Classifications

• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D3/164—Organic compounds containing a carbon-carbon triple bond
• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
  • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
  • C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond

Definitions

• This invention relates to corrosion restraining compounds and more particularly it relates to compounds for restraining the corrosion of ferrous metals in acid pickling baths.
• Ferrous metals such as steel, which are subjected to working at elevated temperatures during the course of manufacture become coated with a layer of oxide impurity, often referred to as mill scale.
• a layer of oxide impurity often referred to as mill scale.
• acid pickling an operation referred to as acid pickling.
• the acids commonly used for this purpose are sulphuric acid and hydrochloric acid, although other acids such as phosphoric acid and sulphamic acid may be used.
• polyoxyalkylene derivatives of certain acetylenic alcohols are particularly valuable corrosion restraining compounds for addition to acid pickling baths, and are especially suitable for use with hydrochloric acid pickling baths.
• the oxyalkylene derivatives of this invention are relatively involatile and have a much longer lifetime in the acid pickling bath.
• acid pickling baths incorporating the products of the present invention as corrosion restraining compounds show little tendency to foam, and this is particularly important when recovering hydrochloric acid from spent liquors for re-use.
• polyalkylene derivatives of acetylenic alcohols having the general formula:
• R represents a straight chain or branched chain alkyl radical having from 1 to carbon atoms
• R represents a hydrogen atom or an alkyl radical having from 1 to 10 carbon atoms
• each Y represents either an oxyethylene group or an oxypropylene group, at least one Y being an oxypropylene group
• n is an integer of from 2 to 30.
• straight chain or branched chain alkyl radicals which are represented by R there may be mentioned methyl, ethyl, n-propyl, l-ethylpentyl, isopropyl, butyl, isobutyl, hexyl and heptyl, and as examples of the alkyl radicals which are represented by R there may be mentioned methyl, ethyl and butyl.
• a process for the manufacture of polyoxyalkylene derivatives of acetylenic alcohols having the general Formula I above which comprises condensing an acetylenic alcohol having the formula RRC(OH)CECH wherein R and R have the meanings stated above, with propylene oxide or both ethylene oxide and propylene oxide in the presence of a catalyst.
• the alcohol of Formula I may be condensed with the two oxides in admixture, when the product will have a random poly(oxyethylene/oxypropylene)copolymer chain, or the oxides may be reacted in any desired sequence to give a product having a block copolymer chain.
• tertiary amines for example trimethylamine, triethylamine, dimethylcyclohexylamine, N,N,N,N-tetramethyl-ethylenediamine and 4-dimethylaminopyridine
• alkali and alkaline earth metal hydroxides for example sodium hydroxide, potassium hydroxide, and barium hydroxide
• acids such as sulphuric acid and phosphoric acid
• Lewis acid catalysts for example aluminium chloride, boron trifluoride either as such or as complexes such as the etherate, titanium tetrachloride and stannic chloride.
• reaction between the acetylenic alcohol and the propylene oxide or ethylene and propylene oxides is conveniently carried out at temperatures of from 70 C. to C., but lower or higher temperatures, for example from l0 C. to C. may be used if desired.
• an acid pickling bath for ferrous metals which comprises an aqueous acid containing a polyoxyalkylene derivative of an acetylenic alcohol having the general formula:
• the amount of corrosion restraining compound which is added to the acid pickling bath may be varied over wide limits but we prefer to add between 0.05% and 0.4% by weight of the compound calculated on the weight of commercial acid used.
• hydrochloric acid we prefer to add from 1 lb. to 8 lbs. of compound per ton of 28% hydrochloric acid in the acid pickling liquors.
• concentration of hydrochloric in the acid pickling bath is usually between 1% and 20% by weight.
• the compound In order to make up the acid pickling bath the compound is simply stirred into the pickling acid, which is then ready for use, or the compound may be added to the concentrated acid prior to dilution.
• Pickling can be carried out at temperatures of from 10 C. to 95 C. in the case of a hydrochloric acid bath.
• the compounds of the present invention are also effective in restraining the corrosion of ferrous metals under other conditions, for example in the in situ descaling of plant, in the acidisation of oil and water wells where hydrochloric acd is used to open or enlarge the limestone fissures and protection of the ferrous metal well casing is essential, and in degreasing plants which use highly chlorinated solvents. These solvents are liable to contain traces of hydrogen chloride which are very corrosive to the degreasing plant itself and to ferrous metal articles which are being degreased. Addition of a compound of the present invention to the degreasing solvent minimises the corrosive effect of any acid which may be present.
