WO2016089507A1 - Water-based polyolefin corrosion inhibitors based on vinyl/vinylidene terminated polyolefins - Google Patents
Water-based polyolefin corrosion inhibitors based on vinyl/vinylidene terminated polyolefins Download PDFInfo
- Publication number
- WO2016089507A1 WO2016089507A1 PCT/US2015/057395 US2015057395W WO2016089507A1 WO 2016089507 A1 WO2016089507 A1 WO 2016089507A1 US 2015057395 W US2015057395 W US 2015057395W WO 2016089507 A1 WO2016089507 A1 WO 2016089507A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl
- vinylidene
- corrosion inhibitor
- inhibitor composition
- terminated polyolefin
- Prior art date
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 106
- 230000007797 corrosion Effects 0.000 title claims abstract description 106
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 103
- 239000003112 inhibitor Substances 0.000 title claims abstract description 92
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 79
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 12
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 229920000768 polyamine Polymers 0.000 claims abstract description 51
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- -1 polypropylene Polymers 0.000 claims description 31
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 7
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 6
- 238000007037 hydroformylation reaction Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 229920001400 block copolymer Polymers 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000012279 sodium borohydride Substances 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecanal Chemical compound CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- UOUILILVWRHZSH-UHFFFAOYSA-N dimethyl-tris[(dimethyl-$l^{3}-silanyl)oxy]silyloxysilicon Chemical compound C[Si](C)O[Si](O[Si](C)C)(O[Si](C)C)O[Si](C)C UOUILILVWRHZSH-UHFFFAOYSA-N 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 229920002312 polyamide-imide Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 0 CCCCOCC(CNC(C)(*)CC(*)OC(C)(C)C(C)N)O Chemical compound CCCCOCC(CNC(C)(*)CC(*)OC(C)(C)C(C)N)O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 101710175987 Testin-2 Proteins 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SFLOAOINZSFFAE-UHFFFAOYSA-N aziridine;ethane-1,2-diamine Chemical compound C1CN1.NCCN SFLOAOINZSFFAE-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 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
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/46—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
Definitions
- the present invention relates to functionalized polyolefins suitable as corrosion inhibitors.
- Corrosion inhibitors are usually surface-active compounds that form dynamic coatings on the metal surface to minimize metal surface contacts to corrosive and erosive components and to suppress corrosion.
- dynamic it is meant that there is an exchange of the corrosion inhibitor between the solution that the metal surface is exposed to and the metal surface. This dynamic exchange necessitates a continuous injection of the corrosion inhibitors into the fluid streams of metal pipes, or treatment of outer pipe/piling surfaces.
- the corrosion inhibitor it is advantageous for the corrosion inhibitor to bind to the metal surface tightly in order to reduce the rate of exchange.
- a polyolefin with a molecular weight of at least 500 g/mole, preferably with a carbon number greater than 14, is used as the building block for the corrosion inhibitor.
- a vinyl terminated polyolefin is used for the corrosion inhibitor assembly. Raising the alkane carbon numbers requires the redesign of the hydrophilic part from a polar head to blocks of hydrophilic polymers so that the polyolefin block can be dispersed in water. Multiple blocks of hydrophilic, amine-containing, polymers also improve the metal surface affinity and adhesion strength.
- a corrosion inhibitor composition comprising the reaction product of a vinyl/ vinylidene-terminated polyolefin having within the range from 14 to 2000 carbon atoms and a polyamine having a molecular weight of at least 500 g/mole.
- the corrosion inhibitor composition can be formed by the process of reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin; reacting the siloxane functionalized vinyl/vinylidene- terminated polyolefin with a allyl-glycol to form a glycol-siloxane vinyl/vinylidene- terminated polyolefin; and reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
- the corrosion inhibitor composition can also be formed by the process of reacting the vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an aldehyde-terminated polyolefin; and reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
- Figure 1 is a 1H NMR of a polyolefin-polyethyleneimine block copolymer of the invention, at (CDCI 3 , 25°C) on a 500 MHz machine, where "aPP" is atactic polypropylene, one block of the block copolymer.
- Figure 2a is a drawing of the corrosion testing apparatus for examples 1-3, 5.
- Figure 2b is a drawing of the corrosion testing apparatus for examples 6-10.
- Figure 3 is a comparison chart, with error bars, showing the results of corrosion testing.
- the invention described herein includes amphiphilic, polyolefin-based corrosion inhibitors and the synthesis of these materials.
- the corrosion inhibitors described herein are preferably water (at least at 23 °C) soluble, but, when contacted with a metal surface (e.g., steel, iron, copper, etc.), will preferentially bind/adhere or "precipitate" to the metal surface.
- the amphiphilic polyolefin-based polymer is a block copolymer of one or more polyolefin blocks and one or more hydrophilic polymer blocks, preferably polyamine ("PA") blocks.
- the polyolefin block can be a homopolymer or a random copolymer of linear alpha olefins that is amorphous, crystalline or semi-crystalline, with number average molecular weight (number average) preferred to be at least 500 g/mole, and preferably have a carbon number of at least 14, or 18, or 25.
- CI corrosion inhibitor
- VTP vinyl/vinylidene-terminated polyolefin
- the invention includes a corrosion inhibitor composition
- a corrosion inhibitor composition comprising the reaction product of a vinyl/vinylidene-terminated polyolefin having within the range from 14 to 2000 (or any other value disclosed herein) carbon atoms and a polyalkylimine having a molecular weight of at least 500 g/mole (or any other value disclosed herein).
- the composition may include other reaction products, or consist essentially of (or consist of) the polyolefin-polyamine block copolymer.
- the composition may also include other additives such as inorganic salts, lower molecular weight surfactants (e.g., less than 400 g/mole) and/or ionic surfactants, solvents, etc., known in the corrosion inhibitor arts.
- the vinyl/vinylidene-terminated polyolefin is first functionalized before reacting with the polyamine.
- said functionalization converts the vinyl/vinylidene-terminus into an aldehyde, a glycol, and/or a siloxane.
- an agent having a desirable functional group such as an oxide or oxygen, or a silane or siloxane that, upon reaction, will form a covalent bond between the agent and the VTP, leaving the functional group intact and chemically available to react with or bind to a substrate, preferably a metal surface.
- compositions described and claimed herein consistist of the named block copolymer, or and includes less than 3 wt , or 2 wt , or 1 wt , or 0.5, or 0.1 wt of reaction products and additives. Otherwise, reference to “corrosion inhibitor” or “corrosion inhibitor composition” includes minor amounts of reaction products and/or additives as is common in the art.
- the inventive corrosion inhibitor will have a polyolefin block (e.g., polypropylene, polyethylene, or ethylene-propylene copolymer) and a polyamine block (e.g., polyethyleneimine, or poly(glycol)amine), forming a polyolefin-polyamine block copolymer.
- a polyolefin block e.g., polypropylene, polyethylene, or ethylene-propylene copolymer
- a polyamine block e.g., polyethyleneimine, or poly(glycol)amine
- VTPs useful in the inventive functionalized polymers described herein can be made in any number of ways.
- “vinyl/vinylidene” what is meant is that the polyolefin may be a mixture of both vinyl- and vinylidene-terminated polyolefins, or the polyolefin may be substantially all one form or the other.
- the VTP's useful herein are polymers as first described in US 2009/0318644 having at least one terminus (CH 2 CHCH 2 -oligomer or polymer) represented by allylic vinyl end group
- the amount of allyl chain ends is determined using J H NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 13 C NMR. These groups (1) and (2) will react to form a chemical bond with a metal as mentioned above to form the M— CH 2 CH 2 — polymer.
- Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl-terminated propylene polymers in Resconi et al, 1 14, J. AM. CHEM. SOC, 1025- 1032 (1992) that are useful herein.
- the vinyl/vinylidene-terminated propylene -based polymers may also contain an isobutyl chain end.
- "Isobutyl chain end” is defined to be an oligomer having at least one terminus represented by the formula (3):
- the isobutyl chain end is represented by one of the following formulae (4):
- the percentage of isobutyl end groups is determined using C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers.
- the vinyl/vinylidene-terminated polymers described herein have an allylic terminus, and at the opposite end of the polymer an isobutyl terminus.
- the VTPs can be made by any suitable means, but most preferably the VTPs are made using conventional slurry or solution polymerization processes using a combination of bridged metallocene catalyst compounds (especially bridged bis-indenyl or bridged 4- substituted bis-indenyl metallocenes) with a high-molecular volume (at least a total volume of 1000 A 3 ) perfluorinated boron activator, for example, as described in US 2012/0245299.
- bridged metallocene catalyst compounds especially bridged bis-indenyl or bridged 4- substituted bis-indenyl metallocenes
- a high-molecular volume at least a total volume of 1000 A 3
- perfluorinated boron activator for example, as described in US 2012/0245299.
- the vinyl/vinylidene-terminated polyolefin can be any polyolefin having a vinyl/vinylidene-terminal group, and is preferably selected from the group consisting of vinyl/vinylidene-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, propylene-butene copolymers, propylene-hexene copolymers, and propylene-ethylene copolymers (wherein the copolymers may be random, elastomeric, impact and/or block), and combinations thereof, each having a number- average molecular weight (Mn) of at least 300 g/mole.
