US3220866A - Corrosion inhibition - Google Patents

Corrosion inhibition Download PDF

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Publication number
US3220866A
US3220866A US197595A US19759562A US3220866A US 3220866 A US3220866 A US 3220866A US 197595 A US197595 A US 197595A US 19759562 A US19759562 A US 19759562A US 3220866 A US3220866 A US 3220866A
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United States
Prior art keywords
solution
weight
cellulose
corrosion
maleate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US197595A
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English (en)
Inventor
Rosenthal Arnold Joseph
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Corp
Original Assignee
Celanese Corp
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
Priority to NL292689D priority Critical patent/NL292689A/xx
Priority to BE632815D priority patent/BE632815A/xx
Application filed by Celanese Corp filed Critical Celanese Corp
Priority to US197595A priority patent/US3220866A/en
Priority to NL63292689A priority patent/NL143285B/nl
Priority to DEC30009A priority patent/DE1235703B/de
Priority to GB20369/63A priority patent/GB1039938A/en
Priority to FR935921A priority patent/FR1362768A/fr
Application granted granted Critical
Publication of US3220866A publication Critical patent/US3220866A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • 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
    • C23F11/12—Oxygen-containing compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process

Definitions

  • This solution or dope is then dry spun into filamentary cellulose triacetate, the solvent being evaporated by a current of warm air followed by recovery and purification prior to re-use.
  • the spinning is effected by passage of the solution through one or more orifices in a metallic member generally referred to as a jet. It has been found that these jet-s, as well as other metal equipment contacted by the solvent during use and recovery, corrode rapidly and require frequent replacement.
  • Another object is to provide a solution of cellulose triacetate in methylene chloride, which solution can be dry spun without rapid corrosion of the spinning jet.
  • a further object of the invention is to provide a cellulose triacetate solution which is sufiiciently non-corrosive on metals to permit spinning through stainless steel jets.
  • a stabilizer or mixture of stabilizers which inhibits corrosion of metallic members.
  • the stabilizers must satisfy certain requirements in order to be suitable for use, viz., they must themselves be non-corrosive, they should not have any particular afiinity for the cellulose ester lest they contaminate articles produced therefrom, they should not deleteriously affect the physical properties of the cellulose esters, under conditions of use they should not endanger the operators, they should not irritate or sensitize the skin when worn and preferably they should be sufficiently inexpensive so that their cost will be compensated for by savings in the replacement cost of metal equipment or by improvements in the properties of the esters as a result of elimination of metallic contaminants.
  • the carboxylic acid from which the organotin derivative is formed may be either a mono carboxylc acid, e.g., acetic acid, butyric acid, caproic acid, la-uric acid, palmitic acid, oleic acid, be'henic acid, etc, or a dicarboxylic acid, e.g., maleic acid, fumaric acid, etc.
  • a suitable organotin derivative of a mono carboxylic acid is a dibutyltin dilaurate.
  • Suitable derivatives of dicarboxylic acids include alkyltin maleates wherein the alkyl group contains from about 2 to 10 carbon atoms. We have found that dibutyltin maleate is particularly suitable.
  • organotin derivatives of mixed maleic acid and a mono carboxylic acid are also suitable.
  • Such mixed organotin derivatives are described in US. Patent 2,826,597, and may be illustrated by the following structural formula:
  • R is an alkyl, aryl or aralkyl group, and R is an alkyl radical.
  • R may be any organic radical such as methyl, ethyl, propyl, butyl, lauryl, phenyl, benzyl, etc.
  • R may be derived from any monobasic aliphatic acid such as acetic, butyric, caproic, lauric, palmitic, oleic, behenic, etc.
  • organotin derivatives of a carboxylic acid is extremely effective in preventing corrosion of metal jets in a dynamic situation, i.e., under actual spinning conditions.
  • This result is quite unexpected because when such an organotin derivative of a carboxylic acid is incorporated into a spinning solution and such solution is caused to contact a metal specimen under static conditions, i.e., wherein the metal specimen is simply placed into the spinning solution, no particular inhibition to corrosion is apparent.
  • the explanaton of the unexpected efficacy of the organotin derivatives of a carboxylic acid in preventing corrosion under dynamic situations and not under static situations is not presently understood, the fact remains that in actual spinning conditions the incorporation of such derivative markedly reduces corrosion.
  • organotin derivative of a carboxylic acid will exert some beneficial action when present even in the most minute quantities.
  • such stabilizer when used alone, should be present in an amount at least 0.005 percent by weight of the solution.
  • the range will be from about 0.005 to 0.5% of the solution, with a more preferred range being from about 0.01 to 0.1%. Even more than about 0.5% of stabilizer can be used, but since corrosion is substantially completely eliminated with lesser amounts, there is no need.
  • cellulose acetates havequivalent corrosion inhibition when using either the 5 ing an acetyl value in excess of 59.5% by weight expressed organotin stabilizer or the lower alkyl amine nitrite alone.
  • organotin stabilizer herein referred to as cellulose tria'cetate
  • Patent 2,927,031 teaches the incorporation of a lower dissolved in methylene chloride-methanol to a concentraalkyl amine nitrite into a halogen-containing organic sol tion of above 15% and preferably from 17 to 27%.
  • vent solution of an organic acid ester of cellulose and methylene chloride can range upwards from 80% of the further teaches that the amount of amine nitrite so incombined weights of methylene chloride and methanol corporatcd may be from about 0.005 to 0.5% by weight with about 90% or more p These Solutions of the solution.
  • the solution of organic acid ester of rials are normally subjected.
  • cellulose in halogen-containing solvent will induce con-
