WO2004002994A2 - Novel phosphonocarboxylic acid esters - Google Patents

Novel phosphonocarboxylic acid esters Download PDF

Info

Publication number
WO2004002994A2
WO2004002994A2 PCT/GB2003/002721 GB0302721W WO2004002994A2 WO 2004002994 A2 WO2004002994 A2 WO 2004002994A2 GB 0302721 W GB0302721 W GB 0302721W WO 2004002994 A2 WO2004002994 A2 WO 2004002994A2
Authority
WO
WIPO (PCT)
Prior art keywords
ester
acid
oil
composition
carboxylic acid
Prior art date
Application number
PCT/GB2003/002721
Other languages
French (fr)
Other versions
WO2004002994A3 (en
Inventor
Gary Woodward
Christopher Raymond Jones
Keith Philip Davis
Original Assignee
Rhodia Consumer Specialities Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Consumer Specialities Limited filed Critical Rhodia Consumer Specialities Limited
Priority to CA002490931A priority Critical patent/CA2490931A1/en
Priority to EP03732752A priority patent/EP1527078A2/en
Priority to AU2003240137A priority patent/AU2003240137A1/en
Publication of WO2004002994A2 publication Critical patent/WO2004002994A2/en
Publication of WO2004002994A3 publication Critical patent/WO2004002994A3/en
Priority to NO20050394A priority patent/NO20050394L/en

Links

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
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3869—Polyphosphonic acids containing carboxylic acid or carboxylic acid derivative substituents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
    • 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
    • C23F11/167—Phosphorus-containing compounds

Definitions

  • the invention relates to novel phosphonocarboxylic acid esters and to a method for their production, as well as to their use as scale inhibitors, corrosion inhibitors and asphaltene and wax dispersants.
  • scale and/or corrosion inhibitors which are oil soluble, e.g. inhibitors for use in oil production and also for more effective oil soluble surfactants, as well as for surfactants that can perform dual function as scale inhibitors and as asphaltene dispersants.
  • Oil-soluble scale inhibitors can be introduced in an oil phase, e.g. xylene, which does not damage the formation or interfere with the normal flow of oil. They are required to be able to pass from solution in the oil phase into aqueous inclusions by partitioning or hydrolysis so as to inhibit scale formation in the aqueous phase.
  • a major problem in oil production is the precipitation of asphaltenes or of waxes which, like mineral scales, can block the flow of oil through the formation or through pipelines and other well-head, storage or refinery equipment.
  • the present invention in a first aspect provides the aforesaid novel esters.
  • the present invention provides a process for making said novel esters by refluxing the corresponding phosphono carboxylic acid with from 1 to n moles of a C 6 . 20 alcohol in a solvent having a boiling point greater than that of water, where n is the number of carboxy groups, and removing water from the system.
  • the present invention provides the use of said novel esters as oil-soluble corrosion and/or scale inhibitors and/or as wax or asphaltene inhibitors and/or dispersants. A small stoichiometric excess of the alcohol, e.g. up to 1.3n, can generally be tolerated.
  • the reflux temperature is preferably 110 to 170 °C, e.g. 120 to 160°C.
  • novel esters may be prepared by telomerising an ester of an unsaturated carboxylic acid with a phosphite or hypophosphite telogen.
  • H(CHCO 2 ) folk PO 3 M "n" is preferably 2 or more preferably 4, but may be higher, e.g. up to 12 or, less preferably, up to 100.
  • n is 2 and 4 such as may be obtained by using in the above preparation an acid derived from the reaction product of a maleate salt with a phosphite salt at a pH above 5 as taught in EP 0 491 391.
  • the invention also provides compounds in which the phosphono or phosphino group is esterified with a C 6 . 20 group, their use and their preparation by esterifying the aforesaid acids with more than n moles of alcohol, and using higher temperatures and/or dehydrating agents which permit the esterification of phosphonic acid groups, or by reacting a mixture of a phosphite or hypophosphite ester with fatty alkyl ester of an unsaturated carboxylic acid.
  • the invention further provides solutions of the aforesaid esters in oil, and especially in aromatic oil such as xylene or in mineral oils, and methods of inhibiting scaling and/or precipitation of asphaltene, or of dissolving or dispersing scale or asphaltene or wax deposits by injecting said solutions into oil wells, pipelines or formations.
  • the aforesaid esters may also be used as gas hydrate inhibitors
  • the phosphonocarboxylic acid may for example be phosphonoacetic acid or, preferably, phosphonosuccinic acid. Alternatively it may be 1 phosphono-2, 3, 4- tricarboxy butane or preferably a telomer of the type described in EP 0 491 391 which may be obtained by reacting a water soluble salt of an unsaturated carboxylic acid such as maleic, acrylic, methacrylic, fumaric, crotonic, isocrotonic, citraconic, mesaconic, aconitic, itaconic, angelic, tiglic, cinammic, allocinammic, oleic or elaidic acid with a phosphite at a pH above 5, in the presence of free radicals.
  • an unsaturated carboxylic acid such as maleic, acrylic, methacrylic, fumaric, crotonic, isocrotonic, citraconic, mesaconic, aconitic, itac
  • M is a C6-20 alkyl, alkaryl or alkenyl group and M 1 is preferably H or an alkali metal, ammonium or alkaline earth metal and n is a number from 1 to 20, and preferably an even number from 2 to 10.
  • Compounds of the latter type may be prepared by reacting maleate with phosphite.
  • phosphono polyacrylates and phosphono acrylate/maleate copolymers include phosphono polyacrylates and phosphono acrylate/maleate copolymers.
  • Other monomers which may be used in addition with any of the above include vinyl phosphonic, vinylidine diphosphonic, vinyl sulphonic and styrene.
  • the telogen may a hypophosphite or a phosphonophosphino compound such as the compounds X 2 O 3 PCHYCZ 2 PO 2 X 2 wherein X is hydrogen or alkali metal ammonium or alkaline earth metal and Y and Z are each hydrogen, a PO 3 X 2 , SO 3 X or CO 2 X group or an alkyl or aryl moiety.
  • X is hydrogen or alkali metal ammonium or alkaline earth metal
  • Y and Z are each hydrogen, a PO 3 X 2 , SO 3 X or CO 2 X group or an alkyl or aryl moiety.
  • alkyl groups in our esters comprise from 10 to 25 carbon atoms, e.g. 12 to 22.
  • esters of our invention are preferably xylene-soluble, e.g. to the extent of at least 1 % by wt.
  • Example 3 The products of Examples 1 and 2 were soluble in mineral oil and provided effective inhibitions of scaling, corrosion and asphaltene precipitation.
  • Example 2 The product of Example 2 was tested for its ability to disperse asphaltene deposits.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Lubricants (AREA)