- Mn number- average molecular weight
- the VTP may be a copolymer or terpolymer wherein the C2 content (ethylene derived units) of the vinyl/vinylidene- terminated polyolefin is from 3 to 50 wt%, the C3 content (propylene derived units) is from 50 to 97 wt%; in yet another embodiment, the VTP may contain a third comonomer, thus, the C4 through C14 content (units derived from C4 to C14 a-olefins or dienes) is from 5 to 30 wt% in those embodiments, while the C2 content is from 5 to 50 wt% and the C3 content is from 20 to 90 wt%.
- greater than 70, or 80, or 90, or 94, or 96% of the VTP polymer chains comprises terminal vinyl or vinylidene groups; or within the range of from 50, or 60 wt% to 70, or 80, or 90, or 95, or 98 or 99% of the polymer chains.
- the vinyl/vinylidene-terminated polyolefins preferably have a number average molecular weight (Mn) value of at least 200, or 500, or 1000, or 5000, or 20,000 g/mole, or within a range from 200, or 600, or 800 g/mole to 1000, or 1400, or 1600, or 1800, or 2000, or 4000, or 6000, or 8000, or 10,000 g/mole.
- Mn number average molecular weight
- the vinyl/vinylidene-terminated polyolefins preferably have a weight-average molecular weight (Mw) value of at least 500, or 800, or 1000, or 5000, or 20,000 g/mole, or within the range of from 500, or 800, or 1000, or 2000, g/mole to 6,000, or 10,000, or 12,000, or 20,000, or 30,000, or 40,000 or 50,000, or 100,000, or 200,000, or 300,000 g/mole.
- Mw weight-average molecular weight
- the VTP useful herein is amorphous polypropylene, and desirably has a glass transition temperature (Tg) of less than 10 or 5 or 0°C, more preferably less than -10°C; or within the range of from 0, or -5, or -10°C to -30, or -40, or -50°C or as described herein.
- Tg glass transition temperature
- the VTPs are preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or described quantitatively, having a branching index "g" (or g'( V is avg)) °f at l east 0-90 or 0.96 or 0.97 or 0.98, wherein the "branching index" is well known in the art and measurable by published means, and the value of such branching index referred to herein is within 10 or 20% of the value as measured by any common method of measuring the branching index for polyolefins as is known in the art such as in US 2013/0090433.
- VTP is one wherein the vinyl terminated polyolefin is a compound or mixture of compounds represented by the formula (5):
- each "R” is selected from hydrogen and CI to C4 or CIO alkyls, preferably hydrogen or methyl, or a mixture thereof; and n is an integer from 14, or 16, or 18, or 20, or 25, or 50 to 100, or 200, or 500, or 800, or 1000, or 1500, or 2000.
- the vinyl/vinylidene-terminated polyolefin is a vinyl/vinylidene-terminated atactic polypropylene or polyethylene, or mixture thereof, meaning that it is an ethylene-propylene copolymer.
- PA polyamine
- X a polymeric amine (or, “imine) having multiple amine and/or imine groups.
- Useful PAs can be represented by the formula: (R- NH) X , where "R-NH” is a polymeric or monomelic unit where "R” contains from 1 to 4, or 6, or 10, or 20 carbon atoms; "x" is an integer from 1 to 50, or 100, or 200, or 500 or 100,000.
- the number average molecular weight (Mn) of the polyamine is within a range from 500, or 1000 g/mole to 800, or 1000, or 1200, or 1600, or 2000, or 2200, or 2600, or 3000 g/mole.
- the polyalkyleneimine may comprise one or more ether or glycol groups as well, and most preferably, as at least one terminal amine group, preferably each end of the polymer chains is a terminal amine.
- the PA is a "polyalkylimine” (PAI) and may be represented by the following general formula: (-NHCHzCHz- f-N CHzCHzNF ⁇ CHzCHz-], wherein m is from 10, or 20, or 50 to 200, or 500, or 1,000, or 10,000, or 20,000, and n is from 10, or 20, or 50 to 200, or 500, or 1 ,000, or 10,000, or 20,000.
- PAI polyalkylimine
- Useful PAIs may also comprise secondary amines and/or tertiary amines, such as represented in (-NRCH 2 CH 2 -) m [-N(CH 2 CH 2 NR 2 )CH 2 CH 2 -], wherein each "R” is independently a CI to CIO, or C20 alkyl, alkylamine, aryl, or arylamine.
- the PAIs preferably have a level of secondary amines within the range of from 20 or 30 or 40% to 60 or 70 or 80% relative to all the nitrogens on the PAI.
- the PAIs preferably have, independently, a level of primary and tertiary amines within the range of from 5 or 10 or 15% to 30 or 35 or 40 or 50% relative to all the nitrogens on the PAI.
- the PAIs that are useful herein have a weight average molecular weight (Mw) of from 400, or 500, or 600, or 800 or 1,000 g/mole to 10,000 or 20,000 or 30,000 or 50,000 g/mole.
- Mw weight average molecular weight
- Mn number average molecular weight of the polyalkylimine is within a range from 500, or 1000 g/mole to 800, or 1000, or 1200, or 1600, or 2000, or 2200, or 2600, or 3000 g/mole.
- PAIs examples include those sold by Sigma-AldrichTM, or LupasolTM FG, G20, G35, G100, HF, and P from BASF, and EpominTM SP012, SP018, SP200, and P1050 from Nippon Shokubai.
- the polyalkylimine is a polyalkylimine having the following general structure (6):
- n has a value within the range from 2, or 6, or 10, to 20, or 40, or 60; and wherein the branching depicted in the structure can vary such that the value of a, b, and c can independently be within a range of from 0, or 1, or 2, or 4, to 5 or 10.
- the polyamine also comprises glycol subgroups in the backbone and/or side chains (poly(glycol)amine). More particularly, the polyamine may have glycol subgroups in the backbone and/or side chains (poly(glycol)amine). More particularly, the polyamine may have glycol subgroups in the backbone and/or side chains (poly(glycol)amine). More particularly, the polyamine may have glycol subgroups in the backbone and/or side chains (poly(glycol)amine). More particularly, the polyamine may have
- values of x, y, and z can be, independently within a range of from 2, or 4, or 6, or 10, or 20 to 30, or 40, or 50, or 60, and wherein each R is, independently, selected from hydrogen and CI to CIO alkyls, or C6 to C20 aryls or alkylaryls.
- the corrosion inhibitors can be formed by any chemical reaction that will couple the VTP block to a siloxane block.
- the corrosion inhibitor is formed by the process of first reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin. With or without isolating and/or purifying the first reaction product, the siloxane functionalized vinyl/vinylidene-terminated polyolefin is reacted with an allyl-glycol to form a glycol- siloxane vinyl/vinylidene-terminated polyolefin.
- glycol-siloxane vinyl/vinylidene-terminated polyolefin is reacted with the polyamine such as a polyalkylimine to form the corrosion inhibitor composition (polyolefin-siloxane -polyamine block copolymers, or simply "polyolefin-polyamine block copolymer”).
- polyolefin-siloxane -polyamine block copolymers or simply “polyolefin-polyamine block copolymer”
- reacting what is meant is that the components that will form the desired end product are combined together as a liquid or in a desirable solvent at a desirable temperature, and optionally, with catalysts or promoters that facilitate the formation of the desired end product.
- Other types of reactions can also be used to form the inventive corrosion inhibitor composition.
- a vinyl/vinylidene-terminated polyolefin is reacted with a hydroformylation agent to form an aldehyde-terminated polyolefin. Then, with or without isolating and/or purifying the product, the aldehyde-terminated polyolefin is reacted with a reducing agent and the polyamine such as a polyalkylimine to form the corrosion inhibitor composition.
- a suitable reducing agents include lithium aluminum hydride, boron hydride compounds, atomic hydrogen, oxalic acid, diisobutylaluminum hydride, diborane, sodium amalgam, and other electron donating chemical compounds capable of facilitating the desired reaction.
- the inventive corrosion inhibitor will have a polyolefin block (e.g., polypropylene, polyethylene, or ethylene-propylene copolymer) and a polyamine block(s), forming a block copolymer.
- the inventive corrosion inhibitor composition is a reaction product having a 1 : 1, or 2: 1, or 3: 1, or 4: 1 molar ratio of the polyolefin block and the polyamine block, the polyolefin block having a number average molecular weight (Mn) within the range from 500 g/mole to 1000 g/mole.
- the corrosion inhibitor has an overall carbon number of greater than 25, or 30, or 40, or 100; or within a range from 25, or 30 to 500, or 800, or 1000 carbons.
- the corrosion inhibitor will have in any embodiment a high affinity for polar surfaces, especially metal (iron, aluminum, nickel, etc.) surfaces. This can be determined by any number of means, but in one embodiment, weight loss from a steel surface due to corrosion (reaction and/or loss to the surrounding medium of iron, typically in the form of iron oxide, from the metal surface being tested) by acidic solution and carbon dioxide is a desirable indicator of a corrosion inhibitor's affinity for metal surfaces, and the inventive corrosion inhibitor in any embodiment herein will have a weight loss of less than 3.5 or 3.0 or 2.5 wt a week, meaning that, by weight, only that percentage of the corrosion inhibitor will detach from the metal surface.
