CA1180186A - Anti-misting of hydrocarbon fluid - Google Patents
Anti-misting of hydrocarbon fluidInfo
- Publication number
- CA1180186A CA1180186A CA000421896A CA421896A CA1180186A CA 1180186 A CA1180186 A CA 1180186A CA 000421896 A CA000421896 A CA 000421896A CA 421896 A CA421896 A CA 421896A CA 1180186 A CA1180186 A CA 1180186A
- Authority
- CA
- Canada
- Prior art keywords
- hydrocarbon
- molecular weight
- percent
- process according
- epoxybutane
- 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.)
- Expired
Links
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 37
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 37
- 239000012530 fluid Substances 0.000 title description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000000446 fuel Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 20
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 230000035939 shock Effects 0.000 claims abstract description 8
- 239000002173 cutting fluid Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 description 27
- -1 ethylene, propylene Chemical group 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 12
- 239000003595 mist Substances 0.000 description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 238000005755 formation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000010730 cutting oil Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001748 polybutylene Polymers 0.000 description 6
- 150000003335 secondary amines Chemical group 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical compound CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical group CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003975 aryl alkyl amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002085 enols Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 150000002991 phenoxazines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- 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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Polyethers (AREA)
- Colloid Chemistry (AREA)
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
ABSTRACT
Hydrocarbon liquids such as fuels for gas turbine engines and metal cutting fluids are inhibited to the formation of dispersions upon application of shock or stress thereto by an effective amount to prevent such dispersion formation of a high molecular weight addition polymer of 1,2-epoxybutane.
24,801B-F
Hydrocarbon liquids such as fuels for gas turbine engines and metal cutting fluids are inhibited to the formation of dispersions upon application of shock or stress thereto by an effective amount to prevent such dispersion formation of a high molecular weight addition polymer of 1,2-epoxybutane.
24,801B-F
Description
ANTI MISTING ADDITIVE
FOR ~I~lDROCARBON FLUIDS
The invention relates to a process for pre~
venting the dissemination of a hydrocarbon liquid having a free surface into a dispersion of fine liquid droplets under conditions of shock or stress. It is often desirable to control the extent of misting or dispersion-in-air of hydrocarbon liquids having rather low flash points. More particularly, hydrocarbon fuels such as are employed in aircraft are desirably protected from misting under conditions of shock or stress as produced, for example, during an aircraft crash, or whenever such ~uels are subjected to shock or stress while exposed to an ignition source. Additionally it is also desirable to control mist formation in hydrocarbon-based metal cutting fluids employed in metal cutting, grinding and machining operations.
In U.S. Patent 3,996,023, several polymers suitably employed in preventing the misting of hydrocarbon fuels aré disclosed. Preferred compounds include non-crystalline polymers substantially devoid of polar groups, especially polymers of ethylenically unsaturated hydrocarbons such as ethylene, propylene, 24,801B-F
IL80~
isobutylene, and butadiene. Polymers formed by the addition polymerization of alkylene oxides are briefly discussed. In U.S. Patent 3,557,017, ultra high molecular weight oxyalkylene polymers are taught as demulsifiers and thickeners for hydrocarbon systems used in oil well fracturing. Preferred oxyalkylene oxide polymers were those derived from propylene oxide.
Numerous catalyst systems are known for prep-aration of high molecular weight alkylene oxides.
Illustrative are a combination of ferric halide salts and propylene oxide disclosed in U.S. Patent 2,706,181, or organoaluminum, organozinc and organomagnesium compounds taught in U.S. Patent 2,870,100. Improved coordination anionic polymerization systems include chelated forms of organoaluminum such as disclosed in U.S.Patents 3,219,591; 3,186,958; 3,301,796; and 3,135,705.
In recent investigations the important contri-bution of elongation deformation to polymeric rheo-logical behavior has been identified. It has now beenrecognized that various properties of significant commercial application cannot be adequately predicted by viscometric (shear) flow behavior alone. Often, due to inherent differences in elongation or tensile deformation versus shear deformation, the corresponding elongational viscosity and shear viscosity may be related in only the extremely limited case where the material is Newtonian in both elongation and shear.
Because of this recognized difference between elonga-tional and shear flow, the researcher is not necessarilyable to predict the response to elongational flow of a viscoelastic material based on knowledge of its shear 24,801B-F -2-flow behavior. Such elongational deformation properties are in fact particularly relevant in imparting improved performance to anti-misting agents.
Because the tensile or elongational viscosity of various materials appears to be affected by molecular weight considerations, particularly the average molecular weight and the distribution thereof, as well as by molecular geometry, the elongation properties of polymeric compounds and therefore the anti-misting properties thereof are not necessarily predictable on the basis of shear viscosity considerations.
Another important property of an anti-misting agent is the shear stability of the material. Application of relatively mild shear should not significantly degrade the polymer and thereby destroy the polymer's ability to prevent the dispersion of the hydrocarbon liquid. For example, normal pumping and handling procedures used in transporting a jet fuel should not cause deterioration of the anti-misting properties of the polymer. Shear stability is particularly desired in cutting fluids due to repeated use under conditions of relatively high shear.
It would be desirable to provide a polymer that is effective in preventing the formation of hydro-carbon-air dispersions or mists at low levels of con-centration, that is highly soluble in the hydrocarbon liguid, such that even at extremely low temperatures essentially no precipitate or colloidal state forms, and that is relatively stable and not degraded by shear forces.
24,801B-F -3-Accordingly, there is now provided an improved process for preventing the dispersion o~ a hydrocarbon liquid having a free surface upon application of shock or stress comprising adding to the hydrocarbon liquid an effective amount to prevent the dispersion thereof of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane. Also provided is a compo-sition comprising a hydrocarbon liquid and an effective amount to prevent the formation of a dispersion thereof upon application of shock or stress thereto of a high molecular weight addition polymer comprising polymer-ized 1,2-epoxybutane.
Addition polymers comprising polybutylene oxide, e.g., addition polymers of 1,2-epoxybutane, use-ful herein may be prepared by any technique suited tothe preparation of extremely high molecular weight polymers. Examples include the anionic polymerization of U.S. Patents, 2,870,100 and 3,219,591.
A preferred catalyst for polymerizing 1,2-epoxybutane to extremely high molecular weight polybutyl-ene oxide comprises a composition prepared by contacting:
Component A/ a compound represented by the formula RR'AlX wherein R and R' each independently represent an alkyl group of 1 to 4 carbon atoms, and X represents hydrogen or an alkyl or alkoxy group of 1 to 4 carbon atoms;
Component B, an organic nitrogen base com-pound selected from secondary nitrogen-containing compounds having basicity about e~ual to cr less than the basicity of dimethylamine and having no active hydrogen atoms other than those of the secondary nitrogen;
24,801B-F -4-Component C, a ~-diketone; and Component D, water;
in the molar ratios o~
B:A - 0.01:1 to 2.5:1 C:A - 0.1:1 to 1.5:1 D:A - 0.01:1 to 1.5:1 provided that when the molar ratio o~ (C + 2D):A is greater than 3:1, the B:A molar ratio is at least 1:1.
