that m1 and m2 are not both 0 at the same time.
3. Polyether according to claim 1 or 2, characterized in that in formula (I), n is an integer from 1 to 4;
R1、R2identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by C1-3Straight or branched alkyl substituted C2-4An alkylene group of (a);
m1 and m2 are identical or different and are each independently selected from a number from 0 to 100, with the proviso that m1 and m2 are not both 0 at the same time;
R3is selected from C1-6Straight or branched chain alkyl, unsubstituted or optionally substituted by 1 to 3C1-6Straight or branched chain alkyl, halogen substituted as follows: c5-12Cycloalkyl radical, C5-12Aryl or C1-6Straight or branched alkyl C5-12And (4) an aryl group.
4. A process for preparing a polyether according to any one of claims 1 to 3, comprising:
S1)
reacting with olefin oxide to obtain polyether shown in the following formula (II),
s2) reacting the polyether obtained in step S1) with an isocyanate R3-NCO reaction to obtain the polyether with high ignition point shown in formula (I);
wherein ,
R1、R2、R3m and n have the definitions as defined in any one of claims 1 to 3;
the alkylene oxide is ring-opened to obtain-R1O-and/or-R2Alkylene oxide of O-.
5. The method for preparing polyether according to claim 4, wherein the reaction of step S1) is performed in the presence of a catalyst selected from basic catalysts.
6. The method for preparing polyether according to claim 4 or 5, wherein the amount of the catalyst is 0.01-10.0% of the total raw material mass.
7. The method for preparing polyether according to any one of claims 4-6, wherein the temperature of the reaction in step S1) is 40-180 ℃;
in the step S2), the reaction temperature is 50-160 ℃.
8. The process for preparing a polyether according to any one of claims 4 to 7, wherein in step S2), the polyether of formula (II) is reacted with the isocyanate R3The molar ratio of-NCO is 1: 0.01-6.1.
9. A hydraulic fluid or oil comprising a polyether according to any one of claims 1 to 3.
10. Use of a polyether according to any one of claims 1 to 3 for the preparation of a hydraulic or hydraulic fluid.
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| CN112521594A (en) * | 2020-11-27 | 2021-03-19 | 广东石油化工学院 | Polyether derivative and process for producing the same |
| CN112608465A (en) * | 2020-11-27 | 2021-04-06 | 广东石油化工学院 | Antioxidant and preparation method thereof |
| WO2022110068A1 (en) * | 2020-11-27 | 2022-06-02 | 广东石油化工学院 | Polyether derivative and preparation method therefor |
| CN116240066A (en) * | 2023-03-17 | 2023-06-09 | 安徽中天石化股份有限公司 | High-wear-resistance flame-retardant hydraulic fluid and preparation method thereof |
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| 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 |
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112521594A (en) * | 2020-11-27 | 2021-03-19 | 广东石油化工学院 | Polyether derivative and process for producing the same |
| CN112608465A (en) * | 2020-11-27 | 2021-04-06 | 广东石油化工学院 | Antioxidant and preparation method thereof |
| WO2022110068A1 (en) * | 2020-11-27 | 2022-06-02 | 广东石油化工学院 | Polyether derivative and preparation method therefor |
| CN112608465B (en) * | 2020-11-27 | 2023-04-28 | 广东石油化工学院 | Antioxidant and preparation method thereof |
| CN112521594B (en) * | 2020-11-27 | 2023-08-18 | 广东石油化工学院 | Polyether derivative and process for producing the same |
| CN116240066A (en) * | 2023-03-17 | 2023-06-09 | 安徽中天石化股份有限公司 | High-wear-resistance flame-retardant hydraulic fluid and preparation method thereof |
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