Abstract

Phosphono or phosphino acids, in which at least one carboxyl group is esterified with a C6-25 alkyl, alkaryl or alkenyl group, are effective as oil-soluble scale inhibitors, and as wax or asphaltene inhibitors or dispersants. A method for making and the use of the aforesaid esters is also disclosed.

Description

NOVEL PHOSPHONOCARBOXYLIC ACID ESTERS
The invention relates to novel phosphonocarboxylic acid esters and to a method for their production, as well as to their use as scale inhibitors, corrosion inhibitors and asphaltene and wax dispersants.
It is known to use various salts, and in particular salts of the formula H(CHCO2M)„ PO3 M'2 where each M and M1 is a cation and "n" is an even number, as scale and/or corrosion inhibitors in aqueous systems (see, for example, EP 0 491 391)
It is also known to use various oil soluble surfactants to inhibit or prevent the deposition of asphaltenes or of waxes or to disperse previously formed deposits.
There is, however, a need for scale and/or corrosion inhibitors which are oil soluble, e.g. inhibitors for use in oil production and also for more effective oil soluble surfactants, as well as for surfactants that can perform dual function as scale inhibitors and as asphaltene dispersants.
A common problem in oil production arises when potentially scale forming aqueous inclusions occur in a production well which is wet with oil. It is often impossible to introduce conventional, water-soluble scale inhibitors into such systems without damaging water sensitive formations or inhibiting the flow of oil by introduction of aqueous solutions into the well. Oil-soluble scale inhibitors can be introduced in an oil phase, e.g. xylene, which does not damage the formation or interfere with the normal flow of oil. They are required to be able to pass from solution in the oil phase into aqueous inclusions by partitioning or hydrolysis so as to inhibit scale formation in the aqueous phase. A major problem in oil production is the precipitation of asphaltenes or of waxes which, like mineral scales, can block the flow of oil through the formation or through pipelines and other well-head, storage or refinery equipment. There is a major requirement for compounds which can inhibit the precipitation of asphaltenes and/or waxes or which can disperse asphaltene or wax deposits.
Existing scale inhibitors are unable to meet these requirements.
We have discovered that novel esters of phosphono or phosphino acids, wherein at least one carboxyl group is esterified with a C6-25 alkyl, alkaryl or alkenyl group, are effective as oil-soluble scale inhibitors, and as wax or asphaltene inhibitors or dispersants
Accordingly, the present invention in a first aspect provides the aforesaid novel esters. According to a second aspect the present invention provides a process for making said novel esters by refluxing the corresponding phosphono carboxylic acid with from 1 to n moles of a C6.20 alcohol in a solvent having a boiling point greater than that of water, where n is the number of carboxy groups, and removing water from the system. According to a third aspect the present invention provides the use of said novel esters as oil-soluble corrosion and/or scale inhibitors and/or as wax or asphaltene inhibitors and/or dispersants. A small stoichiometric excess of the alcohol, e.g. up to 1.3n, can generally be tolerated. The reflux temperature is preferably 110 to 170 °C, e.g. 120 to 160°C.
Alternatively the novel esters may be prepared by telomerising an ester of an unsaturated carboxylic acid with a phosphite or hypophosphite telogen.
H(CHCO2)„ PO3 M "n" is preferably 2 or more preferably 4, but may be higher, e.g. up to 12 or, less preferably, up to 100. We particularly prefer a mixture of compounds wherein n is 2 and 4 such as may be obtained by using in the above preparation an acid derived from the reaction product of a maleate salt with a phosphite salt at a pH above 5 as taught in EP 0 491 391.
Although not generally preferred the invention also provides compounds in which the phosphono or phosphino group is esterified with a C6.20 group, their use and their preparation by esterifying the aforesaid acids with more than n moles of alcohol, and using higher temperatures and/or dehydrating agents which permit the esterification of phosphonic acid groups, or by reacting a mixture of a phosphite or hypophosphite ester with fatty alkyl ester of an unsaturated carboxylic acid.
