GB2203156A - Corrosion inhibitors - Google Patents
Corrosion inhibitors Download PDFInfo
- Publication number
- GB2203156A GB2203156A GB08808124A GB8808124A GB2203156A GB 2203156 A GB2203156 A GB 2203156A GB 08808124 A GB08808124 A GB 08808124A GB 8808124 A GB8808124 A GB 8808124A GB 2203156 A GB2203156 A GB 2203156A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alkyl
- independently
- composition according
- formula
- composition
- 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.)
- Withdrawn
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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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Corrosion inhibiting compositions comprise a) a compound of formula I <IMAGE> b) a compound of formula II <IMAGE> in which R is selected from C1-22 alkyl, C8-22 alkyl-C5-6 aryl or -CO-C8-22 alkyl or -CO-C8-22 alkenyl; each M independently is hydrogen, an alkali metal ion or a molar equivalent of an alkaline earth metal; R1 is M (as defined above) or a group of formula a> R-(OCnH2n-)x- (a> each n independently is 2 or 3; and each x independently is 0 or an integer from 1 to 15 inclusive. R2 has a significance of R independently of R defined above; each m independently is 2 or 3; and y is 0 or an integer from 1 to 15 inclusive.
Description
Improvements in or relating to Organic Compounds
The invention relates to mixtures of phosphates and phosphites and the use of such mixtures as corrosion inhibitors, especially for the surfaces of metals.
According to the invention, there is provided a composition (hereinafter referred to as a corrosion inhibiting composition) comprising a) a compound of formula I
b) a compound of formula II
in which
R is selected from C1~22 alkyl,C822 alkyl-C56 aryl or -CO-C8~22 alkyl or -CO-C8-22 alkenyl;
each M independently is hydrogen, an alkali metal ion or a molar equivalent of an alkaline earth metal;
R1 is M (as defined above) or a group of formula a) R-(OCnH2n-)x (a)
each n independently is 2 or 3; and
each x independently is O or an integer from 1 to 15 inclusive.
R2 has a significance of R independently of R defined above;
each m independently is 2 or 3; and
y is O or an integer from 1 to 15 inclusive.
For the avoidance of doubt in this Specification, any group capable of being linear or branched is linear or branched, unless indicated to the contrary. Further where any symbol appears more than once in a formula, its significances are independent of one another, unless indicated to the contrary.
Preferably R is R' where R' is selected from C6is alkyl and C818 alkylphenyl; more preferably R is R where R'' is selected from C8~12 alkylphenyl; most preferably R is R''' where R " ' is selected from octylphenyl, nonylphenyl and dodecylphenyl.
Preferably R2 is R2' where R2' has a significance of R', independently of R'. More preferably R2 is R2,1 where R2 " is C6~le alkyl.
Most-preferably R2 is R2 " ' where R2 " ' is C8-12 alkyl.
M is preferably M' where M' is an alkali metal ion, more preferably sodium.
R1 is preferably R1, where R1' is selected from M or C18 alkyl.
n is preferably 2.
m is preferably 2.
x is preferably 0 or an integer from 1 to 10.
y is preferably 0 or an integer from 1 to 10.
Preferably in a corrosion inhibiting composition according to the invention, the ratio of the phosphate to the phosphite is 1:4 to 20:1 (by weight).
The compounds of formula I and II are known or may be prepared from known compounds by known methods.
Corrosion inhibiting compositions according to the invention preferably contain one or more film forming agents. Preferred film forming agents are polyacrylate film forming agents. More preferably the film forming agents are those resulting from aqueous acrylic resin dispersions, especially those described in British Patent 1,266,246, the contents of which are incorporated by reference. These dispersions can be prepared by "emulsion" polymerisation and generally contain 30 to 60% actives.
Compositions according to the invention that contain film forming agents can be diluted with water. Preferably such compositions are added as aqueous dispersions.
Further, according to the invention there is provided a polymeric composition comprising an acrylic resin and a corrosion inhibiting composition according to the invention.
Preferably the amount of phosphate and phosphite present in a polymeric composition according to the invention is from 0.04 to 16t by weight based on the weight of acrylic resin present.