The preferred catalyst is more particularly defined as follows. Component A is a compound repre-sented by the formula RR'AlX wherein R and R' each independently represent an alkyl group of 1 to 4 carbon atoms, and X represents hydrogen or an alkyl or alkoxy group of 1 to 4 carbon atoms. In a preferred mode, X
represents an alkyl group.~ In a more preferred mode, R, R' and X all represent the same alkyl group and most preferably, the compound is triethylaluminum. Examples o~ suitable compounds are trimethylaluminum, triethylalu-minum, triisobutylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, diethylaluminum hydride, dipropyl-aluminum hydride, diisobutylaluminum hydride, diethyl ethoxy aluminum, and diisobutyl ethoxy aluminum. In practice, Component A is normally supplied in a solution of a hydrocarbon OL other solvent.
Component B is an organic nitrogen base com-pound selected from secondary nitrogen-containing com-pounds having basicity about equal to or less than the basicit,v of dimethylamine and having no active hydrogen atoms other than those of the secondary nitrogen. By 24,801B-F -5-~13L8~l86 "active hydrogen atoms" are mear.t Zerewitinoff hydrogen atoms (see J. Am. Chem. Soc., 49:3181 (19Z8)) which initiate alkylene oxide polymerization as are found on hydroxyl, thio or primary and secondary amine functional groups. Such secondary amines are commonly those bear-ing electron-withdrawing groups in close proximity to the nitrogen atom such as carbonyl groups, phenyl rings, cyano groups, halo groups, carboxylic acids or ester groups, and other such groups that have strong electron-withdrawing effects on -the secondary amine.
For example, such compounds are N-alkyl or -aryl amides, arylalkylamines, diarylamines, and other weak bases.
Secondary amines having a PKb Of greater than 4 are suitable and those having PKb of greater than 6 are preferred. Examples of suitable secondary amines are dimethylamine, diethylamine, N-methylaniline, N-methyl--p-nitroaniline, N alkylacetamide, N-arylacetamide, succinimide, diphenylamine, phenothiazines, and phen-oxazines. Especially preferred are phenoxazine, phenothiazine and N-acetamide.
The strengths of organic bases are compiled for a large number of such bases in the IUPAC work by D. D. Perrin, "Dissociation Constants of Organic Bases in Aqueous Solutions", Butterworths (London, 1965).
For most secondary organic amines not listed therein, relative base strength may be deduced by examining the value noted for a structurally related amine then estimating the effect of structural differences on the base strength. For example, conjugation of the amino group with electron-withdrawing groups lowers the base strength of the amino group. The effects of structural changes in organic amines are discussed in great detail in numerous works, for example in "The Chemistry of the 24,801B-F -6-~8~
Amino Group", S. Patai, Ed., Chapter 4, "Basicity and Complex Formatlon" by J. W. Smith, pp. 161-204, Inter-science (New York, 1968).
One simple method for determining whether a secondary amine is less basic than dimethylamine is to employ both in side-by-side preparation of the catalyst, use the resulting catalyst in polymerization of a monomer such as propylene oxide, and then determine the intrinsic viscosities of the resulting polypropylene oxide products. If the intrinsic viscosity of the product derived from the catalyst prepared with dimethylamine is lower than the one from the o-ther amine, then the other amine may be considered less basic than dimethylamine.
The amount of Component B to be employed may be expressed in the molar ratio of Component B per mole of Component A. The lower amount is suitably about 0.01, pref-erably 0.05 and most preferably 0.1. The upper amount is suitably 2.5, preferably 1 and most preferably 0.5. The optimum molar ratio of B:A for producing very high molecular weight polyethers is about 0.25:1.
Component C is selected from ~-diketones or the tautomeric enol form thereof. Suitable, for example, are 2,4-pentanedione, 2,4-hexanedione, 3,5-heptanedione, l-phenyl-1,3-butanedione, ethylacetylacetate, and similar materials. Examples of numerous suitable ~-diketones are described in U.S. Patent 2,866,761.
Preferred for use as Component C is 2,4-pentanedione because of its relative availability.
24,801B-F -7-For the amount of Component C to be employed, expressed as moles of C per mole of A, a lower amount is suitably 0.1 and preferably 0.2. As an upper amount the ratio is suitably 1.5 and preferably 0.8. The optimum molar ratio of C:A is about 0.5:1.
Component D is water and is suitably employed in a lower amoun'c of about 0.1, preferably 0.3 and more preferably 0.4, mole of D per mole of A. The upper amount is suitably 1.5, preferably 1.1 and more preferably 1.0, mole of D per mole of A. The optimum ratio of D:A is 0.5 to 0.8:1.
The above components are employed such that when the molar ratio sum of (C + 2D):A is greater than 3:1, then the B:A molar ratio is at least 1:1.
Preferably the components are combined in the ratio where (B + C + 2D):A is less than or equal to 3:1 and more preferably less than 2:1. In one embodiment, the following molar ratios are employed to form a catalyst which when contacted with a vicinal alkylene oxide pro-duces a polyether of a very high intrinsic viscosity:B:A - about 0.~5:1; C:A - about 0.5:1; and D:A - about 0.6:1. In a second embodiment, a catalyst is prepared which will give moderateIy high intrinsic viscosity polyethers when contacted with vicinal alkylene oxides according to the process described herein. The molar ratios in this second embodiment are: B:A - about
FOR ~I~lDROCARBON FLUIDS
The invention relates to a process for pre~
venting the dissemination of a hydrocarbon liquid having a free surface into a dispersion of fine liquid droplets under conditions of shock or stress. It is often desirable to control the extent of misting or dispersion-in-air of hydrocarbon liquids having rather low flash points. More particularly, hydrocarbon fuels such as are employed in aircraft are desirably protected from misting under conditions of shock or stress as produced, for example, during an aircraft crash, or whenever such ~uels are subjected to shock or stress while exposed to an ignition source. Additionally it is also desirable to control mist formation in hydrocarbon-based metal cutting fluids employed in metal cutting, grinding and machining operations.
In U.S. Patent 3,996,023, several polymers suitably employed in preventing the misting of hydrocarbon fuels aré disclosed. Preferred compounds include non-crystalline polymers substantially devoid of polar groups, especially polymers of ethylenically unsaturated hydrocarbons such as ethylene, propylene, 24,801B-F
IL80~
isobutylene, and butadiene. Polymers formed by the addition polymerization of alkylene oxides are briefly discussed. In U.S. Patent 3,557,017, ultra high molecular weight oxyalkylene polymers are taught as demulsifiers and thickeners for hydrocarbon systems used in oil well fracturing. Preferred oxyalkylene oxide polymers were those derived from propylene oxide.