  • the following examples will further illustrate my insiderable corrosion of the metal jet as such solution is vention.
  • Each jet was made of stainless steel, was linch spun therethrough. in diameter, and contained five holes, each 0.032 mm. in The solvent of the cellulose ester solution can be any diameter.
  • the methylene Rejected hole (fadlus enlarged 0-004II1111- at chloride solvent may contain as much as 20% by weight any Point 3 of volatile alcohols such as methanol, ethanol, propanol, 40 Maximum demeflts Permitted P hole, not isopropanol, and the like, the percentage being based on rejected 2 the combined Weights of methylene chloride and alcohol. Maximum demerits assigned P rejected 1116 3 Although water will decrease the solubility of the ester in the solvent, small amounts can be tolerated.
  • the stabiliztotal demeritsX 100 ing action will be realized even in the presence of water.
  • D amage Score per percent m
  • Organic acid esters of cellulose which can be used are preferably the lower alkanoic acid esters such as the acetate, propionate, butyrate, acetate-propionate, acetate- Examples y a e, and t e llke While the Invention 1s applicable Cellulose acetate having an acetyl value of 61.5% is to any esters which w1ll d1ssolve 1n the indicated solvents, dissolved in a mixture of 91 parts by weight of methylene excellent results are achieved when using cellulose acetate chloride and 9 parts by Weight of methanol to form a havlng all acetyl Content excess of about 595% and solution having a concentration of cellulose acetate of preferably 61.5% by weight calculated as acetic acid.
  • esters are substantially fully acetylated, i.e., free of amounts of dibutyl tin maleate or of Z-hydroxypropyl unreacted hydroxyl groups, and are hereinafter referred amine nitrite are incorporated into the solution, as shown to as cellulose triacetate although a small residue of unin Table I.
  • the solution is spun at a temperature of reacted hydroxy groups may be present. 72 C. at a rate of 1200 meters per minute linear velocity
  • the present invention is particularly useful in the dry of solution through the 0.032 mm. diameter hole type spinning of solutions of cellulose triacetate in methylene 316 stainless steel jets. The results are given in Table I.
  • Dibutyl tin maleate 8 g? 0. 01 500 67 0. 03 54 0 as as a 2a a 3 3 0105 500 0
  • the efiicacy of the dibutyl tin maleate stabilizer in preventing jet corrosion is obvious.
  • Example 4 0.2% by weight and a maximum of the amount which will The procedure described in Examples 1-3 was utilized, lg f j sz gg gg 5g 32 ggg ig g f g; zi zfi ggg gil 3 ⁇ git gg gl g gzigzfi gg tigg gfig g suificient to substantially inhibit the corrosion of metals of iven in Table II and are com ared with the use of either an alkyl tin maleate wherein the alkyl groups contain 2 to g. p 10 carbon atoms as stabilizer, said maleate also being itlbutyl tm maleat?
  • a stable composition of matter non-corrosive to hydrqxypmpylamme the .corr 081.011 mhlbmon 1S metallic spinnerets contacted therewith in a spinning superior to that obtained using dlbutyl tin maleate alone process comprisino a Solution in a halogemcontaining D Exampla Wherem 003% dlbutyl tm maleate organic solvent of a lower alkanoic acid ester of cellulose showed a.damage Score i 9 i 500 q i 1S and a small amount suflicient to substantially inhibit the also Supenor to i corrpslon mhlbmon obtamed usmg corrosion of metals of an alkyl tin maleate wherein the hydroiiypmpylamme mtme alone
  • Example alkyl groups contain 2 to 10 carbon atoms and of a hyz g ig g 23 3 g gf ggg ggfig
  • a stable composition of matter, non-corrosive to p metallic spinnerets contacted therewith in a spinning procsplnperets conticted therewlth m ilspmmnlg Process ess corn rising a solution of cellulose triacetate in prising a solution of cellulose triacetate in a concentramthyleng chloride Said solution containing a small tion of at least 15% by weight in a solvent comprising methylene chloride and a lower alkanol, the methylene z ggig j gggg f gfigffififig i g gl glf g gzg 5 chlonde cqnstltutlpg at leas-t about 80% by Weight of the maleate said maleate and nitrite bein themselves nonsolvent, said solution containmg about 0 .0 05 to 0.5% by ormsiv t metals not havin an aftic
  • a process for stabilizing a solution against corrosion of metal contacted therewith, said solution comprising cellulose triacetate dissolved in methylene chloride which process comprises incorporating a small amount sufficient to substantially inhibit the corrosion of metals of dibutyl tin maleate in said solution, said maleate also being itself non-corrosive to metals, not having any particular atfinity for said cellulose ester, and not deleteriously affecting the physical properties of said cellulose tn'acetate.
  • '8 halogen-containing organic solvent is extruded through'an orifice in a metallic member under conditions such that said cellulose ester is converted to filamentary material
  • the improvement which comprises incorporating in said solution a small amount of a hydroxy lower alkyl amine nitrite and of an alkyl tin maleate wherein the alkyl groups contain 2 to 10 carbon atoms, whereby corrosion of said metallic member and transfer of metal to said solution and said filamentary material are inhibited, said maleate and nitrite also being themselves non-corrosive t-o metals, not having any particular aflinity for said cellulose ester, and not deleteriously afiecting the physical properties of said cellulose ester.
  • composition of claim 1 wherein said organotin carboxylate is dibutyltin dilaurate.
  • composition of claim 1 wherein said organotin carboxylate is a compound of the formula:
  • R is selected from the group consisting of alkyl, aryl and aralkyl, and wherein R is alkyl.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US197595A 1962-05-25 1962-05-25 Corrosion inhibition Expired - Lifetime US3220866A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL292689D NL292689A (nl) 1962-05-25
BE632815D BE632815A (nl) 1962-05-25
US197595A US3220866A (en) 1962-05-25 1962-05-25 Corrosion inhibition
NL63292689A NL143285B (nl) 1962-05-25 1963-05-14 Werkwijze voor het verspinnen van een oplossing van een cellulose-ester van een organisch zuur in een halogeenbevattend organisch oplosmiddel.
DEC30009A DE1235703B (de) 1962-05-25 1963-05-22 Verwendung von Organozinnderivaten von Carbonsaeuren als Korrosionsinhibitoren
GB20369/63A GB1039938A (en) 1962-05-25 1963-05-22 Corrosion inhibited cellulose ester solutions
FR935921A FR1362768A (fr) 1962-05-25 1963-05-24 Procédé d'inhibition de la corrosion de métaux