- inventive corrosion inhibitors highly desirable as a pipe coating, on its inside, outside, or both surfaces. It can also be used on other surfaces, especially metal surfaces that are exposed to the elements, such as metal pilings, ship hulls, etc., and those surfaces can comprise any type of metal such as iron, steel, zinc, nickel, copper, aluminum, and combinations thereof as is known in the art.
- Polymer molecular weight (weight-average molecular weight, Mw number- average molecular weight, Mn and z-averaged molecular weight, Mz), and molecular weight distribution (Mw/Mn) were determined using Size-Exclusion Chromatography ("GPC").
- Equipment consists of a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer (SEC-DRI-LS-VIS).
- DRI differential refractive index detector
- SEC-DRI-LS-VIS viscometer
- Three Polymer Laboratories PLgel 10mm Mixed-B columns are used.
- the nominal flow rate is 0.5 cm 3 /min and the nominal injection volume is 300 ⁇ L ⁇ .
- the various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135°C.
- Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
- Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
- the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135°C.
- the injection concentration can range from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
- Example 1 Synthesis of aPP-polvetheramine copolymer.
- TDMS tetrakis(dimethylsiloxy)silane
- toluene 10 milliliters.
- TDMS tetrakis(dimethylsiloxy)silane
- toluene 10 milliliters.
- Vinyl-terminated atactic polypropylene 1.5 grams, Mn 978 g/mole, 1.63 millimoles
- platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in toluene (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask.
- TMDS tetrakis(dimethylsiloxy)silane
- toluene 10 milliliters.
- TMDS tetrakis(dimethylsiloxy)silane
- vinyl-terminated aPP 1.2 grams, Mn 908 g/mole, 1.32 millimoles
- platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in toluene (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was stirred for overnight.
- a round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (0.8 gram, 2.43 millimoles) and xylene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated aPP (2.0 grams, Mn 908 g/mole, 2.20 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in xylene (50 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was heated to 50°C for 2 hours.
- a round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (1.0 grams, 3.04 millimoles) and xylene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated aPP (1.0 gram, Mn 2077 g/mole, 0.48 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in xylene (30 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was heated to 50°C for 2 hours.
- a bottle was charged with vinyl polyethylene (1.0 gram, 0.728 millimole), platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex and xylene (80 milliliters) and was then sealed and sonicated for 99 minutes, generating a slurry, which was transferred to an addition funnel.
- a round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (1.0 grams, 3.04 millimoles) and xylene (40 milliliters). The solution was heated to 110°C under nitrogen with stirring. The mixture was stirred under nitrogen at 110°C. The slurry in the addition funnel was then added to the flask dropwise.
- Conditioned water was prepared by first adjusting the pH of deionized water using sulfuric acid until pH reaches 5, then 100 ppm NaCl were added. Corrosion inhibitor was subsequently added to the conditioned water and agitated vigorously to form a homogeneous solution. The solution was then filled into the flask to the brim. Air was blown into the flask. The flask was maintained at certain temperature for 14 days, after which the steel coupons were removed from the glass rod, cleaned and dried, and weighed individually using the following procedure:
- the weight loss on each steel coupon is the weight loss due to corrosion. Greater than 50% reduction in weight loss is demonstrated for all except for the aPP-polyetheramine. These results are shown in Table 1. Note that Example 4 was not tested.
- a stir bar containing the sample was introduced into the three-neck flask as in Figure lb and described above for Examples 1-5.
- a condenser column kept cool with flowing air was attached to the flask.
- the C0 2 was continuously fed into the solution through a Teflon tube.
- the metal (steel) coupons were attached to a glass rod with elastic O-rings.
- the rod was introduced through the middle neck as shown in the figure.
- the round bottom flask was kept at 60°C.
- the apparatus was kept under these conditions for 7 days, at which point the metal coupons were removed, rinsed with water, and treated with a Clarke solution (10 g Stannous Chloride and 4 g Antimony Trioxide in 200 g Hydrochloric Acid).
- Clarke Solution Application The coupons were removed from the testing apparatus to assess their final weight. The coupons were washed with distilled water. The coupon were then placed in the Clarke solution and stirred for one minute. The coupons were then taken out of the Clarke solution and placed in a beaker filled with distilled water. The coupons were then placed in a jar with acetone and blown dry with N 2 , and finally heated under N 2 at 50°C for 30 minutes. (The acetone was used to help facilitate the drying of the coupon.) The coupons were then weighed. Figure 2 shows the results, documented more fully in Table 2. Note that "Low" flow of C0 2 was used; every test was done with 3 coupons; No CI and aPP-PEI are averages of 2 tests; Variability is shown with pooled variance. The key to Table 2:
- a corrosion inhibitor composition comprising (or consisting essentially of, or consisting of) the reaction product of a vinyl/vinylidene-terminated polyolefin having a carbon number of at least 14 or 18 or 25, or more preferably within the range from 14, or 16, or 18, or 20, or 25, or 50 to 100, or 200, or 500, or 800, or 1000, or 1500, or 2000 carbon atoms, and a polyamine having a molecular weight of at least 500, or 800, or 1000, or 5000, or 20,000 g/mole.
- the corrosion inhibitor composition of numbered paragraph 1 (e.g., PI, P2, etc.), wherein the vinyl/vinylidene-terminated polyolefin is first functionalized before reacting with the polyamine.
- P5. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the number average molecular weight (Mn) of the vinyl/vinylidene-terminated polyolefin is within a range from 200, or 600, or 800 g/mole to 1000, or 1400, or 1600, or 1800, or 2000, or 4000, or 6000, or 8000, or 10,000 g/mole.
- Mn number average molecular weight
- values of x, y and z can be, independently within a range of from 2, or 4, or 6, or 10, or 20 to 30, or 40, or 50, or 60, and wherein each R is, independently, selected from hydrogen and CI to CIO alkyls, or C6 to C20 aryls or alkylaryls.
- n has a value within the range from 2, or 6, or 10, to 20, or 40, or 60; and wherein the branching depicted in the structure can vary such that the value of a, b, and c can independently be within a range of from 0, or 1, or 2, or 4, to 5 or 10.
- PI 5 The pipe of numbered paragraph 15, wherein the pipe exhibits a weight loss due to corrosion by acidic solution and carbon dioxide of less than 3.5 or 3.0 or 2.5 wt a week.
- P16 A process of forming a corrosion inhibitor of any one of numbered paragraphs 1 to 14 comprising:
- a process of forming a corrosion inhibitor of any one of numbered paragraphs 1 to 14 comprising:
Abstract
A corrosion inhibitor composition useful in pipes, pilings and hulls comprising the reaction product of a vinyl/vinylidene-terminated polyolefin having at least 14 carbon atoms and a polyamine having a molecular weight of at least 500 g/mole.
Description
WATER-BASED POLYOLEFIN CORROSION INHIBITORS
BASED ON VINYL/VINYLIDENE TERMINATED POLYOLEFINS
INVENTORS: Shuji Luo; Andy H. Tsou; Elizabeth L. Walker; Marcia E. Dierolf; and George Rodriguez
PRIORITY
[0001] This invention claims priority to and the benefit of USSN 62,087377, filed December 4, 2015, and EP application 15153708.1 filed February 3, 2015.
FIELD OF THE INVENTION
[0002] The present invention relates to functionalized polyolefins suitable as corrosion inhibitors.
BACKGROUND OF THE INVENTION
[0003] Pipe and metal piling corrosion in aqueous or aqueous/hydrocarbon fluids has always been a problem for the oil and gas industry in production and supply pipelines of municipal water and gas/oil. The corrosion is most severe during the oil and gas production as a result of the corrosive and erosive components present in the extracted fluids, such as brines, organic acids, carbon dioxide, hydrogen sulfide, microorganisms, sands and rocks. These aggressive constituents can cause severe corrosion to metal pipes and can be extremely costly and disruptive in deep-sea operations where replacement of corroded equipment is difficult. Therefore it is common practice to employ corrosion inhibitors during the production, transportation, storage, and separation/purification of crude oil and natural gas.
[0004] Corrosion inhibitors are usually surface-active compounds that form dynamic coatings on the metal surface to minimize metal surface contacts to corrosive and erosive components and to suppress corrosion. By "dynamic" it is meant that there is an exchange of the corrosion inhibitor between the solution that the metal surface is exposed to and the metal surface. This dynamic exchange necessitates a continuous injection of the corrosion inhibitors into the fluid streams of metal pipes, or treatment of outer pipe/piling surfaces. Thus, it is advantageous for the corrosion inhibitor to bind to the metal surface tightly in order to reduce the rate of exchange.
[0005] Present commercial inhibitors are based on the usage of surfactants that have polar heads, most commonly amines, and an alkyl tail, mostly having a carbon number less than 14 to 25 carbons (MW < 500 g/mole). These surfactants can help to slow down the corrosion rate by an average reduction rate of 50%. More particularly, common corrosion inhibitors are typically composed of amines, condensation products of fatty acids with polyamines ("PA"),
for example, imidazolines, or quaternary ammonium compounds. Among the most frequently used corrosion inhibitors in crude oil and natural gas extraction are imidazoline derivatives. Alternative corrosion inhibitors that can be used alone or in combination with known corrosion inhibitors are being sought by the industry.