Numerous catalyst systems are known for prep-aration of high molecular weight alkylene oxides.
Illustrative are a combination of ferric halide salts and propylene oxide disclosed in U.S. Patent 2,706,181, or organoaluminum, organozinc and organomagnesium compounds taught in U.S. Patent 2,870,100. Improved coordination anionic polymerization systems include chelated forms of organoaluminum such as disclosed in U.S.Patents 3,219,591; 3,186,958; 3,301,796; and 3,135,705.
In recent investigations the important contri-bution of elongation deformation to polymeric rheo-logical behavior has been identified. It has now beenrecognized that various properties of significant commercial application cannot be adequately predicted by viscometric (shear) flow behavior alone. Often, due to inherent differences in elongation or tensile deformation versus shear deformation, the corresponding elongational viscosity and shear viscosity may be related in only the extremely limited case where the material is Newtonian in both elongation and shear.
Because of this recognized difference between elonga-tional and shear flow, the researcher is not necessarilyable to predict the response to elongational flow of a viscoelastic material based on knowledge of its shear 24,801B-F -2-flow behavior. Such elongational deformation properties are in fact particularly relevant in imparting improved performance to anti-misting agents.
Because the tensile or elongational viscosity of various materials appears to be affected by molecular weight considerations, particularly the average molecular weight and the distribution thereof, as well as by molecular geometry, the elongation properties of polymeric compounds and therefore the anti-misting properties thereof are not necessarily predictable on the basis of shear viscosity considerations.
Another important property of an anti-misting agent is the shear stability of the material. Application of relatively mild shear should not significantly degrade the polymer and thereby destroy the polymer's ability to prevent the dispersion of the hydrocarbon liquid. For example, normal pumping and handling procedures used in transporting a jet fuel should not cause deterioration of the anti-misting properties of the polymer. Shear stability is particularly desired in cutting fluids due to repeated use under conditions of relatively high shear.
It would be desirable to provide a polymer that is effective in preventing the formation of hydro-carbon-air dispersions or mists at low levels of con-centration, that is highly soluble in the hydrocarbon liguid, such that even at extremely low temperatures essentially no precipitate or colloidal state forms, and that is relatively stable and not degraded by shear forces.
24,801B-F -3-Accordingly, there is now provided an improved process for preventing the dispersion o~ a hydrocarbon liquid having a free surface upon application of shock or stress comprising adding to the hydrocarbon liquid an effective amount to prevent the dispersion thereof of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane. Also provided is a compo-sition comprising a hydrocarbon liquid and an effective amount to prevent the formation of a dispersion thereof upon application of shock or stress thereto of a high molecular weight addition polymer comprising polymer-ized 1,2-epoxybutane.
Addition polymers comprising polybutylene oxide, e.g., addition polymers of 1,2-epoxybutane, use-ful herein may be prepared by any technique suited tothe preparation of extremely high molecular weight polymers. Examples include the anionic polymerization of U.S. Patents, 2,870,100 and 3,219,591.
A preferred catalyst for polymerizing 1,2-epoxybutane to extremely high molecular weight polybutyl-ene oxide comprises a composition prepared by contacting:
Component A/ a compound represented by the formula RR'AlX wherein R and R' each independently represent an alkyl group of 1 to 4 carbon atoms, and X represents hydrogen or an alkyl or alkoxy group of 1 to 4 carbon atoms;
Component B, an organic nitrogen base com-pound selected from secondary nitrogen-containing compounds having basicity about e~ual to cr less than the basicity of dimethylamine and having no active hydrogen atoms other than those of the secondary nitrogen;
24,801B-F -4-Component C, a ~-diketone; and Component D, water;
in the molar ratios o~
B:A - 0.01:1 to 2.5:1 C:A - 0.1:1 to 1.5:1 D:A - 0.01:1 to 1.5:1 provided that when the molar ratio o~ (C + 2D):A is greater than 3:1, the B:A molar ratio is at least 1:1.
The preferred catalyst is more particularly defined as follows. Component A is a compound repre-sented by the formula RR'AlX wherein R and R' each independently represent an alkyl group of 1 to 4 carbon atoms, and X represents hydrogen or an alkyl or alkoxy group of 1 to 4 carbon atoms. In a preferred mode, X
represents an alkyl group.~ In a more preferred mode, R, R' and X all represent the same alkyl group and most preferably, the compound is triethylaluminum. Examples o~ suitable compounds are trimethylaluminum, triethylalu-minum, triisobutylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, diethylaluminum hydride, dipropyl-aluminum hydride, diisobutylaluminum hydride, diethyl ethoxy aluminum, and diisobutyl ethoxy aluminum. In practice, Component A is normally supplied in a solution of a hydrocarbon OL other solvent.
Component B is an organic nitrogen base com-pound selected from secondary nitrogen-containing com-pounds having basicity about equal to or less than the basicit,v of dimethylamine and having no active hydrogen atoms other than those of the secondary nitrogen. By 24,801B-F -5-~13L8~l86 "active hydrogen atoms" are mear.t Zerewitinoff hydrogen atoms (see J. Am. Chem. Soc., 49:3181 (19Z8)) which initiate alkylene oxide polymerization as are found on hydroxyl, thio or primary and secondary amine functional groups. Such secondary amines are commonly those bear-ing electron-withdrawing groups in close proximity to the nitrogen atom such as carbonyl groups, phenyl rings, cyano groups, halo groups, carboxylic acids or ester groups, and other such groups that have strong electron-withdrawing effects on -the secondary amine.
For example, such compounds are N-alkyl or -aryl amides, arylalkylamines, diarylamines, and other weak bases.
Secondary amines having a PKb Of greater than 4 are suitable and those having PKb of greater than 6 are preferred. Examples of suitable secondary amines are dimethylamine, diethylamine, N-methylaniline, N-methyl--p-nitroaniline, N alkylacetamide, N-arylacetamide, succinimide, diphenylamine, phenothiazines, and phen-oxazines. Especially preferred are phenoxazine, phenothiazine and N-acetamide.
The strengths of organic bases are compiled for a large number of such bases in the IUPAC work by D. D. Perrin, "Dissociation Constants of Organic Bases in Aqueous Solutions", Butterworths (London, 1965).
For most secondary organic amines not listed therein, relative base strength may be deduced by examining the value noted for a structurally related amine then estimating the effect of structural differences on the base strength. For example, conjugation of the amino group with electron-withdrawing groups lowers the base strength of the amino group. The effects of structural changes in organic amines are discussed in great detail in numerous works, for example in "The Chemistry of the 24,801B-F -6-~8~
Amino Group", S. Patai, Ed., Chapter 4, "Basicity and Complex Formatlon" by J. W. Smith, pp. 161-204, Inter-science (New York, 1968).