Preferably a polymeric composition according to the invention contains a softening agent to plasticize the polymeric material present. Examples of such softening agents include di C1-4alkyl esters of aromatic or aliphatic dicarboxylic acids.
Polymeric film forming agents of compositions according to the invention may be copolymerised with one or more comonomers. Such comonomers preferably are selected from one or more of acrylic acid, methacrylic acid, crotonic acid, acrylic amide, styrene, ethylene and propylene.
Compositions according to the invention preferably contain one or more further additives selected from pH adjusting agents, biocides, surfactants, alkali metal salts of benzoic acid (for example sodium benzoate), benztriazole, tolyltriazole and light stabilisers.
Preferred pH adjusting agents include sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, mono- or di- sodium ortho phosphate and mono-, di- or tri-ethanolamine (preferably monoethanolamine).
Preferred biocides include formaldehyde, p-chlorophenylpropanediol and dilauryldimethyl-ammonium chloride.
Preferred surfactants include anionic and nonionic surfactants.
Preferred light stabilisers include N- unsubstituted, N-alkyl or
N-acyl substituted 2,2,6,6-tetramethylpiperidinyl light stabilisers and U.V.absorbers.
Preferably a polymeric composition according to the invention comprises
100 parts of a 30-60X aqueous acrylic resin dispersion
0.01 - 1.2 parts of a compound of formula I
0.01 - 6.0 parts of a compound of formula II
0 - 2.5 parts of a alkali metal salt of benzoic acid;
0 - 0.3 parts of a mixture of benztriazole and tolyltriazole; and
0 - 5 parts of a softening agent.
When compositions according to the invention contain a film forming agent, they are particularly suitable as corrosion inhibitors for the protection of metallic surfaces.
Compositions according to the invention are particularly useful to combat oxidative corrosion of metallic objects and surfaces made of, for example steel, grey cast iron, aluminium, magnesium, iron, zinc, copper or tin and alloys thereof. Compositions according to the invention that contain a film forming agent are useful for protecting any material that can be protected against the effects of corrosion by a film. Examples of such materials can be found in " Wellinger
Gimmel- Bodenstein, Werkstoff-Tabellen der Metalle," 7.Auflage, Alfred Körner Verlage, Stuttgart; the contents of which are incorporated herein by reference.
Compositions according to the invention containing a film forming agent are useful for long term indoor corrosion protection and temporary outdoor corrosion protection.
Preferably compositions according to the invention containing a film forming agent form a film or coating at a minimal film forming temperature (MFT) of 5 to 400C. These compositions can be applied to the surfaces which they are to protect by known methods, for example by dipping, spraying or brushing on. Depending on the use of the material to be coated, the thickness of a single film is preferably up to 60p. It is also possible to form a two layer film coating with an intermediate drying step ; preferably such a two layer film would be up to 80 thick. After applying the composition to the material to be coated, the composition according to the invention is dried, preferably at a temperature between 20 and 700C inclusive with or without the presence of a stream of air. The compositions according to the invention may be prewarmed preferably up to a temperature of 450C prior to setting the film.
For an optimum adhesion of the film layer to the surface, it is preferable to degrease the surface prior to application of a composition according to the invention. A composition according to the invention may also be applied to a rusty surface, provided all the loose rust particles are removed beforehand, and will assist in preventing further rusting.
Surfaces to which a composition according to the invention has been applied, can (after drying of the composition to form a film or coating) have a further coating or film applied
Polymeric compositions according to the invention form colourless transparent films or coatings that are heat stable up to 2300C. A further advantage of the compositions according to the invention is that they are dilutable with water, do not require the presence of lead and zinc ions (that are ecologically undesirable), are not poisonous and are biologically degradable.
For the sake of clarity reference to a compound of formula I also includes a mixture of compounds of formula I and reference to a compound of formula II also includes a mixture of compounds of formula II except in the Examples below.
The invention will now be illustrated by the following examples, in which all parts and percentages are by weight and all temperatures are in OC unless indicated to the contrary.