[0006] In this invention, a polyolefin with a molecular weight of at least 500 g/mole, preferably with a carbon number greater than 14, is used as the building block for the corrosion inhibitor. Most specifically, a vinyl terminated polyolefin is used for the corrosion inhibitor assembly. Raising the alkane carbon numbers requires the redesign of the hydrophilic part from a polar head to blocks of hydrophilic polymers so that the polyolefin block can be dispersed in water. Multiple blocks of hydrophilic, amine-containing, polymers also improve the metal surface affinity and adhesion strength.
[0007] Related disclosures include: US 2009/0318644; WO 2009/1555517; WO 2009/155510; WO 2009/1555471; WO 2009/155472; US 8,816,027; US 2013/0197180; PCT/US2013/060953; PCT/US2012/027682; US 8,623,974; US 2012/0245293; US 2012/0245300; PCT/US/2012/027677, filed March 5, 2012; USSN 61/704,611, filed on September 23, 2012; USSN 61/704,725, filed on September 23, 2012; USSN 61/866,702, filed August 16, 2013; USSN 61/860,407, filed July 31, 2013; and Atty. Docket No. 2014EM266; also, "Hybrid Materials of Different Molecular Architectures," 39 CHEM. LETT. 1028-1029 (2010); "Value-added olefin-based materials originating from FI catalysis: Production of vinyl- and Al-terminated PEs, end-functionalized PEs, and PE/polyethylene glycol hybrid materials," 164 CATALYSIS TODAY 2-8 (2011).
SUMMARY OF THE INVENTION
[0008] Disclosed herein is a corrosion inhibitor composition comprising the reaction product of a vinyl/ vinylidene-terminated polyolefin having within the range from 14 to 2000 carbon atoms and a polyamine having a molecular weight of at least 500 g/mole.
[0009] The corrosion inhibitor composition can be formed by the process of reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin; reacting the siloxane functionalized vinyl/vinylidene- terminated polyolefin with a allyl-glycol to form a glycol-siloxane vinyl/vinylidene- terminated polyolefin; and reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
[0010] The corrosion inhibitor composition can also be formed by the process of reacting the vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an
aldehyde-terminated polyolefin; and reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
DESCRIPTION OF FIGURES
[0011] Figure 1 is a 1H NMR of a polyolefin-polyethyleneimine block copolymer of the invention, at (CDCI3, 25°C) on a 500 MHz machine, where "aPP" is atactic polypropylene, one block of the block copolymer.
[0012] Figure 2a is a drawing of the corrosion testing apparatus for examples 1-3, 5.
[0013] Figure 2b is a drawing of the corrosion testing apparatus for examples 6-10.
[0014] Figure 3 is a comparison chart, with error bars, showing the results of corrosion testing.
DETAILED DESCRIPTION
[0015] The invention described herein includes amphiphilic, polyolefin-based corrosion inhibitors and the synthesis of these materials. The corrosion inhibitors described herein are preferably water (at least at 23 °C) soluble, but, when contacted with a metal surface (e.g., steel, iron, copper, etc.), will preferentially bind/adhere or "precipitate" to the metal surface. The amphiphilic polyolefin-based polymer is a block copolymer of one or more polyolefin blocks and one or more hydrophilic polymer blocks, preferably polyamine ("PA") blocks. The polyolefin block can be a homopolymer or a random copolymer of linear alpha olefins that is amorphous, crystalline or semi-crystalline, with number average molecular weight (number average) preferred to be at least 500 g/mole, and preferably have a carbon number of at least 14, or 18, or 25. Inventive polyolefin-polyamine block copolymer, and in particular embodiments polyolefin-polyalkylimine and polyolefin-poly(glycol)amine block copolymers are described herein for corrosion inhibitor ("CI") applications were synthesized in the following sequence:
(1) Synthesis of, or otherwise obtaining, a vinyl/vinylidene-terminated polyolefin (VTP);
(2) End-functionalization of vinyl-terminated polyolefin; and
(3) Coupling the end-functionalized polyolefin with a polyamine, such as a poly (glycol) amine or polyalkyleneimine.
[0016] Thus, the invention includes a corrosion inhibitor composition comprising the reaction product of a vinyl/vinylidene-terminated polyolefin having within the range from 14 to 2000 (or any other value disclosed herein) carbon atoms and a polyalkylimine having a
molecular weight of at least 500 g/mole (or any other value disclosed herein). The composition may include other reaction products, or consist essentially of (or consist of) the polyolefin-polyamine block copolymer. The composition may also include other additives such as inorganic salts, lower molecular weight surfactants (e.g., less than 400 g/mole) and/or ionic surfactants, solvents, etc., known in the corrosion inhibitor arts. In any embodiment, the vinyl/vinylidene-terminated polyolefin (VTP) is first functionalized before reacting with the polyamine. Preferably, said functionalization converts the vinyl/vinylidene-terminus into an aldehyde, a glycol, and/or a siloxane. By "functionalize" what is meant is that the VTP is reacted with an agent having a desirable functional group such as an oxide or oxygen, or a silane or siloxane that, upon reaction, will form a covalent bond between the agent and the VTP, leaving the functional group intact and chemically available to react with or bind to a substrate, preferably a metal surface.
[0017] By "consisting essentially of what is meant is that the named composition includes only the named block copolymer with less than 3 wt , or 2 wt , or 1 wt , by weight of the composition, of any other component such as a reaction product (e.g., unreacted polyolefin and/or polyamine, reducing agents, reaction catalysts, etc.), but may still include additives as described above. In a particular embodiment, the compositions described and claimed herein "consist" of the named block copolymer, or and includes less than 3 wt , or 2 wt , or 1 wt , or 0.5, or 0.1 wt of reaction products and additives. Otherwise, reference to "corrosion inhibitor" or "corrosion inhibitor composition" includes minor amounts of reaction products and/or additives as is common in the art.
[0018] Thus, the inventive corrosion inhibitor will have a polyolefin block (e.g., polypropylene, polyethylene, or ethylene-propylene copolymer) and a polyamine block (e.g., polyethyleneimine, or poly(glycol)amine), forming a polyolefin-polyamine block copolymer.
[0019] The VTPs useful in the inventive functionalized polymers described herein can be made in any number of ways. By "vinyl/vinylidene", what is meant is that the polyolefin may be a mixture of both vinyl- and vinylidene-terminated polyolefins, or the polyolefin may be substantially all one form or the other. Preferably, the VTP's useful herein are polymers as first described in US 2009/0318644 having at least one terminus (CH2CHCH2-oligomer or polymer) represented by
allylic vinyl end group
(1)
where the 'yvw " here represents the "PO" block of the inventive functionalized poly olefins. In a preferred embodiment the allyl chain ends are represented by the formula (2):
[0020] The amount of allyl chain ends is determined using JH NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 13 C NMR. These groups (1) and (2) will react to form a chemical bond with a metal as mentioned above to form the M— CH2CH2— polymer. In any case, Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl-terminated propylene polymers in Resconi et al, 1 14, J. AM. CHEM. SOC, 1025- 1032 (1992) that are useful herein.
[0021] The vinyl/vinylidene-terminated propylene -based polymers may also contain an isobutyl chain end. "Isobutyl chain end" is defined to be an oligomer having at least one terminus represented by the formula (3):
[0022] In a preferred embodiment, the isobutyl chain end is represented by one of the following formulae (4):
[0023] The percentage of isobutyl end groups is determined using C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers. Preferably, the vinyl/vinylidene-terminated polymers described herein have an allylic terminus, and at the opposite end of the polymer an isobutyl terminus.
[0024] The VTPs can be made by any suitable means, but most preferably the VTPs are made using conventional slurry or solution polymerization processes using a combination of bridged metallocene catalyst compounds (especially bridged bis-indenyl or bridged 4- substituted bis-indenyl metallocenes) with a high-molecular volume (at least a total volume of 1000 A3) perfluorinated boron activator, for example, as described in US 2012/0245299.
[0025] The vinyl/vinylidene-terminated polyolefin can be any polyolefin having a vinyl/vinylidene-terminal group, and is preferably selected from the group consisting of vinyl/vinylidene-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, propylene-butene copolymers, propylene-hexene copolymers, and propylene-ethylene copolymers (wherein the copolymers may be random, elastomeric, impact and/or block), and combinations thereof, each having a number- average molecular weight (Mn) of at least 300 g/mole. In any embodiments, the VTP may be a copolymer or terpolymer wherein the C2 content (ethylene derived units) of the vinyl/vinylidene- terminated polyolefin is from 3 to 50 wt%, the C3 content (propylene derived units) is from 50 to 97 wt%; in yet another embodiment, the VTP may contain a third comonomer, thus, the C4 through C14 content (units derived from C4 to C14 a-olefins or dienes) is from 5 to 30 wt% in those embodiments, while the C2 content is from 5 to 50 wt% and the C3 content is from 20 to 90 wt%.