The invention further provides solutions of the aforesaid esters in oil, and especially in aromatic oil such as xylene or in mineral oils, and methods of inhibiting scaling and/or precipitation of asphaltene, or of dissolving or dispersing scale or asphaltene or wax deposits by injecting said solutions into oil wells, pipelines or formations. The aforesaid esters may also be used as gas hydrate inhibitors
The phosphonocarboxylic acid may for example be phosphonoacetic acid or, preferably, phosphonosuccinic acid. Alternatively it may be 1 phosphono-2, 3, 4- tricarboxy butane or preferably a telomer of the type described in EP 0 491 391 which may be obtained by reacting a water soluble salt of an unsaturated carboxylic acid such as maleic, acrylic, methacrylic, fumaric, crotonic, isocrotonic, citraconic, mesaconic, aconitic, itaconic, angelic, tiglic, cinammic, allocinammic, oleic or elaidic acid with a phosphite at a pH above 5, in the presence of free radicals. Particularly preferred are compositions of the formula
Figure imgf000005_0001
where M is a C6-20 alkyl, alkaryl or alkenyl group and M1 is preferably H or an alkali metal, ammonium or alkaline earth metal and n is a number from 1 to 20, and preferably an even number from 2 to 10. Compounds of the latter type may be prepared by reacting maleate with phosphite. Also included are phosphono polyacrylates and phosphono acrylate/maleate copolymers. Other monomers which may be used in addition with any of the above include vinyl phosphonic, vinylidine diphosphonic, vinyl sulphonic and styrene.
Apart from a phosphite the telogen may a hypophosphite or a phosphonophosphino compound such as the compounds X2O3PCHYCZ2PO2X2 wherein X is hydrogen or alkali metal ammonium or alkaline earth metal and Y and Z are each hydrogen, a PO3X2, SO3X or CO2X group or an alkyl or aryl moiety. The preparation of such compounds and of carboxylic acid telomers derived therefrom is described in EP 0 861 846.
We prefer that the alkyl groups in our esters comprise from 10 to 25 carbon atoms, e.g. 12 to 22.
The esters of our invention are preferably xylene-soluble, e.g. to the extent of at least 1 % by wt.
The invention is illustrated by the following examples:
Example 1
An aqueous solution of phosphonosuccinic acid (50%) (0.252 mol) was mixed with 1 dodecanol (0.504 mol), 100 ml of xylene was also added plus a few drops of concentrated sulphuric acid. The mixture was heated using a Dean and Stark apparatus until water began to distil out of the reaction. Refluxing began at 105°C and water distilled out over 5-6 hours, until the temperature finally reached 131 °C, at which point the reaction was cooled to give a homogeneous solution. The xylene solvent was then stripped to give a sticky orange oil.
H2O3P CO2H CH3(CH2)„OH H2O3P CO2(CH2)„CH3
Figure imgf000006_0001
HO2C Xylene CH3(CH2)uO2C
Example 2
A mixture of phosphonosuccinic acid and the telomer (n = 4, M and M1 = H) in aqueous solution (48.5%) (0.16 mol) was mixed with lauryl alcohol (0.32 mol) and xylene (80ml) with 0.5ml of concentrated H2SO4 also added. Again a Dean and Stark apparatus was used to remove water from the reaction. The reaction was heated to 144°C over 10 hours until the distillation of water had stopped. Cooling followed by removal of the xylene afforded a sticky oil.
HA P C02H CH,(CH2(„OH H2θ,P CO CHj .CH,
Figure imgf000006_0002
Xylene CH3(CH2)„02C m average m = 1 .2
The products of Examples 1 and 2 were soluble in mineral oil and provided effective inhibitions of scaling, corrosion and asphaltene precipitation. Example 3
The product of Example 2 was tested for its ability to disperse asphaltene deposits.
Test Methodology
• Dissolve 1.14g asphaltene into 50ml toluene - asphaltene stock solution.
• Add 1 ml stock solution to 50 ml hexane and shake for 1 minute.
• Measure % transmittance at 640nm versus time.
• Repeat above but add lOOppm product of Example 2 (previously prepared as a 1 % stock solution in toluene - only partially soluble) prior to shaking for one minute.
• Results as follows
Time ( minutes) % Transmittance
Blank ITC1310
0 4.0 3.9
5 8.5 4.0
10 15.4 4.1
15 17.8 4.3
As the asphaltene drops to the bottom the transmittance increases , i.e. the higher the transmittance the greater the amount of asphaltene that is still suspended.