One simple method for determining whether a secondary amine is less basic than dimethylamine is to employ both in side-by-side preparation of the catalyst, use the resulting catalyst in polymerization of a monomer such as propylene oxide, and then determine the intrinsic viscosities of the resulting polypropylene oxide products. If the intrinsic viscosity of the product derived from the catalyst prepared with dimethylamine is lower than the one from the o-ther amine, then the other amine may be considered less basic than dimethylamine.
The amount of Component B to be employed may be expressed in the molar ratio of Component B per mole of Component A. The lower amount is suitably about 0.01, pref-erably 0.05 and most preferably 0.1. The upper amount is suitably 2.5, preferably 1 and most preferably 0.5. The optimum molar ratio of B:A for producing very high molecular weight polyethers is about 0.25:1.
Component C is selected from ~-diketones or the tautomeric enol form thereof. Suitable, for example, are 2,4-pentanedione, 2,4-hexanedione, 3,5-heptanedione, l-phenyl-1,3-butanedione, ethylacetylacetate, and similar materials. Examples of numerous suitable ~-diketones are described in U.S. Patent 2,866,761.
Preferred for use as Component C is 2,4-pentanedione because of its relative availability.
24,801B-F -7-For the amount of Component C to be employed, expressed as moles of C per mole of A, a lower amount is suitably 0.1 and preferably 0.2. As an upper amount the ratio is suitably 1.5 and preferably 0.8. The optimum molar ratio of C:A is about 0.5:1.
Component D is water and is suitably employed in a lower amoun'c of about 0.1, preferably 0.3 and more preferably 0.4, mole of D per mole of A. The upper amount is suitably 1.5, preferably 1.1 and more preferably 1.0, mole of D per mole of A. The optimum ratio of D:A is 0.5 to 0.8:1.
The above components are employed such that when the molar ratio sum of (C + 2D):A is greater than 3:1, then the B:A molar ratio is at least 1:1.
Preferably the components are combined in the ratio where (B + C + 2D):A is less than or equal to 3:1 and more preferably less than 2:1. In one embodiment, the following molar ratios are employed to form a catalyst which when contacted with a vicinal alkylene oxide pro-duces a polyether of a very high intrinsic viscosity:B:A - about 0.~5:1; C:A - about 0.5:1; and D:A - about 0.6:1. In a second embodiment, a catalyst is prepared which will give moderateIy high intrinsic viscosity polyethers when contacted with vicinal alkylene oxides according to the process described herein. The molar ratios in this second embodiment are: B:A - about
2.5:1; C:A -about 0.5:1; and D:A - about 0.5:1. The most preferred species of the ca-talyst are prepared in the form where B is phenothiazine or N-methylacetamide or C is 2,4-pentanedione.
Additional components may be present in the catalyst and certain additives have in fact been found 24,801B-F -8-~, to provide improved catalytic performance. In particu-lar, a small but effective amount of a Lewis base such as a tertiary amine or an aliphatic ether capable of forming a complex with Component A may be added to the catalyst mixture. Preferred Lewis base compounds are the aliphatic ethers, most suitably cyclic aliphatic ethers such as tetrahydrofuran or dioxane. These compounds are employed in minor amounts sufficient to form a complex with Component A in the presence of the remaining components of the catalys-t. Suitably the aliphatic ether is present in molar amounts from 1 to 6 for each mole of Component A.
Additional components may also be present in the catalyst if desixed. For example, ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, and lower alkyl monoethers of diethylene glycol or dipropylene glycol may be added to the catalyst in purified form as an aid in rendering the catalyst soluble in various solvents.
The catalyst formation and polymerization are carried out according to known techniques such as those of U.S. Patents 3,186,958 and 3,219,591. Suitably the catalyst is prepared by contacting the components in the desired ratios in any of the common hydrocarbon or chlorinated hydrocarbon diluents employed for organic reactions so long as they do not bear Zerewitinoff hydrogen atoms. Suitable diluents, for example, are hexane, toluene, benzene, styrene, decane, chloroben-zene, trichloroethane, perchloroethylene and the like.
A preferred diluent is the hydrocarbon fluid, e.g., fuel or cutting oil, to which the polymer will be later added.
24,801B-F -9-While the catalyst components may be combined in any order desired, because it has been found most effective to employ polymers of relatively high intrinsic viscosity in the present invention, it is preferable, S particularly where the catalyst consists essentially of only Components A, B, C and D, that Components B, C and D be first combined by mixing them well and thereafter adding Component A to the mixture of the other three components. It is also convenient to prepare the catalyst ln situ in the butylene oxide monomer to be polymerized. This is most preferably done by combining Components B, C and D in a solvent witk the desired quantity of butylene oxide monomer and thereafter adding Component A to the mixture after which the polymerization is allowed to proceed. In this fashion, the butylene oxide monomer acts as a cosolvent for the catalyst prior to initiation of the polymerization.
Butylene oxide for polymerization and use herein may first be purified as by the technique described in U.S.
Patent 3,987,065.
After preparation of the high molecular weight polymer, the catalyst may be "killed'l or deactivated by addition of a reactive hydroxyl compound such as water, alcohols or organic acids. Where the polymer is prepared in the hydrocarbon fluid, such as jet fuel, the catalyst may be effectively "killed" by exposure to the atmosphere for a short time. It is believed that water vapor present in the air is sufficient to deactivate the catalyst.
The polymer employed in the instant process comprises polybutylene oxide. Where the hydrocarbon liquid is a fuel, for example, a jet fuel for gas 24,801B-F -10-turbines, it is highly desirable that the polymeric anti-misting additive not detrimentally form a pre-cipitate or colloidal state, particularly at low temperatuxes. The temperature at which such formation occurs, e.g., the theta temperature of the solution, is desirably less than -50C. Further discussion of theta temperature as well as a more detailed description of suitable components of fuels for gas turbines is con-tained in U.S. Patent 3,996,0Z3.
In other applications such as where the hydrocarbon liquid is a cutting fluid, extremely low theta temperatures are not as necessary. Accordingly, a theta temperature of greater than -50C may be sui-table.
At the same time certain hydrocarbon liquids, especially cutting fluids, may contain substantial amounts of a non-hydrocarbon component, such as an alkylene glycol, an alkylene glycol ether or even water. Therefore under conditions where an extremely low theta temperature is not requisite or the hydrocarbon liquid additionally comprises non-hydrocarbon components, the polybutylene oxide anti-misting agent may include comonomers of additional alkylene oxides. Compatibility with fluids consisting essentially of hydrocarbon liquids is impaired by use of excessive amounts of lower alkylene oxide comonomers such as propylene oxide and especially ethylene oxide. Accordingly, only relatively minor amounts of such lower alkylene oxide comonomers are suitably employed where compatibility with hydrocarbon liquids, particularly a jet fuel, is desired. Higher vicinal alkylene oxides such as 1,2-epoxypentane, 1,2-epoxyhexane, etc., or glycidyl ethers such as n-butyl glycidyl ether, tertiarybutyl glycidyl ether, n-octyl glycidyl ether, etc., may be employed as 24,801B-F -11-. . .
comonomers without as significant a detrimen-tal effect on compatibility with the hydrocarbon fluid.