[0026] In any embodiment, greater than 70, or 80, or 90, or 94, or 96% of the VTP polymer chains comprises terminal vinyl or vinylidene groups; or within the range of from
50, or 60 wt% to 70, or 80, or 90, or 95, or 98 or 99% of the polymer chains. As described above, the vinyl/vinylidene-terminated polyolefins preferably have a number average molecular weight (Mn) value of at least 200, or 500, or 1000, or 5000, or 20,000 g/mole, or within a range from 200, or 600, or 800 g/mole to 1000, or 1400, or 1600, or 1800, or 2000, or 4000, or 6000, or 8000, or 10,000 g/mole. The vinyl/vinylidene-terminated polyolefins preferably have a weight-average molecular weight (Mw) value of at least 500, or 800, or 1000, or 5000, or 20,000 g/mole, or within the range of from 500, or 800, or 1000, or 2000, g/mole to 6,000, or 10,000, or 12,000, or 20,000, or 30,000, or 40,000 or 50,000, or 100,000, or 200,000, or 300,000 g/mole. Preferably, the VTP useful herein is amorphous polypropylene, and desirably has a glass transition temperature (Tg) of less than 10 or 5 or 0°C, more preferably less than -10°C; or within the range of from 0, or -5, or -10°C to -30, or -40, or -50°C or as described herein.
[0027] The VTPs are preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or described quantitatively, having a branching index "g" (or g'(Vis avg)) °f at least 0-90 or 0.96 or 0.97 or 0.98, wherein the "branching index" is well known in the art and measurable by published means, and the value of such branching index referred to herein is within 10 or 20% of the value as measured by any common method of measuring the branching index for polyolefins as is known in the art such as in US 2013/0090433.
[0028] A particularly preferred VTP is one wherein the vinyl terminated polyolefin is a compound or mixture of compounds represented by the formula (5):
wherein each "R" is selected from hydrogen and CI to C4 or CIO alkyls, preferably hydrogen or methyl, or a mixture thereof; and n is an integer from 14, or 16, or 18, or 20, or 25, or 50 to 100, or 200, or 500, or 800, or 1000, or 1500, or 2000. In any embodiment, the vinyl/vinylidene-terminated polyolefin is a vinyl/vinylidene-terminated atactic polypropylene or polyethylene, or mixture thereof, meaning that it is an ethylene-propylene copolymer. It is these VTPs that are reacted, under suitable conditions, with a functionalizing agent to form the functionalized polyolefins which can react with the functionalized siloxanes described herein to form siloxane functionalized polyolefins.
[0029] The "polyamine" ("PA") as used herein is a polymeric amine (or, "imine") having multiple amine and/or imine groups. Useful PAs can be represented by the formula: (R- NH)X, where "R-NH" is a polymeric or monomelic unit where "R" contains from 1 to 4, or 6, or 10, or 20 carbon atoms; "x" is an integer from 1 to 50, or 100, or 200, or 500 or 100,000. In any embodiment, the number average molecular weight (Mn) of the polyamine is within a range from 500, or 1000 g/mole to 800, or 1000, or 1200, or 1600, or 2000, or 2200, or 2600, or 3000 g/mole. The polyalkyleneimine may comprise one or more ether or glycol groups as well, and most preferably, as at least one terminal amine group, preferably each end of the polymer chains is a terminal amine.
[0030] More particularly, the PA is a "polyalkylimine" (PAI) and may be represented by the following general formula: (-NHCHzCHz- f-N CHzCHzNF^CHzCHz-], wherein m is from 10, or 20, or 50 to 200, or 500, or 1,000, or 10,000, or 20,000, and n is from 10, or 20, or 50 to 200, or 500, or 1 ,000, or 10,000, or 20,000. Useful PAIs may also comprise secondary amines and/or tertiary amines, such as represented in (-NRCH2CH2-)m[-N(CH2CH2NR2)CH2CH2-], wherein each "R" is independently a CI to CIO, or C20 alkyl, alkylamine, aryl, or arylamine. The PAIs preferably have a level of secondary amines within the range of from 20 or 30 or 40% to 60 or 70 or 80% relative to all the nitrogens on the PAI. Also, the PAIs preferably have, independently, a level of primary and tertiary amines within the range of from 5 or 10 or 15% to 30 or 35 or 40 or 50% relative to all the nitrogens on the PAI.
[0031] In any embodiment, the PAIs that are useful herein have a weight average molecular weight (Mw) of from 400, or 500, or 600, or 800 or 1,000 g/mole to 10,000 or 20,000 or 30,000 or 50,000 g/mole. In any embodiment, the number average molecular weight (Mn) of the polyalkylimine is within a range from 500, or 1000 g/mole to 800, or 1000, or 1200, or 1600, or 2000, or 2200, or 2600, or 3000 g/mole. Examples of desirable commercial PAIs include those sold by Sigma-Aldrich™, or Lupasol™ FG, G20, G35, G100, HF, and P from BASF, and Epomin™ SP012, SP018, SP200, and P1050 from Nippon Shokubai.
[0032] In any embodiment, the polyalkylimine is a polyalkylimine having the following general structure (6):
wherein n has a value within the range from 2, or 6, or 10, to 20, or 40, or 60; and wherein the branching depicted in the structure can vary such that the value of a, b, and c can independently be within a range of from 0, or 1, or 2, or 4, to 5 or 10.
[0033] In any embodiment, the polyamine also comprises glycol subgroups in the backbone and/or side chains (poly(glycol)amine). More particularly, the polyamine may have
wherein the values of x, y, and z can be, independently within a range of from 2, or 4, or 6, or 10, or 20 to 30, or 40, or 50, or 60, and wherein each R is, independently, selected from hydrogen and CI to CIO alkyls, or C6 to C20 aryls or alkylaryls.
[0034] The corrosion inhibitors can be formed by any chemical reaction that will couple the VTP block to a siloxane block. In any embodiment, the corrosion inhibitor is formed by the process of first reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin. With or without isolating and/or purifying the first reaction product, the siloxane functionalized vinyl/vinylidene-terminated polyolefin is reacted with an allyl-glycol to form a glycol- siloxane vinyl/vinylidene-terminated polyolefin. Finally, the glycol-siloxane vinyl/vinylidene-terminated polyolefin is reacted with the polyamine such as a polyalkylimine to form the corrosion inhibitor composition (polyolefin-siloxane -polyamine block copolymers, or simply "polyolefin-polyamine block copolymer"). By "reacted with" or "reacting" what is meant is that the components that will form the desired end product are combined together as a liquid or in a desirable solvent at a desirable temperature, and optionally, with catalysts or promoters that facilitate the formation of the desired end product.
[0035] Other types of reactions can also be used to form the inventive corrosion inhibitor composition. In any embodiment, a vinyl/vinylidene-terminated polyolefin is reacted with a hydroformylation agent to form an aldehyde-terminated polyolefin. Then, with or without isolating and/or purifying the product, the aldehyde-terminated polyolefin is reacted with a reducing agent and the polyamine such as a polyalkylimine to form the corrosion inhibitor composition. Examples of a suitable reducing agents include lithium aluminum hydride, boron hydride compounds, atomic hydrogen, oxalic acid, diisobutylaluminum hydride, diborane, sodium amalgam, and other electron donating chemical compounds capable of facilitating the desired reaction.
[0036] In any case, the inventive corrosion inhibitor will have a polyolefin block (e.g., polypropylene, polyethylene, or ethylene-propylene copolymer) and a polyamine block(s), forming a block copolymer. In any preferred embodiment, the inventive corrosion inhibitor composition is a reaction product having a 1 : 1, or 2: 1, or 3: 1, or 4: 1 molar ratio of the polyolefin block and the polyamine block, the polyolefin block having a number average molecular weight (Mn) within the range from 500 g/mole to 1000 g/mole. In any preferred embodiment, the corrosion inhibitor has an overall carbon number of greater than 25, or 30, or 40, or 100; or within a range from 25, or 30 to 500, or 800, or 1000 carbons.
[0037] The corrosion inhibitor will have in any embodiment a high affinity for polar surfaces, especially metal (iron, aluminum, nickel, etc.) surfaces. This can be determined by any number of means, but in one embodiment, weight loss from a steel surface due to corrosion (reaction and/or loss to the surrounding medium of iron, typically in the form of iron oxide, from the metal surface being tested) by acidic solution and carbon dioxide is a desirable indicator of a corrosion inhibitor's affinity for metal surfaces, and the inventive corrosion inhibitor in any embodiment herein will have a weight loss of less than 3.5 or 3.0 or 2.5 wt a week, meaning that, by weight, only that percentage of the corrosion inhibitor will detach from the metal surface. This makes the inventive corrosion inhibitors highly desirable as a pipe coating, on its inside, outside, or both surfaces. It can also be used on other surfaces, especially metal surfaces that are exposed to the elements, such as metal pilings, ship hulls, etc., and those surfaces can comprise any type of metal such as iron, steel, zinc, nickel, copper, aluminum, and combinations thereof as is known in the art.
[0038] The various descriptive elements and numerical ranges disclosed herein for the inventive corrosion inhibitor composition and methods of forming such can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit
described herein, including the examples. The features of the inventions are demonstrated in the following non-limiting examples.