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US197595A US3220866A (en) 1962-05-25 1962-05-25 Corrosion inhibition

Publications (1)

Publication Number Publication Date
US3220866A true US3220866A (en) 1965-11-30

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US197595A Expired - Lifetime US3220866A (en) 1962-05-25 1962-05-25 Corrosion inhibition

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US (1) US3220866A (nl)
BE (1) BE632815A (nl)
DE (1) DE1235703B (nl)
GB (1) GB1039938A (nl)
NL (2) NL143285B (nl)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314807A (en) * 1963-10-17 1967-04-18 Georgia Pacific Corp Water-base adhesive containing a hydroxylamine stabilizer
US8772390B1 (en) 2011-07-13 2014-07-08 Oxifree Holdings Corp Sprayable polymeric coating system for the protection of complex metal structures against corrosion
US9988537B2 (en) 2013-05-10 2018-06-05 Oxifree Global Limited Coating composition and method for the protection of complex metal structures and components used in submerged environments
CN111748269A (zh) * 2019-03-29 2020-10-09 青岛海尔智能技术研发有限公司 一种铝合金微通道换热器用防腐剂及其防护方法和换热器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826597A (en) * 1953-01-22 1958-03-11 Metal & Thermit Corp Stabilizer for resins
US2857413A (en) * 1954-03-22 1958-10-21 Metal & Thermit Corp Organotin compounds and process of preparation
US2927031A (en) * 1957-05-31 1960-03-01 Celanese Corp Corrosion inhibition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3034210A (en) * 1959-09-03 1962-05-15 Dow Chemical Co Inhibition of corrosion of magnesium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826597A (en) * 1953-01-22 1958-03-11 Metal & Thermit Corp Stabilizer for resins
US2857413A (en) * 1954-03-22 1958-10-21 Metal & Thermit Corp Organotin compounds and process of preparation
US2927031A (en) * 1957-05-31 1960-03-01 Celanese Corp Corrosion inhibition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314807A (en) * 1963-10-17 1967-04-18 Georgia Pacific Corp Water-base adhesive containing a hydroxylamine stabilizer
US8772390B1 (en) 2011-07-13 2014-07-08 Oxifree Holdings Corp Sprayable polymeric coating system for the protection of complex metal structures against corrosion
US9988537B2 (en) 2013-05-10 2018-06-05 Oxifree Global Limited Coating composition and method for the protection of complex metal structures and components used in submerged environments
CN111748269A (zh) * 2019-03-29 2020-10-09 青岛海尔智能技术研发有限公司 一种铝合金微通道换热器用防腐剂及其防护方法和换热器
CN111748269B (zh) * 2019-03-29 2022-08-19 青岛海尔智能技术研发有限公司 一种铝合金微通道换热器用防腐剂及其防护方法和换热器

Also Published As

Publication number Publication date
NL143285B (nl) 1974-09-16
BE632815A (nl)
NL292689A (nl)
DE1235703B (de) 1967-03-02
GB1039938A (en) 1966-08-24

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