The preferred anti-misting agent for use in hydrocarbon fuels consists essentially of polymerized 1,2-epoxybutane.
While in most applications the catalyst resl-due may be left in the polymer solution without disadvan-tageous results, it is also possible to remove catalyst residue. For example, the aluminum compound which exists as a hydroxide or oxide after deactivation is only sparingly soluble in hydrocarbon liquids, particu-larly at low temperatures and may be removed by filtration.
This process may be particularly desired where the polymer solution is employed as a jet fuel.
Conventional approaches to molecular weight measure of polyethers employed herein are often not appropriate. This is usually due to plugging effects because of the propensity of high molecular weight polyethers to "thicken with shear". It is especially troublesome with such techniques as gel permeation chromatography for molecular weight estimation. None-theless, dissolved concentrations of less than 0.06 weight percent of the polyethers generally do not undergo the shear thickening phenomenon.
In view of the difficulties in employing gel permeation chromatography to compare the relative molecular weights of polyethers produced herein, the alternate method of comparing intrinsic viscosities was instead employed. Intrinsic viscosity [~] is related to molecular weight by the equation:
24,801B-F -12-1~81D~
[~] = MK~
wherein K is a constant, M is molecular weight and ~ is another constant (correlated to the degree of configura-tional coiling in the architecture of an involved poly-mer).
The value of [~] is determined by plotting the measured specific viscosity divided by concentration of polymer in solution (~Sp/conc.) vs. conc. and extrapolating to zero concentration. It is dependent upon the solvent and temperature used during measurements.
Toluene is a good solvent for the purpose. And, 100F
(38C) is an apt temperature at which to measure ~sp' per the equation:
~sp = t wherein t is the efflux time of solution and to is the efflux time of solvent.
Efflux times are readily measurable in an Ostwald viscometer taking values of solutions at four different concentrations. Usually 1-2 g of the polymer solution ( 30 percent solids) is dissolved in toluene overnight with stirring. It is then volumetrically diluted to ~100 ml. Aliquots of 2 ml, 5 ml, and 15 ml from this stock solution are then further diluted to:
10 ml, 10 ml, and 25 ml, respec~tively, with more toluene.
Efflux times are then measured on the stock solution, each of the three solutions and on toluene. With the 24,801B-F -13-~8~
viscometer employed, toluene had a to of 30.6 seconds, while t for the most concentrated solution being tested is best kept below 200 seconds by adjusting concentration.
Concentration for each diluted solution is simply calculable from the concentration of the stock solution. Three samples of this stock solution are then ordinarily weighed into aluminum dishes from T~hich they are devolatilized in a vacuum oven at 100C over-night (under a normal line vacuum). The aluminum dishes are then reweighed to determine the weight of pure polymer remaining. Concentratlon is then calcu-lated as weight percent. This method of determining concentration is quite convenient since concentration normally associated with measuring [~] is reported in the literature as "grams/deciliter". Therefore, values for concentration so determined are higher by a factor corresponding to the density of toluene (0.8502 g/cc at 38C). Values for ~sp/conc. and [~] are correspondingly, therefore, lower by this factor also. Consistent with this, the herein given [~] values are corrected for the density factor, with [~] being herein reported in units of dl/g.
Of particular value in the present invention as anti-misting agents in hydrocarbon fuels are poly-meriæed 1,2-epoxybutanes having relatively high intrinsic viscosity, e.g., intrinsic viscosities in toluene at 38C of at least and preferably 2 and up to 30. Because of the greater effectiveness toward preventing misting of higher molecular weight polybutylene oxide polymers, such polymers of higher molecular weight may be employed in reduced concentrations thereby resulting in more economical operation. Preferred are concentrations by 24,801B-F -14-weight from 0.05 percent to 1 percent, and preferably from 0.1 percent to 0.5 percent by weight.
In other applications, such as the prevention of cutting oil misting, polybutylene oxide polymers of reduced molecular weight and therefore intrinsic viscosity may be more suitably employed in order to avoid the necessary reduction in polymer effectiveness due to shear degradation of the polymer under long-life service conditions. A-t the same time, increased levels of polymer may be employed in order to offset the loss in effectiveness due to decreased molecular chain length.
Preferred for use in cutting fluids are amounts of polymer by weight from 0.1 percent to 5.0 percent, most preferably from 0.2 percent to 1.0 percent.
In particular regard to hydrocarbon fuels, it should be noted that while the extremely high molecular weight butylene oxide polymers herein employed are highly shear stable, they will in fact degrade under application of sufficien-tly high shear. Accordingly, 20; it is possible, employing mechanical shearing or other treatment, to degrade the polymer and thereby render the fuel atomizable or dispersible prior to injection into -the gas turbine.
The following examples are provided as further illustrations of the invention.
Example 1 - Cutting Oil Twenty-five grams of 1,2-butylene oxide, Mobilmet 308~ metal cutting and working oil available commercially from Mobil Oil Corporation (225 g), pheno-thiazine (1.17 g) and 2,4-pentanedione (1.18 g) are 24,801B-F -15-combined in a glass reactor. A sample is removed for water analysis and found to contain 86 ppm water.
Additional water (0.19 g) is added by syringe to produce a total water content of 0.21 g, triethyl-aluminum (14.8 percent in hexane) (18.0 g) is addedunder a nitrogen blanket. The reactor is sealed and placed in a tumbling cage inside a warm water ba-th at about 86C for 44 hours.
After polymerization, cutting oil containing polymerized 1,2-butylene oxide is tested for mist formation. A solution of Mobilmet 308~ cutting oil containing 0.25 percent by weight of the above polyrner is prepared by rapidly stirring a portion of the above product in the cutting oil. Viscosity of the solution as determined by the cone-plate method is 0.055 Pa S
(55 cps). Unmodified oil has a viscosity of 0.051 Pa S
(51 cps).
Mist control is tested by comparing mist for-mation upon injecting air (0.38 MPa; 40 psig) through a drop tube immersed in the fluid to be tested. Mist formation is noted by visual reference and assigned values of no-mist, low mist or fail. The fluid is then exposed to high shear in a laboratory blender for one hour and retested for anti-mist properties. The cutting oil containing 0.25 weight percent polybutylene oxide showed no mist formation even after blending for one hour. Untreated Mobilmet 308~ produced large amounts of mist under all testing conditions.
