WO2016089507A1 - Inhibiteurs de corrosion polyoléfiniques à base aqueuse comprenant des polyoléfines à terminaison vinyle/vinylidène - Google Patents

Inhibiteurs de corrosion polyoléfiniques à base aqueuse comprenant des polyoléfines à terminaison vinyle/vinylidène Download PDF

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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
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vinyl
vinylidene
corrosion inhibitor
inhibitor composition
terminated polyolefin
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PCT/US2015/057395
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English (en)
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Shuji Luo
Andy H. Tsou
Elizabeth L. Walker
Marcia E. DIEROLF
George Rodriguez
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Exxonmobil Chemical Patents Inc.
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Publication of WO2016089507A1 publication Critical patent/WO2016089507A1/fr

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    • 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
    • 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
    • C08G73/0213—Preparatory process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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:

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Abstract

L'invention concerne une composition inhibitrice de corrosion utile pour des conduits, des piles et des coques, comprenant le produit réactionnel d'une polyoléfine à terminaison vinyle/vinylidène possédant au moins 14 atomes de carbone et d'une polyamine présentant un poids moléculaire d'au moins 500 g/mole.
PCT/US2015/057395 2014-12-04 2015-10-26 Inhibiteurs de corrosion polyoléfiniques à base aqueuse comprenant des polyoléfines à terminaison vinyle/vinylidène WO2016089507A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
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 (fr) * 1996-06-10 1997-12-18 Bp Chemicals Limited Derives carboxyles substitues
EP0815150B1 (fr) * 1995-03-13 1999-12-08 Basf Aktiengesellschaft Copolymeres d'acides dicarboxyliques insatures ou de leurs anhydrides et oligoolefines a terminaison vinylique ainsi que leurs produits de reaction avec des agents nucleophiles
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
EP0815150B1 (fr) * 1995-03-13 1999-12-08 Basf Aktiengesellschaft Copolymeres d'acides dicarboxyliques insatures ou de leurs anhydrides et oligoolefines a terminaison vinylique ainsi que leurs produits de reaction avec des agents nucleophiles
WO1997047666A1 (fr) * 1996-06-10 1997-12-18 Bp Chemicals Limited Derives carboxyles substitues
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BUGAI, B. I. ET AL.: "Corrosion inhibitors based on various polyolefins", CHEMISTRY AND TECHNOLOGY OF FUELS AND OILS, vol. 19, 1983, pages 381 - 383 *

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