• EXAMPLE 1 3-methyl-1-butyn-3-ol (42 parts) and boron trifluoride etherate (1.5 parts) were stirred at 3040 C. while a mixture of ethylene oxide (60.5 parts) and propylene oxide (79.8 parts) was added. During the latter part of the addition the temperature was allowed to rise to 60 C. and was maintained at 60 C. for 1% hours on completion of the addition. After removal of volatile products at 60 C. and 20 mm. pressure the residual product was a light brown oil consisting of 161.1 parts of an adduct of methyl butynol with 4.68 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar proportions.
• EXAMPLE 2 The adduct of Example 1 (128.9 parts) and boron trifluoride etherate (1.2 parts) were stirred at 60 C. While a mixture of ethylene oxide (48.4 parts.) and propylene oxide (63.8 parts) were added. After stirring for a further 1 hour at 60 C. and removal of volatile products at 60 C. and 20 mm. pressure the residual product consisted of 218.9 parts of an adduct of methyl butynol with 9.09 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar ratio.
• EXAMPLE 3 An adduct of 3-methyl-1-pentyn-3-ol with 9.98 molar proportions of ethylene oxide/propylene oxide in an approximately 1:1 molar ratio (75.8 parts) and boron trifluoride etherate (0.45 part) were stirred at 60 C. while a mixture of ethylene oxide (18.2 parts) and propylene oxide (24 parts) was added. After stirring at 60 C. for 1 hour, followed by removal of volatile products at 60 C. and 20 mm. pressure the residual product consisted of 107.3 parts of an adduct of methyl pentynol with 14.92 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar ratio.
• EXAMPLE 4 1-hexyn-3-ol (49 parts) and boron trifluoride etherate (1.4 parts) were stirred at 30-40 C. while a mixture of ethylene oxide (60.5 parts) and propylene oxide (79.8 parts) was added. During the latter half of the addition the temperature was allowed to rise to 60 C. and was maintained at 60 C. for 1% hours following the addition. After removal of volatile products at 60 C. and 20 mm. pressure the residual product consisted of 179.9 parts of an adduct of hexynol with 5.13 molar proportions of ethylene oxide/ propylene oxide in approximately 1:1 molar ratio.
• EXAMPLE 5 The adduct of Example 4 (89.9 parts) and boron trifluoride etherate (0.9 part) were stirred at 60 C while a mixture of ethylene oxide (36.3 parts) and propylene oxide (47.9 parts) was added. After subsequent treatment as in Example 2 the residual product consisted of 158.4 parts of an adduct of hexynol with 10.5 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar ratio.
• EXAMPLE 6 The adduct of Example 5 (79.2 parts) and boron trifluoride etherate (0.45 part) were stirred at 60 C. while a mixture of ethylene oxide (18.2 parts) and propylene oxide (24 parts) was added. After subsequent treatment as in Example 2 the residual product consisted of 111.7 parts of an adduct of hexynol with 15.6 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar proportions.
• EXAMPLE 8 The aduct of Example 7 (44.3 parts) and boron trifiuoride etherate (0.22 part) were stirred at 60 C. while propylene oxide (23.2 parts) was added. After further treatment as in Example 2 the residual product consisted of 66.8 parts of an adduct of hexynol with 5.8 molar proportions of propylene oxide.
• EXAMPLE 9 4-ethyl-1-octyn-3-ol (61.6 parts) and boron trifluoride etherate (1.4 parts) were stirred at 3040 C. while a mixture of ethylene oxide ,(67.8 parts) and propylene oxide (89.3 parts) were added. During the latter half of the addition the temperature was allowed to rise to 60 C. and was maintained at 60 C. for 1% hours on completion of the addition. After removal of volatile products at 60 C. and 20 mm. presure the residual product consisted of 205.8 parts of an adduct of ethyl octynol with 7.07 molar proportions of ethylene oxide/ propylene oxide in approximately 1:1 molar ratio.
• EXAMPLE 10 The adduct of Example 9 (102.9 parts) and boron trifiuoride etherate (0.75 part) were stirred at 60 C. while a mixture of ethylene oxide (33.9 parts) and propylene oxide (44.7 parts) was added. After further treatment as in Example 2 the residual product consisted of an adduct of ethyl octynol with 13.22 molar proportions of ethylene oxide/propylene oxide in approximately 1:1 molar ratio.
• the strip was withdrawn, washed under cold running water, immersed in dilute amomnia solution, washed under hot running water, immersed in acetone and wiped dry with a clean dry absorbent duster. The strip was then reweighed and the weight loss determined.
• R represents methyl, ethyl, propyl and represents hydrogen, methyl or ethyl oxyethylene and oxypropylene in about a 1:1 ratio and n is an integer of from 4.68 to 15.6.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Detergent Compositions (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (7)

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• 1968
  • 1968-08-08 GB GB37954/68A patent/GB1245943A/en not_active Expired
• 1969
  • 1969-07-15 ZA ZA695010A patent/ZA695010B/xx unknown
  • 1969-07-24 US US844622A patent/US3644535A/en not_active Expired - Lifetime
  • 1969-07-31 DE DE1939042A patent/DE1939042C3/de not_active Expired
  • 1969-08-07 SE SE6911040A patent/SE372956B/xx unknown
  • 1969-08-07 BE BE737220D patent/BE737220A/xx unknown

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