EXAMPLES
[0039] Polyolefin-polyetheramine and polyolefin-polyamine block copolymers for corrosion inhibitor ("CI") applications were synthesized in the following general sequence:
(1) Synthesis of the VTP;
(2) End-functionalization of the VTP; and
(3) Coupling the end-functionalized polyolefin with a polyamine, such as a poly (glycol) amine or polyalkyleneimine.
The Molecular Weight Characteristics of the Polymers
[0040] Polymer molecular weight (weight-average molecular weight, Mw number- average molecular weight, Mn and z-averaged molecular weight, Mz), and molecular weight distribution (Mw/Mn) were determined using Size-Exclusion Chromatography ("GPC"). Equipment consists of a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer (SEC-DRI-LS-VIS). For purposes of the claims, SEC-DRI-LS-VIS shall be used. Three Polymer Laboratories PLgel 10mm Mixed-B columns are used. The nominal flow rate is 0.5 cm3/min and the nominal injection volume is 300 μL·. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135°C. Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μιη glass pre-filter and subsequently through a 0.1 μιη Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
[0041] Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135°C. The injection concentration can range from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
Example 1. Synthesis of aPP-polvetheramine copolymer.
[0042] A round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (TDMS, 1.5 grams, 4.56 millimoles) and toluene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated atactic polypropylene (1.5 grams, Mn 978 g/mole, 1.63 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in toluene (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was stirred for another 2 hours, after which NMR showed that the vinyl was gone. Allyl glycidyl ether (6 grams, 52.6 millimoles) was then added. Platinum(0)-1,3- divinyl-l,l,3,3-tetramethyldisiloxane complex was replenished. The reaction mixture was stirred for 2 hours, after which !H NMR showed that the Si-H was not present (CDC13, 25°C). The reaction mixture was slowly poured into pre-chilled methanol with stirring, the liquid phase was decanted, and the product aPP-epoxide was dried under vacuum.
[0043] A round-bottomed flask was charged with Jeffamine™ ED-2003 (approx. Mw 2000 g/mole, poly(ethylene oxide-co-propylene oxide)diamine) and xylene (10 milliliters). The Jeffamine used here has the following structure, where y is an average value of 39, and x+z is an
[0044] The mixture was stirred under nitrogen at 110°C. Atactic PP-epoxide (0.7 gram, 0.51 millimoles) was dissolved in xylene (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was stirred at 110°C overnight, after which the solvent was removed under vacuum. NMR of aPP-polyetheramine copolymer (CDCI3, 25°C) confirmed the product. The Scheme (1) below shows the synthesis of aPP-polyetheramine copolymer (Example 1):
Example 2. Synthesis of aPP-polvethyleneimine copolymer
[0045] A round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (TMDS, 1.5 grams, 4.56 millimoles) and toluene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated aPP (1.2 grams, Mn 908 g/mole, 1.32 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in toluene (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was stirred for overnight. Allyl glycidyl ether (6 grams, 52.6 millimoles) was then added. Platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex was replenished. The reaction mixture was stirred for 4 hours, after which NMR showed that the Si-H was gone. The reaction mixture was slowly poured into pre-chilled methanol with stirring, the liquid
phase was decanted, and the product was dried under vacuum. NMR of aPP-epoxide (CDCI3, 25 °C) confirmed the product.
[0046] A round-bottomed flask was charged with polyethyleneimine (branched, Mn about 600 g/mole, 2.69 grams) and chloroform (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Atactic PP-epoxide (0.76 gram) was dissolved in chloroform (40 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete over 3 days, the solvent was removed under vacuum. NMR of aPP-polyethyleneimine copolymer (CDCI3, 25°C) confirmed the product, as shown in Figure 1. The Scheme (2) below shows the synthesis of aPP-polyethyleneimine copolymer (example 2):
vinyl a
Example 3. Synthesis of aPP-polvethyleneimine copolymer
[0047] A round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (0.8 gram, 2.43 millimoles) and xylene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated aPP (2.0 grams, Mn 908 g/mole, 2.20 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in xylene (50 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was heated to
50°C for 2 hours. Allyl glycidyl ether (0.82 gram, 7.18 millimoles) was then added. Platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex was replenished. The reaction mixture was stirred for 2 hours, after which the reaction mixture was transferred into an addition funnel. A second flask was charged with polyethyleneimine (branched, Mn about 600 g/mole, 4.3 grams) and chlorobenzene (10 milliliters). The mixture was stirred under nitrogen and heated to reflux (132°C). The reaction mixture in the addition funnel was then added to the second flask dropwise. When the addition was complete, the reaction mixture was maintained at reflux for overnight, after which the solvent was distilled out and final product was dried under vacuum.
Example 4. Synthesis of aPP-polyethyleneimine copolymer
[0048] A round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (1.0 grams, 3.04 millimoles) and xylene (10 milliliters). The mixture was stirred under nitrogen at ambient temperature. Vinyl-terminated aPP (1.0 gram, Mn 2077 g/mole, 0.48 millimoles) and platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex were dissolved in xylene (30 milliliters) and the solution was transferred into an addition funnel, then dropwise added into the round-bottomed flask. After the addition was complete, the mixture was heated to 50°C for 2 hours. Allyl glycidyl ether (1.8 grams, 15.8 millimoles) was then added. Platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex was replenished. The reaction mixture was stirred for 2 hours, after which heat was removed and the reaction mixture was slowly added to pre-chilled methanol (300 milliliters) with stirring. The solid was isolated by centrifuging and dried under vacuum. NMR (CDCI3, 25°C) showed that all vinyl was consumed and glycidyl ether was attached to aPP. There was still some unreacted Si-H.
[0049] The above product was dissolved in chlorobenzene (30 milliliters) and the solution was transferred to an addition funnel. A round-bottomed flask was charged with polyethyleneimine (branched, avg. Mn (GPC) of 600 g/mole, 1.0 gram) and chlorobenzene (20 milliliters). The mixture was stirred under nitrogen and heated to reflux (132°C). The solution in the addition funnel was then added to the flask dropwise. When the addition was complete, the reaction mixture was maintained at reflux for overnight, after which the solvent was distilled out and final product was dried under vacuum.
Example 5. Synthesis of PE-polyethyleneimine copolymer
[0050] A bottle was charged with vinyl polyethylene (1.0 gram, 0.728 millimole), platinum(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex and xylene (80 milliliters) and was then sealed and sonicated for 99 minutes, generating a slurry, which was transferred to
an addition funnel. A round-bottomed flask was charged with tetrakis(dimethylsiloxy)silane (1.0 grams, 3.04 millimoles) and xylene (40 milliliters). The solution was heated to 110°C under nitrogen with stirring. The mixture was stirred under nitrogen at 110°C. The slurry in the addition funnel was then added to the flask dropwise. After the addition was complete, the reaction mixture was maintained at 110°C for 2 hours. Allyl glycidyl ether (2.4 grams, 21.0 millimoles) was added. Platinum(0)-l,3-divinyl-l,l ,3,3-tetramethyldisiloxane complex was replenished. The mixture was maintained at 110°C for 2 hours. The solvent was removed by vacuum distillation. Pentane (100 milliliters) was added to the solid and stirred for 30 minutes. Then the mixture was filtered and the solid was collected and dried under vacuum. *H NMR (CDC12CDC12, 110°C) showed that vinyl and Si-H were gone and glycidyl ether was attached to PE.
[0051] The above product was mixed with xylene (80 milliliters) in a bottle and the mixture was sonicated for 60 minutes. The resulting slurry was transferred to an addition funnel. A round-bottomed flask was charged with polyethyleneimine (branched, avg. Mn (GPC) of 600 g/mole, 1.0 grams, 1.67 millimoles) and chlorobenzene (40 milliliters) and the mixture was heated to reflux (132°C) under nitrogen with stirring. The slurry in the addition funnel was then added to the flask dropwise. After the addition was complete, the reaction mixture was maintained at reflux for overnight. The solvents were distilled out, and the solid was washed with hexanes and dried under vacuum. The Scheme (3) below shows the synthesis of PE-polyethyleneimine copolymer (example 5):
Corrosion tests of PP-PA Examples 1-3, 5
[0052] Three pre-weighed steel coupons were secured to a glass rod by three O-rings as shown in Figure la. The glass rod was then inserted into a Teflon adaptor that fits the 24/40 joint of a two-neck round-bottom flask. To the other neck of the flask was equipped with a rubber septum penetrated by two Teflon tubing, one for flowing air in and the other for venting. Air flow was adjusted by a flow meter and vent was connected to an oil bubbler.
[0053] Conditioned water was prepared by first adjusting the pH of deionized water using sulfuric acid until pH reaches 5, then 100 ppm NaCl were added. Corrosion inhibitor was
subsequently added to the conditioned water and agitated vigorously to form a homogeneous solution. The solution was then filled into the flask to the brim. Air was blown into the flask. The flask was maintained at certain temperature for 14 days, after which the steel coupons were removed from the glass rod, cleaned and dried, and weighed individually using the following procedure:
(1) blow dry the coupons with air, weigh scaled coupons
(2) rinse with deionized water and blow dry with air
(3) rinse with chloroform and blow dry with air
(4) clean coupon scale with Clarke solution (passivated acid) (ASTM G-l), then rinse with deionized water and methanol sequentially and blow dry with air, record final weight.