Claims

1. An ester of a phosphono- substituted or phosphino- substituted mono-or poly- carboxylic acid in which at least one carboxyl group of said acid is esterified with a C6-C25 alkyl, alkaryl or alkenyl group.
2. An ester as claimed in Claim 1, in which the carboxylic acid is phosphonoacetic acid.
3. An ester as claimed in Claim 1, in which the carboxylic acid is phosphonosuccinic acid.
4. An ester as claimed in Claim 1, in which the carboxylic acid is 1- phosphono - 2,3,4 - tricarboxybutane.
5. An ester as claimed in Claim 1, in which the phosphonocarboxylic acid is a telomer obtained by reacting a water soluble salt of an unsaturated carboxylic acid with a phosphite at a pH above 5, in the presence of free radicals.
6. An ester as claimed in Claim 5, in which the unsaturated carboxylic acid is, maleic, acrylic, methacrylic, fumaric, crotonic, isocrotonic, citraconic, mesaconic, aconitic, itaconic, angelic, tiglic, cinnamic, allocinnamic, oleic or elaidic acid.
7. An ester as claimed in any one of the preceding claims, in which the ester is represented by the formula
H (CHCO2 M)nPO3M' wherein M is a C6C25 alkyl, alkaryl or alkenyl group, M1 is H or an alkali metal, ammonium or alkaline earth metal and n is a number from 1 to 20.
8. An ester as claimed in Claim 7, in which n is an even number from 2 to 10.
9. An ester as claimed in Claim 5, in which the telomer is represented by the formula
X2 O3 PCHYCZ2PO2X2
wherein X is hydrogen , alkali metal, ammonium or alkaline earth metal and Y and Z are each hydrogen, a PO3X2, SO3 X or CO2 X group or an alkyl or aryl moiety.
10. An ester as claimed in any one of preceding claims, in which the alkyl group composes 10 to 25 carbon atoms.
11. A method of making an ester as claimed in any one of the preceding claims, in which said method comprises the steps of refluxing the corresponding phosphono or phosphino carboxylic acid with from 1 to n moles of a C6-C20 alcohol in a solvent having a boiling point greater than that of water, where n is the number of carboxyl groups in said acid, followed by the removal of water from the reflux system.
12. A method as claimed in Claim 11, in which n is 2.
13. A method as claimed in Claim 11, in which n is 100.
14. A method of making an ester according to any one of Claims 1 to 10, in which the phosphono or phosphino group of the acid has been esterified with a C6 - C20 alkyl group.
15. A method as claimed in Claim 14, in which the method comprises esterfying the phosphono or phosphino acid with more than n moles of an alcohol at high temperatures and optionally in the presence of one or more dehydrating agents, where n is the number of carboxyl groups in the acid.
16. An ester produced by the method of any one of Claims 11 to 15.
17. A composition comprising an ester as claimed in any one of claims 1 to 10 and 16.
18. A composition comprising a mixture of esters as claimed in any one of Claims 1 to 10 and 16.
19. A composition as claimed in Claims 17 or 18, in which the ester is dissolved in an oil.
20. A composition as claimed in Claim 19, in which the oil is an aromatic oil.
21. A composition claimed in Claim 20, in which the aromatic oil is xylene.
22. A composition as claimed in Claim 19, in which the oil is a mineral oil.
23. The use of an ester according to any of Claims 1 to 10 and 16 or a composition according to any one of Claims 17 to 22 as a scale inhibitor, a corrosion inhibitor, an asphaltene dispersant or a wax dispersant.
24. The use of an ester according to any of Claims 1 to 10 and 16 or a composition according to any one of Claims 17 to 22 as a gas hydrate inhibitor.
PCT/GB2003/002721 2002-06-26 2003-06-25 Novel phosphonocarboxylic acid esters WO2004002994A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002490931A CA2490931A1 (en) 2002-06-26 2003-06-25 Novel phosphonocarboxylic acid esters
EP03732752A EP1527078A2 (en) 2002-06-26 2003-06-25 Novel phosphonocarboxylic acid esters
AU2003240137A AU2003240137A1 (en) 2002-06-26 2003-06-25 Novel phosphonocarboxylic acid esters
NO20050394A NO20050394L (en) 2002-06-26 2005-01-25 New phosphonocarboxylic acid esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0214711.4 2002-06-26
GB0214711A GB0214711D0 (en) 2002-06-26 2002-06-26 Novel phosphonocarboxylic acid esters