Example 1
The following composition is made up at room temperature (20-250C) mixing well together:
850 Parts of a commercially available (from Degussa) aqueous dispersion of an acrylic resin based on a mixture of the methyl ester of methacrylic acid and the butyl ester of acrylic acid (containing 50% actives);
1.34 Parts of a mixture of phosphates resulting from reacting a mixture (at a ratio of 28:1) of n-butyl alcohol and the compound of the formula la CBH1-C6H4-O-(CH2-CH2-0-)8-H (la) with phosphorus pentaoxide at pH 8;
4.00 Parts of sodium octylphosphite;
4.30 Parts of sodium benzoate
0.12 Parts of benztriazole
0.03 Parts of tolyltriazole
0.05 Parts of the sodium salt of xylene sulphonic acid;
10 Parts of the dibutyl ester of sebacic acid; and
130.16 Parts of water.
The viscosity of the resulting composition is 220 cP on a
Brookfield viscometer at 50 rpm and at a pH of 7.7.
Example 2
A composition is made up as follows at room temperature and stirred well:
82 Parts of a 57% aqueous solution of the mixture of phosphates of Example 1 (containing 47% actives);
5 Parts of sodium octyl phosphite;
6.5 Parts of benztriazole
1.9 Parts of tolyltriazole; and
4.6 Parts of water.
Example 3
80 by 150 mms sheets of unalloyed steel 37 are sanded and degreased and are then immersed in a bath containing the composition of Example 1 at room temperature. After 10 seconds, the sheets are removed and air dried.
The treated sheets are then subjected to the sweat water test according to the Deutsche Industrie Norm (DIN) test procedure 50 017 and to a salt spray mist test according to DIN SS 50 021.
Compared to untreated steel sheets, the sheets treated according to Example 3 exhibit an excellent corrosion inhibition. After exposure to the elements for six months, the sheets, treated according to
Example 3 exhibit no corrosion.
Example 4
The same sheets of unalloyed steel 37 as in Example 3 are sanded and degreased and then immersed in a bath of the composition according to
Example 2 at room temperature. The composition of Example 2 can also be sprayed on the steel sheets. After drying during 30 minutes the same procedure is repeated. After weathering in industrial environment during 4-5 months the sheets exhibit no corrosion at all.
If the sheets are only sanded and not degreased and only one application of the composition according to Example 2 takes place, the protection against corrosion after 6 months of weathering is still sufficient for the conservation of tubes.
Claims (15)
1. A composition (hereinafter referred to as a corrosion inhibiting composition) comprising a) a compound of formula I
b) a compound of formula II
in which
R is selected from C1-22 alkyl,C8~22 alkyl- C56 aryl or -CO-C8~22 alkyl or -CO-C8-22 alkenyl;
each M independently is hydrogen, an alkali metal ion or a molar equivalent of an alkaline earth metal;
R1 is M (as defined above) or a group of formula a) R-(0CnH2n-)x- (a)
each n independently is 2 or 3; and
each x independently is O or an integer from 1 to 15 inclusive.
R2 has a significance of R independently of R defined above;
each m independently is 2 or 3; and
y is O or an integer from 1 to 15 inclusive.
2. A composition according to Claim 1 containing a film forming agent.
3. A composition according to Claim 1 or Claim 2 containing one or more further additives selected from pH adjusting agents, biocides, surfactants, alkali metal salts of benzoic acid , benztriazole, tolyltriazole and light stabilisers.
4. A composition according to any one of Claims 1 to 3 in which R is
R' where R' is selected from C6-18 alkyl and C8~18 alkylphenyl.
5. A composition according toany one of Claims 1 to 4 in which R2 is
R2' where R2, is selected from C6~18 alkyl and C8~18 alkylphenyl.
6. A composition according to any one of Claims 1 to 5 in which R1 is R1' where R1, is M as defined in Claim 1 or C18 8 alkyl.