[0054] The weight loss on each steel coupon is the weight loss due to corrosion. Greater than 50% reduction in weight loss is demonstrated for all except for the aPP-polyetheramine. These results are shown in Table 1. Note that Example 4 was not tested.
[0055] To a round bottom flask containing atactic polypropylene with an aldehyde end- group (2 g, 2.70 mmol) was added THF (15 mL) and PEI (CAS#25987-06-8, avg. Mn (GPC) of 600 g/mole, 1.62 g, 2.70 mmol, very viscous oil, will solidify in THF at approximately 22° C). The reaction mixture was refluxed at 105°C under N2 atmosphere for 3 hours. Imine formation/incorporation was confirmed by NMR (400 MHz). The reaction mixture exhibited no color change. It was allowed to reach room temperature (approximately 22°C) and was treated with methanol (5 mL, turned cloudy), followed by addition of NaBH4 (Mw: 37.83 g/mole, 166.45 mg, 4.40 mmol) in 5 portions. The resulting homogeneous solution was stirred at room temperature for 2 hours. The solvents were removed to afford a colorless, viscous oil which was further dried under 50°C vacuum oven (theoretical yield 3.62 g, 2.70 m
Aldehyde of Propylene Oligomers (S4)
1 ) THF/N2/reflux
2) MeOH/NaBH4
aPP-PEI
Mn:~1341
Example 7-Preparation of (741aPP)?-PEI
[0056] To a round bottom flask containing atactic polypropylene with an aldehyde end- group (3.6 g, 4.86 mmol) was added THF (35 mL) and PEI (avg. Mn (GPC) of 600 g/mole, 1.46 g, 2.43 mmol, very viscous oil, will solidify in THF at approximately 22°C). The reaction mixture was refluxed at 105°C under N2 atmosphere for 3 hrs. Imine formation/incorporation was confirmed by NMR (400 MHz). The reaction mixture exhibited no color change. It was allowed to reach room temperature (approximately 22°C) and was
treated with methanol (10 mL, turned cloudy), followed by addition of NaBH4 (Mw: 37.83 g/mole, 340 mg, 9 mmol) in 5 portions. The resulting homogeneous solution was stirred at room temperature for 2 hours. The solvents were removed to afford a colorless, viscous oil which was further dried under 50°C vacuum oven (theoretical yield 4.97 g, 2.43 mmol).
Example 8 -Preparation of 1316aPP-PEI
[0057] To a round bottom flask containing atactic polypropylene with an aldehyde end- group (1.20 g, 0.91 mmol) was added THF (35 mL) and PEI (avg. Mn (GPC) of 600 g/mole, 546 mg, 0.91 mmol, very viscous oil, will solidify in THF at approximately 22°C). The reaction mixture was refluxed at 105°C under N2 atmosphere for 3 hrs. The imine formation/incorporation was confirmed by NMR (400 MHz). The reaction mixture exhibited no color change. It was cooled to room temperature (approximately 22°C) and was treated with methanol (2 mL, turned cloudy), followed by addition of NaBH4 (Mw: 37.83 g/mole, 56.75 mg, 1.5 mmol) in 5 portions. The reaction mixture was stirred at approximately 22°C for 2 hours. The solvents were removed to afford a colorless, viscous oil which was further dried under 50°C vacuum oven (theoretical yield 2.26 g, 0.91 mmol).
Example 9- -Preparation of C18-PEI
[0058] Adapted from 61(11) J. Org. Chem. (1996): The reaction vessel system was purged with N2 for 1 min. While purging with N2, to the 100 mL round bottom flask was added PEI (avg. Mn (GPC) of 600 g/mole, 1.87 g, 3.12 mmol), Octadecanal (C18) (CAS#638-66-4, molecular mass of 268.5 g/mole, 836 mg, 3.12 mmol) and THF (20 mL). After addition, N2 was turned off but the adaptor was still connected to the condenser without security clip to keep the system under N2 atmosphere throughout the experiment and release pressure if necessary. Reaction mixture was refluxed at 105°C (heating metal temperature, otherwise not collecting) for 3 hrs. NMR (JH, 400 MHz) confirmed reaction completion. The reaction mixture was run almost until colorless and cooled to room temperature. To the mixture was added methanol (5 mL) and NaBH4 (Mw: 37.83 g/mole, 340 mg, 9.00 mmol) in portions. Bubbles formed every time NaBH4 was added. After NaBH4 was all consumed
and bubbles were all gone, it was stirred at room temperature for 1 hour to afford an oil, which was further dried under vacuum. Scheme (6) shows this reaction:
Octadecanal
C18-PEI
Corrosion Testin2 of Examples 6-9
[0059] A stir bar containing the sample was introduced into the three-neck flask as in Figure lb and described above for Examples 1-5. An aqueous brine solution (1% NaCl acidified to pH = 5) was added to the flask. A condenser column kept cool with flowing air was attached to the flask. The C02 was continuously fed into the solution through a Teflon tube. The metal (steel) coupons were attached to a glass rod with elastic O-rings. The rod was introduced through the middle neck as shown in the figure. The round bottom flask was kept at 60°C. The apparatus was kept under these conditions for 7 days, at which point the metal coupons were removed, rinsed with water, and treated with a Clarke solution (10 g Stannous Chloride and 4 g Antimony Trioxide in 200 g Hydrochloric Acid).
[0060] Clarke Solution Application: The coupons were removed from the testing apparatus to assess their final weight. The coupons were washed with distilled water. The coupon were then placed in the Clarke solution and stirred for one minute. The coupons were then taken out of the Clarke solution and placed in a beaker filled with distilled water. The coupons were then placed in a jar with acetone and blown dry with N2, and finally heated under N2 at 50°C for 30 minutes. (The acetone was used to help facilitate the drying of the coupon.) The coupons were then weighed. Figure 2 shows the results, documented more fully in Table 2. Note that "Low" flow of C02 was used; every test was done with 3 coupons; No CI and aPP-PEI are averages of 2 tests; Variability is shown with pooled variance. The key to Table 2:
• No CI : Test without any corrosion inhibitor added to the acidified brine solution
• PEI : polyethyleneimine, Mn = 600 g/mole
• 741aPP-PEI: atactic polypropylene (Mn = 741 g/mole) linked to PEI in 1 :1 ratio
• C18-PEI: CH3(CH2)17-PEI
• (741aPP)2-PEI: atactic polypropylene (Mn = 741 g/mole) linked to PEI in 2: 1 ratio
• 1316aPP-PEI: atactic polypropylene (Mn = 1316 g/mole) linked to PEI in 1 : 1 ratio
• EC1304A: Commercial corrosion inhibitor from Nalco
Table 2. Corrosion Testing Results of Exampli
[0061] Having described the various features of the inventive corrosion inhibitors (polyolefin-siloxane-polyamine block copolymers, or simply "polyolefin-polyamine block copolymers"), described here in numbered paragraphs is:
PI . A corrosion inhibitor composition comprising (or consisting essentially of, or consisting of) the reaction product of a vinyl/vinylidene-terminated polyolefin having a carbon number of at least 14 or 18 or 25, or more preferably within the range from 14, or 16,
or 18, or 20, or 25, or 50 to 100, or 200, or 500, or 800, or 1000, or 1500, or 2000 carbon atoms, and a polyamine having a molecular weight of at least 500, or 800, or 1000, or 5000, or 20,000 g/mole.
P2. The corrosion inhibitor composition of numbered paragraph 1 (e.g., PI, P2, etc.), wherein the vinyl/vinylidene-terminated polyolefin is first functionalized before reacting with the polyamine.
P3. The corrosion inhibitor composition of numbered paragraph 2, wherein the functionalization converts the vinyl/vinylidene-terminus into an aldehyde, a glycol, and/or a siloxane.
P4. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the number average molecular weight (Mn) of the polyamine is within a range from 500, or 1000 g/mole to 800, or 1000, or 1200, or 1600, or 2000, or 2200, or 2600, or 3000 g/mole.
P5. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the number average molecular weight (Mn) of the vinyl/vinylidene-terminated polyolefin is within a range from 200, or 600, or 800 g/mole to 1000, or 1400, or 1600, or 1800, or 2000, or 4000, or 6000, or 8000, or 10,000 g/mole.
P6. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the vinyl/vinylidene-terminated polyolefin is a vinyl/vinylidene-terminated atactic polypropylene or polyethylene, or mixture thereof.
P7. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the polyamine also comprises glycol subgroups in the backbone and/or side chains. P8. The corrosion inhibitor composition of numbered paragraph 7, wherein the polyamine has the following general structure:
wherein the values of x, y and z can be, independently within a range of from 2, or 4, or 6, or 10, or 20 to 30, or 40, or 50, or 60, and wherein each R is, independently, selected from hydrogen and CI to CIO alkyls, or C6 to C20 aryls or alkylaryls.
P9. The corrosion inhibitor composition of any one of the previous numbered paragraphs, having a carbon number of greater than 14, or 25, or 30, or 40; or within a range from 14, or 25, or 30 to 500, or 800, or 1000 carbons.
P10. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the reaction product is a 1:1 molar ratio of the polyolefin block and the polyalkylimine block, the polyolefin block having a number average molecular weight (Mn) within the range from 200 g/mole to 1000 g/mole.
Pl l. The corrosion inhibitor composition of any one of the previous numbered paragraphs, formed by the process of:
a) reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin;
b) reacting the siloxane functionalized vinyl/vinylidene-terminated polyolefin with a allyl-glycol to form a glycol- siloxane vinyl/vinylidene-terminated polyolefin; and c) reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
P12. The corrosion inhibitor composition of any one of the previous numbered paragraphs, formed by the process of:
a) reacting the vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an aldehyde-terminated polyolefin; and
b) reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
P13. The corrosion inhibitor composition of any one of the previous numbered paragraphs, wherein the polyalkylimine is a polyethyleneimine having the following general structure:
wherein n has a value within the range from 2, or 6, or 10, to 20, or 40, or 60; and wherein the branching depicted in the structure can vary such that the value of a, b, and c can independently be within a range of from 0, or 1, or 2, or 4, to 5 or 10.
P14. A pipe coated at least on its interior with the corrosion inhibitor composition of any one of the previous numbered paragraphs.
PI 5. The pipe of numbered paragraph 15, wherein the pipe exhibits a weight loss due to corrosion by acidic solution and carbon dioxide of less than 3.5 or 3.0 or 2.5 wt a week. P16. A process of forming a corrosion inhibitor of any one of numbered paragraphs 1 to 14 comprising:
a) reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin;
b) reacting the siloxane functionalized vinyl/vinylidene-terminated polyolefin with a allyl-glycol to form a glycol-siloxane vinyl/vinylidene-terminated polyolefin; and c) reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
P17. A process of forming a corrosion inhibitor of any one of numbered paragraphs 1 to 14 comprising:
a) reacting a vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an aldehyde-terminated polyolefin; and
b) reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
[0062] Also disclosed is the use of the corrosion inhibitor of any one of the previous numbered paragraphs as a coating on (and/or in) pipes, hulls, and pilings.
[0063] Also disclosed is the use of a polyamine- siloxane-poly olefin block copolymer as described above as a corrosion inhibitor.
[0064] For all jurisdictions in which the doctrine of "incorporation by reference" applies, all of the test methods, patent publications, patents and reference articles are hereby incorporated by reference either in their entirety or for the relevant portion for which they are referenced.
Claims
A corrosion inhibitor composition comprising the reaction product of a vinyl/vinylidene-terminated polyolefin having a carbon number of at least 14 and a polyamine having a molecular weight of at least 500 g/mole.
The corrosion inhibitor composition of claim 1, wherein the vinyl/vinylidene- terminated polyolefin is first functionalized before reacting with the polyamine.
The corrosion inhibitor composition of claim 2, wherein the functionalization converts the vinyl/vinylidene-terminus into an aldehyde, a glycol, and/or a siloxane.
The corrosion inhibitor composition of claim 1, wherein the number average molecular weight (Mn) of the polyamine is within a range from 500 g/mole to 3000 g/mole.
The corrosion inhibitor composition of claim 1, wherein the number average molecular weight (Mn) of the vinyl/vinylidene-terminated polyolefin is within a range from 200 g/mole to 10,000 g/mole.
The corrosion inhibitor composition of claim 1, wherein the vinyl/vinylidene- terminated polyolefin is a vinyl/vinylidene-terminated atactic polypropylene or polyethylene, or mixture thereof.
The corrosion inhibitor composition of claim 1, wherein the polyamine comprises glycol subgroups in the backbone and/or side chains.
wherein the values of x, y and z can be, independently within a range of from 2 to 60, and wherein each R is, independently, selected from hydrogen and CI to CIO alkyls, or C6 to C20 aryls or alkylaryls.
9. The corrosion inhibitor composition of claim 1, having a carbon number of greater than 25 carbons.
10. The corrosion inhibitor composition of claim 1, wherein the reaction product is a 1 :1 molar ratio of a polyolefin block and a polyamine block, the polyolefin block having a number average molecular weight (Mn) within the range from 200 g/mole to 1000 g/mole.
11. The corrosion inhibitor composition of claim 1, formed by the process of:
a) reacting the vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin; b) reacting the siloxane functionalized vinyl/vinylidene-terminated polyolefin with a allyl-glycol to form a glycol-siloxane vinyl/vinylidene-terminated polyolefin; and
c) reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
12. The corrosion inhibitor composition of claim 1, formed by the process of:
a) reacting the vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an aldehyde-terminated polyolefin; and
b) reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
13. The corrosion inhibitor composition of claim 1, wherein the polyamine the PA is a polyalkylimine represented by the following general formula: (-NHCH2CH2-)m[-N(CH2CH2NH2)CH2CH2-], wherein m is from 10 to 20,000, and n is from 20 to 2,000.
14. The corrosion inhibitor composition of claim 1, wherein the polyamine is a polyalkylimine having the following general structure:
wherein n has a value within the range from 2 to 60; and wherein the branching depicted in the structure can vary such that the value of a, b, and c can independently be within a range of from 0 to 10.
15. A pipe coated at least on its interior with the corrosion inhibitor composition of claim 1.
16. The pipe of claim 15, wherein the pipe exhibits a weight loss due to corrosion by acidic solution and carbon dioxide of less than 3.5 wt a week.
17. A process of forming a corrosion inhibitor comprising:
a) reacting a vinyl/vinylidene-terminated polyolefin with a siloxane to form a siloxane functionalized vinyl/vinylidene-terminated polyolefin; b) reacting the siloxane functionalized vinyl/vinylidene-terminated polyolefin with a allyl-glycol to form a glycol-siloxane vinyl/vinylidene-terminated polyolefin; and
c) reacting the glycol-siloxane vinyl/vinylidene-terminated polyolefin with the polyamine to form the corrosion inhibitor composition.
18. A process of forming a corrosion inhibitor comprising:
a) reacting a vinyl/vinylidene-terminated polyolefin with a hydroformylation agent to form an aldehyde-terminated polyolefin; and
b) reacting the aldehyde-terminated polyolefin with a reducing agent and the polyamine to form the corrosion inhibitor composition.
19. The process of any one of claims 17 or 18, wherein the vinyl/vinylidene-terminated polyolefin is first functionalized before reacting with the polyamine.
20. The process of claim 19, wherein the functionalization converts the vinyl/vinylidene- terminus into an aldehyde, a glycol, and/or a siloxane.
21. The process of any one of claims 17 to 20, wherein the number average molecular weight (Mn) of the polyamine is within a range from 500 g/mole to 3000 g/mole.
22. The process of any one of claims 17 to 21, wherein the number average molecular weight (Mn) of the vinyl/vinylidene-terminated polyolefin is within a range from 200 g/mole to 10,000 g/mole.
23. The process of any one of claims 17 to 22, wherein the vinyl/vinylidene-terminated polyolefin is a vinyl/vinylidene-terminated atactic polypropylene or polyethylene, or mixture thereof.
24. The process of any one of claims 17 to 23, wherein the polyamine comprises glycol subgroups in the backbone and/or side chains.
25. A process to coat at least the interior surface of a pipe comprising contacting the corrosion inhibitor composition made by the process of any one of claims 16 to 24 with the interior of a pipe.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3275554A (en) * | 1963-08-02 | 1966-09-27 | Shell Oil Co | Polyolefin substituted polyamines and lubricants containing them |
WO1997047666A1 (en) * | 1996-06-10 | 1997-12-18 | Bp Chemicals Limited | Substituted carboxylated derivatives |
EP0815150B1 (en) * | 1995-03-13 | 1999-12-08 | Basf Aktiengesellschaft | Copolymers of unsaturated dicarboxylic acids or their anhydrides and vinyl-terminated oligo-olefines and their reaction products with nucleophilic agents |
US20030057401A1 (en) * | 1999-11-18 | 2003-03-27 | Craig Steven Robert | Inhibitor compositions |
US20140113844A1 (en) * | 2012-10-24 | 2014-04-24 | Exxonmobil Research And Engineering Company | Functionalized polymers and oligomers as corrosion inhibitors and antiwear additives |
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2015
- 2015-10-26 WO PCT/US2015/057395 patent/WO2016089507A1/en active Application Filing
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US3275554A (en) * | 1963-08-02 | 1966-09-27 | Shell Oil Co | Polyolefin substituted polyamines and lubricants containing them |
EP0815150B1 (en) * | 1995-03-13 | 1999-12-08 | Basf Aktiengesellschaft | Copolymers of unsaturated dicarboxylic acids or their anhydrides and vinyl-terminated oligo-olefines and their reaction products with nucleophilic agents |
WO1997047666A1 (en) * | 1996-06-10 | 1997-12-18 | Bp Chemicals Limited | Substituted carboxylated derivatives |
US20030057401A1 (en) * | 1999-11-18 | 2003-03-27 | Craig Steven Robert | Inhibitor compositions |
US20140113844A1 (en) * | 2012-10-24 | 2014-04-24 | Exxonmobil Research And Engineering Company | Functionalized polymers and oligomers as corrosion inhibitors and antiwear additives |
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Title |
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