Publications (2)

Publication Number Publication Date
WO2004002994A2 true WO2004002994A2 (en) 2004-01-08
WO2004002994A3 WO2004002994A3 (en) 2004-04-08

Family

ID=9939289

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/002721 WO2004002994A2 (en) 2002-06-26 2003-06-25 Novel phosphonocarboxylic acid esters

Country Status (7)

Country Link
EP (1) EP1527078A2 (en)
AU (1) AU2003240137A1 (en)
CA (1) CA2490931A1 (en)
GB (1) GB0214711D0 (en)
NO (1) NO20050394L (en)
RU (1) RU2005101765A (en)
WO (1) WO2004002994A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7235161B2 (en) 2003-11-19 2007-06-26 Alcoa Inc. Stable anodes including iron oxide and use of such anodes in metal production cells

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3046986B1 (en) * 2013-09-20 2020-07-22 Baker Hughes Holdings LLC Method of inhibiting fouling on a metallic surface using a surface modifying treatment agent

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300337A (en) * 1960-10-06 1967-01-24 Stauffer Chemical Co Anti-static coated textile fiber
GB1438417A (en) * 1973-10-09 1976-06-09 Procter & Gamble Detergent composition
GB1553344A (en) * 1976-04-30 1979-09-26 Abbott Lab Carboxylic esters of phosphonoacetic acid
EP0238825A2 (en) * 1986-02-22 1987-09-30 Bayer Ag 2-Phosphonobutane-1,2,4-tricarboxylic acid derivatives as emulsifying agents
EP0491391A1 (en) * 1990-12-18 1992-06-24 ALBRIGHT & WILSON UK LIMITED Water treatment agent
EP0636648A1 (en) * 1993-07-29 1995-02-01 Bayer Ag Thermoplastic moulding matters
EP0861846A2 (en) * 1997-02-26 1998-09-02 ALBRIGHT & WILSON UK LIMITED Novel phosphino derivatives
FR2789999A1 (en) * 1999-02-18 2000-08-25 Arc Chimie Process for the treatment of hydrocarbon mixtures uses substituted amino acids to precipitate asphaltenes in heavy fuels and crude petroleum

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5929697A (en) * 1982-08-12 1984-02-16 Sakai Chem Ind Co Ltd Phosphonic ester, its preparation, and metal extraction agent containing it

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300337A (en) * 1960-10-06 1967-01-24 Stauffer Chemical Co Anti-static coated textile fiber
GB1438417A (en) * 1973-10-09 1976-06-09 Procter & Gamble Detergent composition
GB1553344A (en) * 1976-04-30 1979-09-26 Abbott Lab Carboxylic esters of phosphonoacetic acid
EP0238825A2 (en) * 1986-02-22 1987-09-30 Bayer Ag 2-Phosphonobutane-1,2,4-tricarboxylic acid derivatives as emulsifying agents
EP0491391A1 (en) * 1990-12-18 1992-06-24 ALBRIGHT & WILSON UK LIMITED Water treatment agent
EP0636648A1 (en) * 1993-07-29 1995-02-01 Bayer Ag Thermoplastic moulding matters
EP0861846A2 (en) * 1997-02-26 1998-09-02 ALBRIGHT & WILSON UK LIMITED Novel phosphino derivatives
FR2789999A1 (en) * 1999-02-18 2000-08-25 Arc Chimie Process for the treatment of hydrocarbon mixtures uses substituted amino acids to precipitate asphaltenes in heavy fuels and crude petroleum

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 101, no. 13, 24 September 1984 (1984-09-24), Columbus, Ohio, US; abstract no.: 111197, SAKAI CHEMICAL INDUSTRY CO., LTD., SAKAI, JAPAN: "Phosphonic acid esters" XP002257881 & JP 59 029697 A (SAKAI CHEMICAL INDUSTRY CO., LTD., SAKAI, JAPAN) 16 February 1984 (1984-02-16) *
CHEMICAL ABSTRACTS, vol. 83, no. 2, 14 July 1975 (1975-07-14), Columbus, Ohio, US; abstract no.: 17675, MAMAKOV, A. A. ET AL: "Products of electrochemical treatment of some flotation reagents" XP002257882 & ELEKTRONNAYA OBRABOTKA MATERIALOV (1974), (5), 60-4, 1974, *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7235161B2 (en) 2003-11-19 2007-06-26 Alcoa Inc. Stable anodes including iron oxide and use of such anodes in metal production cells

Also Published As

Publication number Publication date
GB0214711D0 (en) 2002-08-07
EP1527078A2 (en) 2005-05-04
WO2004002994A3 (en) 2004-04-08
NO20050394L (en) 2005-01-25
AU2003240137A8 (en) 2004-01-19
CA2490931A1 (en) 2004-01-08
RU2005101765A (en) 2005-06-27
AU2003240137A1 (en) 2004-01-19

Similar Documents

Publication Publication Date Title
US3996062A (en) Method for removing scale from metallic substrates
CA1328885C (en) Cotelomer compounds
US5242599A (en) Polymers for the treatment of boiler water
US10113101B2 (en) Composition and method for dispersing paraffins in crude oils
EP0206814B1 (en) Water-soluble polymers and their use in the stabilization of aqueous systems
CA2022827C (en) Control of corrosion in aqueous systems using certain phosphonomethyl amines
JP4298927B2 (en) Scaling and corrosion inhibiting composition
US8653009B2 (en) Method for preventing the formation of calcium carboxylate deposits in the dewatering process for crude oil/water streams
EP0122013A1 (en) Polymeric additives for water
CA1291635C (en) Composition of corrosion inhibitors for cooling water systems using chemically modified acrylamide or methacrylamide polymers
JPH05208199A (en) Method for controlling scale in device for usein stratum containing petruleum and in relation thereto
JPS6133298A (en) Method of inhibiting precipitation of calcium carbonate
JPH0691296A (en) Method of controlling sedimentation of scale
CA2709332A1 (en) Asphaltene dispersants based on phosphonic acids
NZ207345A (en) Scale and corrosion inhibiting mixtures
EP0375385B1 (en) Scale control
CH635301A5 (en) USE OF SUBSTITUTED PROPANE-1,3-DIPHOSPHONE OR -PHOSPHINIC ACIDS FOR CONDITIONING WATER, AQUEOUS SOLUTIONS AND AQUEOUS SUSPENSIONS.
EP1622838A1 (en) Polymer for water treatment
WO2004002994A2 (en) Novel phosphonocarboxylic acid esters
WO2003062344A2 (en) Acidizing and scale treatment of subterranean formation
van dor Leeden et al. Inhibition of barium sulfate deposition by polycarboxylates of various molecular structures
EP0950029B1 (en) Method for the prevention of scale formation by using an ether-1,1-diphosphonate
AU649149B2 (en) Inhibition of scale formation and corrosion by sulfonated organophosphonates
CA1224999A (en) Composition and method for inhibiting scale
EP1648832A1 (en) Scale inhibition in water systems

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2490931

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2003732752

Country of ref document: EP

ENP Entry into the national phase in:

Ref document number: 2005101765

Country of ref document: RU

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2003732752

Country of ref document: EP

NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWW Wipo information: withdrawn in national office

Ref document number: 2003732752

Country of ref document: EP