ExamPle 2 - Jet Fuel ~n additional quantity of polymerized 1,2-butylene oxide is prepared in hexane solvent. The 24,801B-F -16-`:
catalyst employed is prepared by com~ininy in a dry box under nitrogen atmosphere at ambient temperature wi-th stirring, hexane solutions of triisobutylaluminum (0.015 mole) and phenothiazine (0.004 mole) ~total hex-ane is about 40 ml~. Tetrahydrofuran (0.090 mole) isadded dropwise with stirring over a period of about 10 minutes at reduced temperature of 0C-10C. Next, water (enough to provide 0.006 mole total) is added dropwise over a period of 10 minutes, followed by acetylacetone (0.006 mole) which is added dropwise over a period of 5 minutes. The reaction mixture is stirred for 1 hour and transferred to a Parr bomb reactor and diluted with hexane (100 g) and toluene (30 g). After aging by heating and stirring under nitrogen for one hour at 95~C, catalyst preparation is compléte.
The polymer is formed by adding about one mole of 1,2-butylene oxide to the Paar bomb in incre-ments at 75C over a one-hour period. The reaction mixture is stirred at 75C for 5 hours and then cooled.
Evaporation of solvent leaves the desir~d polymer, a light amber colored rubbery solid.
Jet fuel (Jet A) containing 0.2 percent by weight of polymerized 1,2-butylene oxide prepared employing the catalyst prepared according to the above process is tested for anti-misting properties by means of the Flammability Comparison Test Apparatus (FCTA).
The testing device consists of a compressed air source connected to a sonic orifice and a diffuser cone. Fuel is supplled through a metal tube terminating in the airstream at a point selected to produce high shear to the fuel entering the airstream. The air fuel mist thereby prepared is passed over a propane torch flame.
24,801B-F -17-~18-Mist ignition is determined by fuel type (including the presence or absence of an antl-misting agent), the fuel flow rate and the air velocity.
Passing, marginal and fail grades are assigned according to visual examination of the flame propagation.
No propagation ahead of the torch constitutes a passing grade. Propagation ahead of the torch but not to the diffuser cone constitutes a marginal grade. Propagation ahead of the torch all the way to the diffuser cone constitutes a failing grade.
Jet A fuel at 27C which is not treated with an anti-misting agent consistently fails under all con-ditions of air velocity above 40 m/sec at fuel flow rates above 10 ml/sec. To the contrary, when modified by addition of 0.2 weight percent of polymerized 1,2-butylene oxide, no consistent failure is observed at fuel flow rates less than 15 ml/sec at air velocities less than 70 m/sec.
The above test demonstrates that polymerized 1,2-butylene oxide is an effective anti-misting agent which demonstrates surprisingly good effectiveness at preventing the formation of a hydrocarbon fuel/air dispersion even at extremely low concentrations.
2'~,801B-F -18-
Additional components may be present in the catalyst and certain additives have in fact been found 24,801B-F -8-~, to provide improved catalytic performance. In particu-lar, a small but effective amount of a Lewis base such as a tertiary amine or an aliphatic ether capable of forming a complex with Component A may be added to the catalyst mixture. Preferred Lewis base compounds are the aliphatic ethers, most suitably cyclic aliphatic ethers such as tetrahydrofuran or dioxane. These compounds are employed in minor amounts sufficient to form a complex with Component A in the presence of the remaining components of the catalys-t. Suitably the aliphatic ether is present in molar amounts from 1 to 6 for each mole of Component A.
Additional components may also be present in the catalyst if desixed. For example, ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, and lower alkyl monoethers of diethylene glycol or dipropylene glycol may be added to the catalyst in purified form as an aid in rendering the catalyst soluble in various solvents.
The catalyst formation and polymerization are carried out according to known techniques such as those of U.S. Patents 3,186,958 and 3,219,591. Suitably the catalyst is prepared by contacting the components in the desired ratios in any of the common hydrocarbon or chlorinated hydrocarbon diluents employed for organic reactions so long as they do not bear Zerewitinoff hydrogen atoms. Suitable diluents, for example, are hexane, toluene, benzene, styrene, decane, chloroben-zene, trichloroethane, perchloroethylene and the like.
A preferred diluent is the hydrocarbon fluid, e.g., fuel or cutting oil, to which the polymer will be later added.
24,801B-F -9-While the catalyst components may be combined in any order desired, because it has been found most effective to employ polymers of relatively high intrinsic viscosity in the present invention, it is preferable, S particularly where the catalyst consists essentially of only Components A, B, C and D, that Components B, C and D be first combined by mixing them well and thereafter adding Component A to the mixture of the other three components. It is also convenient to prepare the catalyst ln situ in the butylene oxide monomer to be polymerized. This is most preferably done by combining Components B, C and D in a solvent witk the desired quantity of butylene oxide monomer and thereafter adding Component A to the mixture after which the polymerization is allowed to proceed. In this fashion, the butylene oxide monomer acts as a cosolvent for the catalyst prior to initiation of the polymerization.
Butylene oxide for polymerization and use herein may first be purified as by the technique described in U.S.
Patent 3,987,065.
After preparation of the high molecular weight polymer, the catalyst may be "killed'l or deactivated by addition of a reactive hydroxyl compound such as water, alcohols or organic acids. Where the polymer is prepared in the hydrocarbon fluid, such as jet fuel, the catalyst may be effectively "killed" by exposure to the atmosphere for a short time. It is believed that water vapor present in the air is sufficient to deactivate the catalyst.
The polymer employed in the instant process comprises polybutylene oxide. Where the hydrocarbon liquid is a fuel, for example, a jet fuel for gas 24,801B-F -10-turbines, it is highly desirable that the polymeric anti-misting additive not detrimentally form a pre-cipitate or colloidal state, particularly at low temperatuxes. The temperature at which such formation occurs, e.g., the theta temperature of the solution, is desirably less than -50C. Further discussion of theta temperature as well as a more detailed description of suitable components of fuels for gas turbines is con-tained in U.S. Patent 3,996,0Z3.
In other applications such as where the hydrocarbon liquid is a cutting fluid, extremely low theta temperatures are not as necessary. Accordingly, a theta temperature of greater than -50C may be sui-table.
At the same time certain hydrocarbon liquids, especially cutting fluids, may contain substantial amounts of a non-hydrocarbon component, such as an alkylene glycol, an alkylene glycol ether or even water. Therefore under conditions where an extremely low theta temperature is not requisite or the hydrocarbon liquid additionally comprises non-hydrocarbon components, the polybutylene oxide anti-misting agent may include comonomers of additional alkylene oxides. Compatibility with fluids consisting essentially of hydrocarbon liquids is impaired by use of excessive amounts of lower alkylene oxide comonomers such as propylene oxide and especially ethylene oxide. Accordingly, only relatively minor amounts of such lower alkylene oxide comonomers are suitably employed where compatibility with hydrocarbon liquids, particularly a jet fuel, is desired. Higher vicinal alkylene oxides such as 1,2-epoxypentane, 1,2-epoxyhexane, etc., or glycidyl ethers such as n-butyl glycidyl ether, tertiarybutyl glycidyl ether, n-octyl glycidyl ether, etc., may be employed as 24,801B-F -11-. . .
comonomers without as significant a detrimen-tal effect on compatibility with the hydrocarbon fluid.
The preferred anti-misting agent for use in hydrocarbon fuels consists essentially of polymerized 1,2-epoxybutane.
While in most applications the catalyst resl-due may be left in the polymer solution without disadvan-tageous results, it is also possible to remove catalyst residue. For example, the aluminum compound which exists as a hydroxide or oxide after deactivation is only sparingly soluble in hydrocarbon liquids, particu-larly at low temperatures and may be removed by filtration.
This process may be particularly desired where the polymer solution is employed as a jet fuel.
Conventional approaches to molecular weight measure of polyethers employed herein are often not appropriate. This is usually due to plugging effects because of the propensity of high molecular weight polyethers to "thicken with shear". It is especially troublesome with such techniques as gel permeation chromatography for molecular weight estimation. None-theless, dissolved concentrations of less than 0.06 weight percent of the polyethers generally do not undergo the shear thickening phenomenon.
In view of the difficulties in employing gel permeation chromatography to compare the relative molecular weights of polyethers produced herein, the alternate method of comparing intrinsic viscosities was instead employed. Intrinsic viscosity [~] is related to molecular weight by the equation:
24,801B-F -12-1~81D~
[~] = MK~
wherein K is a constant, M is molecular weight and ~ is another constant (correlated to the degree of configura-tional coiling in the architecture of an involved poly-mer).
The value of [~] is determined by plotting the measured specific viscosity divided by concentration of polymer in solution (~Sp/conc.) vs. conc. and extrapolating to zero concentration. It is dependent upon the solvent and temperature used during measurements.
Toluene is a good solvent for the purpose. And, 100F
(38C) is an apt temperature at which to measure ~sp' per the equation:
~sp = t wherein t is the efflux time of solution and to is the efflux time of solvent.
Efflux times are readily measurable in an Ostwald viscometer taking values of solutions at four different concentrations. Usually 1-2 g of the polymer solution ( 30 percent solids) is dissolved in toluene overnight with stirring. It is then volumetrically diluted to ~100 ml. Aliquots of 2 ml, 5 ml, and 15 ml from this stock solution are then further diluted to:
10 ml, 10 ml, and 25 ml, respec~tively, with more toluene.
Efflux times are then measured on the stock solution, each of the three solutions and on toluene. With the 24,801B-F -13-~8~
viscometer employed, toluene had a to of 30.6 seconds, while t for the most concentrated solution being tested is best kept below 200 seconds by adjusting concentration.
Concentration for each diluted solution is simply calculable from the concentration of the stock solution. Three samples of this stock solution are then ordinarily weighed into aluminum dishes from T~hich they are devolatilized in a vacuum oven at 100C over-night (under a normal line vacuum). The aluminum dishes are then reweighed to determine the weight of pure polymer remaining. Concentratlon is then calcu-lated as weight percent. This method of determining concentration is quite convenient since concentration normally associated with measuring [~] is reported in the literature as "grams/deciliter". Therefore, values for concentration so determined are higher by a factor corresponding to the density of toluene (0.8502 g/cc at 38C). Values for ~sp/conc. and [~] are correspondingly, therefore, lower by this factor also. Consistent with this, the herein given [~] values are corrected for the density factor, with [~] being herein reported in units of dl/g.
Of particular value in the present invention as anti-misting agents in hydrocarbon fuels are poly-meriæed 1,2-epoxybutanes having relatively high intrinsic viscosity, e.g., intrinsic viscosities in toluene at 38C of at least and preferably 2 and up to 30. Because of the greater effectiveness toward preventing misting of higher molecular weight polybutylene oxide polymers, such polymers of higher molecular weight may be employed in reduced concentrations thereby resulting in more economical operation. Preferred are concentrations by 24,801B-F -14-weight from 0.05 percent to 1 percent, and preferably from 0.1 percent to 0.5 percent by weight.
In other applications, such as the prevention of cutting oil misting, polybutylene oxide polymers of reduced molecular weight and therefore intrinsic viscosity may be more suitably employed in order to avoid the necessary reduction in polymer effectiveness due to shear degradation of the polymer under long-life service conditions. A-t the same time, increased levels of polymer may be employed in order to offset the loss in effectiveness due to decreased molecular chain length.
Preferred for use in cutting fluids are amounts of polymer by weight from 0.1 percent to 5.0 percent, most preferably from 0.2 percent to 1.0 percent.
In particular regard to hydrocarbon fuels, it should be noted that while the extremely high molecular weight butylene oxide polymers herein employed are highly shear stable, they will in fact degrade under application of sufficien-tly high shear. Accordingly, 20; it is possible, employing mechanical shearing or other treatment, to degrade the polymer and thereby render the fuel atomizable or dispersible prior to injection into -the gas turbine.
The following examples are provided as further illustrations of the invention.
Example 1 - Cutting Oil Twenty-five grams of 1,2-butylene oxide, Mobilmet 308~ metal cutting and working oil available commercially from Mobil Oil Corporation (225 g), pheno-thiazine (1.17 g) and 2,4-pentanedione (1.18 g) are 24,801B-F -15-combined in a glass reactor. A sample is removed for water analysis and found to contain 86 ppm water.
Additional water (0.19 g) is added by syringe to produce a total water content of 0.21 g, triethyl-aluminum (14.8 percent in hexane) (18.0 g) is addedunder a nitrogen blanket. The reactor is sealed and placed in a tumbling cage inside a warm water ba-th at about 86C for 44 hours.
After polymerization, cutting oil containing polymerized 1,2-butylene oxide is tested for mist formation. A solution of Mobilmet 308~ cutting oil containing 0.25 percent by weight of the above polyrner is prepared by rapidly stirring a portion of the above product in the cutting oil. Viscosity of the solution as determined by the cone-plate method is 0.055 Pa S
(55 cps). Unmodified oil has a viscosity of 0.051 Pa S
(51 cps).
Mist control is tested by comparing mist for-mation upon injecting air (0.38 MPa; 40 psig) through a drop tube immersed in the fluid to be tested. Mist formation is noted by visual reference and assigned values of no-mist, low mist or fail. The fluid is then exposed to high shear in a laboratory blender for one hour and retested for anti-mist properties. The cutting oil containing 0.25 weight percent polybutylene oxide showed no mist formation even after blending for one hour. Untreated Mobilmet 308~ produced large amounts of mist under all testing conditions.
ExamPle 2 - Jet Fuel ~n additional quantity of polymerized 1,2-butylene oxide is prepared in hexane solvent. The 24,801B-F -16-`:
catalyst employed is prepared by com~ininy in a dry box under nitrogen atmosphere at ambient temperature wi-th stirring, hexane solutions of triisobutylaluminum (0.015 mole) and phenothiazine (0.004 mole) ~total hex-ane is about 40 ml~. Tetrahydrofuran (0.090 mole) isadded dropwise with stirring over a period of about 10 minutes at reduced temperature of 0C-10C. Next, water (enough to provide 0.006 mole total) is added dropwise over a period of 10 minutes, followed by acetylacetone (0.006 mole) which is added dropwise over a period of 5 minutes. The reaction mixture is stirred for 1 hour and transferred to a Parr bomb reactor and diluted with hexane (100 g) and toluene (30 g). After aging by heating and stirring under nitrogen for one hour at 95~C, catalyst preparation is compléte.
The polymer is formed by adding about one mole of 1,2-butylene oxide to the Paar bomb in incre-ments at 75C over a one-hour period. The reaction mixture is stirred at 75C for 5 hours and then cooled.
Evaporation of solvent leaves the desir~d polymer, a light amber colored rubbery solid.
Jet fuel (Jet A) containing 0.2 percent by weight of polymerized 1,2-butylene oxide prepared employing the catalyst prepared according to the above process is tested for anti-misting properties by means of the Flammability Comparison Test Apparatus (FCTA).
The testing device consists of a compressed air source connected to a sonic orifice and a diffuser cone. Fuel is supplled through a metal tube terminating in the airstream at a point selected to produce high shear to the fuel entering the airstream. The air fuel mist thereby prepared is passed over a propane torch flame.
24,801B-F -17-~18-Mist ignition is determined by fuel type (including the presence or absence of an antl-misting agent), the fuel flow rate and the air velocity.
Passing, marginal and fail grades are assigned according to visual examination of the flame propagation.
No propagation ahead of the torch constitutes a passing grade. Propagation ahead of the torch but not to the diffuser cone constitutes a marginal grade. Propagation ahead of the torch all the way to the diffuser cone constitutes a failing grade.
Jet A fuel at 27C which is not treated with an anti-misting agent consistently fails under all con-ditions of air velocity above 40 m/sec at fuel flow rates above 10 ml/sec. To the contrary, when modified by addition of 0.2 weight percent of polymerized 1,2-butylene oxide, no consistent failure is observed at fuel flow rates less than 15 ml/sec at air velocities less than 70 m/sec.
The above test demonstrates that polymerized 1,2-butylene oxide is an effective anti-misting agent which demonstrates surprisingly good effectiveness at preventing the formation of a hydrocarbon fuel/air dispersion even at extremely low concentrations.
2'~,801B-F -18-
Claims (9)
1. A process for preventing the dispersion of a hydrocarbon liquid having a free surface upon appli-cation of shock or stress comprising adding to the hydro-carbon liquid an effective amount to prevent the disper-sion thereof of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane.
2. A process according to Claim 1 wherein the hydrocarbon liquid is a hydrocarbon fuel suitable for use in a gas turbine engine.
3. A process according to Claim 2 wherein the addition polymer has a specific viscosity measured in toluene at 38°C of at least 1.
4. A process according to Claim 3 wherein the addition polymer has a specific viscosity measured in toluene at 38°C of at least 2.
5. A process according to Claim 2 wherein the high molecular weight addition polymer consists essentially of polymerized 1,2-epoxybutane.
6. A process according to Claim 2 wherein the polymerized 1,2-epoxybutane is added in an amount from 0.05 percent to 1.0 percent by weight.
24,801B-F -19-
24,801B-F -19-
7. A process according to Claim 6 wherein the polymerized 1,2-epoxybutane is added in an amount from 0.1 percent to 0.5 percent by weight.
8. A process according to Claim 1 wherein the hydrocarbon liquid is a metal cutting fluid.
9. A composition of matter comprising a hydrocarbon liquid and an effective amount to prevent the formation of a dispersion thereof upon application of shock or stress thereto of a high molecular weight addition polymer comprising polymerized 1,2-epoxybutane.
24,801B-F -20-
24,801B-F -20-
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US44580582A | 1982-12-01 | 1982-12-01 | |
US445,805 | 1982-12-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1180186A true CA1180186A (en) | 1985-01-02 |
Family
ID=23770263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000421896A Expired CA1180186A (en) | 1982-12-01 | 1983-02-18 | Anti-misting of hydrocarbon fluid |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0110003A3 (en) |
JP (1) | JPS59105087A (en) |
AU (1) | AU1166883A (en) |
CA (1) | CA1180186A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5084197A (en) * | 1990-09-21 | 1992-01-28 | The Lubrizol Corporation | Antiemulsion/antifoam agent for use in oils |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3708338A1 (en) * | 1987-03-14 | 1988-09-22 | Basf Ag | FUELS CONTAINING LOW QUANTITIES OF ALKOXYLATES AND POLYCARBONIC ACID IMIDES |
DE3844222A1 (en) * | 1988-12-29 | 1990-07-05 | Basf Ag | USE OF ADDUCTS OF 1,2-BUTYLENE OXIDE TO H-AZIDE ORGANIC COMPOUNDS AS LUBRICANTS AND LUBRICANTS CONTAINING THESE ADDUCTS |
US5198135A (en) * | 1990-09-21 | 1993-03-30 | The Lubrizol Corporation | Antiemulsion/antifoam agent for use in oils |
AU2844801A (en) * | 1999-12-23 | 2001-07-09 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3382055A (en) * | 1965-02-24 | 1968-05-07 | Exxon Research Engineering Co | Polyalkylethyleneoxide pour point depressant additive |
BE731123A (en) * | 1968-04-11 | 1969-10-06 | ||
BE757347R (en) * | 1969-10-10 | 1971-04-09 | Ici Ltd | PROCEDURE FOR PREVENTING THE SPILLAGE OF A |
JPS52119607A (en) * | 1976-04-01 | 1977-10-07 | Mobil Oil | Lubricating agent for metal working containing mist inhibitor |
-
1983
- 1983-02-18 CA CA000421896A patent/CA1180186A/en not_active Expired
- 1983-02-18 JP JP58024967A patent/JPS59105087A/en active Pending
- 1983-02-18 AU AU11668/83A patent/AU1166883A/en not_active Abandoned
- 1983-02-18 EP EP83101525A patent/EP0110003A3/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5084197A (en) * | 1990-09-21 | 1992-01-28 | The Lubrizol Corporation | Antiemulsion/antifoam agent for use in oils |
Also Published As
Publication number | Publication date |
---|---|
EP0110003A2 (en) | 1984-06-13 |
EP0110003A3 (en) | 1984-08-22 |
JPS59105087A (en) | 1984-06-18 |
AU1166883A (en) | 1984-06-07 |
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