7. A polymeric composition comprising an acrylic resin and a corrosion inhibiting composition comprising a) a compound of formula I
b) a compound of formula II
in which
R is selected from C1-22 alkyl,C822 alkyl- C56 aryl or -CO-C8-22 alkyl or -CO-C8-22 alkenyl;
each M independently is hydrogen, an alkali metal ion or a molar equivalent of an alkaline earth metal;
R1 is M (as defined above) or a group of formula a) R(0CnH2n-)x- (a)
each n independently is 2 or 3; and
each x independently is O or an integer from 1 to 15 inclusive.
R2 has a significance of R independently of R defined above;
each m independently is 2 or 3; and
y is O or an integer from 1 to 15 inclusive.
8. A polymeric composition according to Claim 7 containing one or more further additives selected from pH adjusting agents, biocides, surfactants, alkali metal salts of benzoic acid , benztriazole, tolyltriazole and light stabilisers.
9. A composition according to Claim 7 or Claim 8 in which R is R' where R' is selected from C6~18 alkyl and C8~18 alkylphenyl.
10. A composition according to any one of Claims 7 to 9 in which R2 is
R2' where R2' is selected from C18 alkyl and C8-18 alkylphenyl.
11. A composition according to any one of Claims 7 to 10 in which R1 is R1, where R1' is M as defined in Claim 1 or C16 alkyl.
12. A corrosion inhibiting composition substantially as herein described in Example 1 or 2.
13. A polymeric composition substantially as herein described in
Example 1.
14. A process for treating a material against corrosion comprising applying to that material a composition according to Claim 1.
15. A process for treating a material against corrosion comprising applying to that material a composition according to Claim 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3711805 | 1987-04-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8808124D0 GB8808124D0 (en) | 1988-05-11 |
| GB2203156A true GB2203156A (en) | 1988-10-12 |
Family
ID=6325110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08808124A Withdrawn GB2203156A (en) | 1987-04-08 | 1988-04-07 | Corrosion inhibitors |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS63262484A (en) |
| KR (1) | KR880012796A (en) |
| FR (1) | FR2614631A1 (en) |
| GB (1) | GB2203156A (en) |
| IT (1) | IT1219522B (en) |
| SE (1) | SE8801264L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368575B2 (en) | 1998-09-11 | 2002-04-09 | Rohm And Haas Company | Method for inhibiting corrosion in an aqueous aerosol or foam hair styling composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180056817A (en) * | 2013-03-16 | 2018-05-29 | 피알시-데소토 인터내쇼날, 인코포레이티드 | Azole compounds as corrosion inhibitors |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL291684A (en) * | 1962-01-28 | 1900-01-01 | ||
| US3133787A (en) * | 1962-09-04 | 1964-05-19 | Socony Mobil Oil Co Inc | Corrosion inhibition |
| GB1225011A (en) * | 1967-03-17 | 1971-03-17 | Ici Ltd | Phosphorus acid esters and their use in the stabilisation of polymers |
| DE3067173D1 (en) * | 1979-10-19 | 1984-04-26 | Ici Plc | Process for the production of anti-static thermoplastics films and the films thereby produced |
-
1988
- 1988-03-30 FR FR8804357A patent/FR2614631A1/en not_active Withdrawn
- 1988-04-05 IT IT47815/88A patent/IT1219522B/en active
- 1988-04-06 KR KR1019880003802A patent/KR880012796A/en not_active Application Discontinuation
- 1988-04-06 JP JP63083211A patent/JPS63262484A/en active Pending
- 1988-04-06 SE SE8801264A patent/SE8801264L/en not_active Application Discontinuation
- 1988-04-07 GB GB08808124A patent/GB2203156A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368575B2 (en) | 1998-09-11 | 2002-04-09 | Rohm And Haas Company | Method for inhibiting corrosion in an aqueous aerosol or foam hair styling composition |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2614631A1 (en) | 1988-11-04 |
| SE8801264D0 (en) | 1988-04-06 |
| IT8847815A0 (en) | 1988-04-05 |
| GB8808124D0 (en) | 1988-05-11 |
| IT1219522B (en) | 1990-05-18 |
| SE8801264L (en) | 1988-10-09 |
| KR880012796A (en) | 1988-11-29 |
| JPS63262484A (en) | 1988-10-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |