[go: up one dir, main page]

CN100365003C - Esters of phosphorus-oxygen acids, these esters comprising alkoxy groups, and their use as corrosion inhibitors and flameproofing agents - Google Patents

Esters of phosphorus-oxygen acids, these esters comprising alkoxy groups, and their use as corrosion inhibitors and flameproofing agents Download PDF

Info

Publication number
CN100365003C
CN100365003C CNB200480012293XA CN200480012293A CN100365003C CN 100365003 C CN100365003 C CN 100365003C CN B200480012293X A CNB200480012293X A CN B200480012293XA CN 200480012293 A CN200480012293 A CN 200480012293A CN 100365003 C CN100365003 C CN 100365003C
Authority
CN
China
Prior art keywords
alkoxyl group
alkyl
group
phosphorus
branched
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 - Fee Related
Application number
CNB200480012293XA
Other languages
Chinese (zh)
Other versions
CN1784413A (en
Inventor
H·维特勒
M·费尔南德斯冈萨雷斯
G·瓦根布拉斯特
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of CN1784413A publication Critical patent/CN1784413A/en
Application granted granted Critical
Publication of CN100365003C publication Critical patent/CN100365003C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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)]
    • C07F9/40—Esters thereof
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
    • 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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
    • 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)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic 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)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C09K21/00—Fireproofing materials
    • 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
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention relates to esters or ester salts of phosphorus-oxygen acids, these esters or ester salts comprising alkoxy groups, and to the use of compounds of this type as corrosion inhibitors, particularly in alkaline media, and as flameproofing agents.

Description

The ester that contains alkoxyl group of phosphorus-oxygen acids and as the purposes of inhibiter and fireproofing agent
What the present invention relates to phosphorus-oxygen acids contains alkoxy ester or ester salt.The invention still further relates to this compounds as inhibiter, especially in alkaline medium as the purposes of inhibiter.
The purposes of Phosphoric acid or phosphonic acid derivative in anticorrosion is known in principle.Yet, Phosphoric acid or phosphonic acid derivative or its hydrolysate common and various gegenions such as Ca 2+In alkaline aqueous medium, form insoluble or slightly soluble salt, so they only can be used for such medium with limited extent.
Alkaline medium can be concrete, mortar etc. for example, or contains finishing agent, coating system of alkaline binder systems for use etc.
Being embedded in the steel bars in concrete strongthener can not be anticorrosion fully, but can corrode in time.Because the corrosion of reinforcing bar strongthener, its intensity and therefore concrete intensity reduce.In addition, corrosion product, for example ferriferous oxide or ferric hydrous oxide have than the bigger volume of corrosion reinforcing bar itself not.Therefore, form stress in concrete, this may cause the fracture of crackle or entire segment.The corrosion of Steel Concrete produces the remarkable economical loss.
The corrosion of reinforcing bar strongthener is basically by the process of diffusion control.Water and oxygen can be diffused in the concrete hole.Water in the hole especially comprises dissolved Ca (OH) 2And in untreated concrete, has about 13 pH.Under this pH, it is anticorrosion because of passivation layer to be embedded in the steel bars in concrete strongthener.Atmospheric CO 2Diffusion in the hole especially causes forming insoluble CaCO 3And the pH of the water in the hole drops to and is lower than 9 value.Yet the passivation layer on reinforcing bar under these pH values becomes invalid.The effect of passivation layer can be subjected to the disadvantageous effect of chlorion or by its elimination.For example contact with seawater or anti-freezing composition by concrete, chlorion may penetrate in the concrete.
When use have seldom the hole and during the concrete of particularly compact, the CO of infiltration 2Or the muriatic amount of infiltration is less.Yet, also can not prevent infiltration by this way fully.In addition, when concrete structure changed, its performance also changed, and this is normally undesirable according to the purposes of expection.Therefore in many cases, use and have seldom that the concrete possibility in hole is infeasible.
Therefore, known inhibiter such as nitrite, amine, alkanolamine, itself and mineral acid or organic acid mixture or phosphoric acid ester can addings in the novel concrete.Also knownly phosphonic acids or phosphonate derivative can be used for the anticorrosion of concrete.DE-A 36 29 234 discloses the salt with various alkyl phosphonic acids, and especially sodium salt adds in concrete and the mortar mix as additive.GB-A 2 248 612 and JP-A-03-159945 disclose and have contained amino or hydroxyl phosphonic acids as concrete additive.
Except the rotproofing of novel concrete, the problem of relevant old concrete protection often appears in practice.For this reason, concrete can be cut from the teeth outwards or blows and expose the reinforcing bar strongthener, available then inhibiter is handled the reinforcing bar strongthener and is finally covered with concrete once more.This method is especially used under concrete structure has been subjected to the serious situation of irreversible lesion.
The also known transport property inhibiter of can using is handled the hardened reinforced concrete surface.This technology for example is disclosed among " M.Haynes, B.Malric, Construction Repair (building is repaired), 1997 7/8 month " or the US 5,071,579.For this reason, apply successively from the teeth outwards or spray corrosion inhibitor solution several times, this inhibiter is moved in the surface.Usually go up to support further diffusion finally to arrive the reinforcing bar strongthener by water being put on repeatedly the surface to inside.Known Na 2PO 3F can be used as the transport property inhibiter.US 5,071, and 579 also disclose Na 2PO 3F and formula R nR lN (CH 2PO 3H 2) 2-nBeing used in combination of phosphonic acids (n=0 or 1).Yet, the fluoro sodium phosphate in water hydrolysis and with the water that is dissolved in the hole in Ca (OH) 2Form insoluble calcium phosphate.Phosphonic acids also forms insoluble calcium phosphate.Therefore, a large amount of inhibiter of applying of surface can not reach the reinforcing bar strongthener at all and therefore can not demonstrate any effect.Therefore must use inhibiter in a large number.This is uneconomic, and concrete is subjected to the pollution of unwanted component in addition.
The purpose of this invention is to provide improved inhibiter, it is specially adapted in the alkaline medium and particularly form insoluble or microsolubility calcium salt.
We find that this purpose is realized by the alkoxy ester that contains of the phosphorus-oxygen acids of following formula:
(A) R 3-NR 4 k-[(CH 2) n-PO (OR 1) (OR 2)] m, or
(B) [(R 1O) (R 2O) OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[(CH 2) n-PO (OR 1) (OR 2)] mWherein
N is the integer of 0-10,
M+k=2, m be 1 or 2 and k be 0 or 1,
Radicals R 1, R 2Also has R with suitable words 3In at least one be formula-[CH 2-CHR 6-O] lR 7Alkoxyl group, wherein l is 2-30 and R 6And R 7H or CH respectively do for oneself 3,
And wherein work as R 1And R 2When being not alkoxyl group, it is straight chain or branching C 1-C 6Alkyl, and wherein work as R 3When being not alkoxyl group, it is the C that does not replace or replace of straight chain or branching 1-C 20Alkyl or aryl,
R 4Be H or straight chain or branching C 1-C 6Alkyl and
R 5Be divalence bridge joint group.
Second aspect present invention found following formula phosphorus-oxygen acids contain alkoxy ester salt:
(C) R 3-NR 4 k-[(CH 2) n-PO (OR 1) (OM)] m, or
(D)[(MO)(R 1O)OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[-(CH 2) n-PO(OR 1)(OM)] m
Wherein
N is the integer of 0-10,
M+k=2, m be 1 or 2 and k be 0 or 1,
Radicals R 1Also has R with suitable words 3In at least one be formula-[CH 2-CHR 6-O] lR 7Alkoxyl group, wherein l is 2-30 and R 6And R 7H or CH respectively do for oneself 3,
And wherein work as R 1When being not alkoxyl group, it is straight chain or branching C 1-C 6Alkyl,
And wherein work as R 3When being not alkoxyl group, it is the C that does not replace or replace of straight chain or branching 1-C 20Alkyl or aryl,
R 4Be H or straight chain or branching C 1-C 6Alkyl and
R 5For divalence bridge joint group and
M is at least a positively charged ion that is selected from basic metal, alkaline-earth metal or ammonium ion.
In addition, we have found ester or ester salt inhibiter, the especially purposes of transport property inhibiter as Steel Concrete.
Be that we find the ester group quantity of each phosphorus atom of diester of the present invention-refer to-to anticorrosion very useful unexpectedly.They are particularly suitable for alkaline medium very much, and suitable words comprise the medium of calcium ion.Ester of the present invention dissolves in saturated Ca (OH) 2Solution and do not form microsolubility precipitation.In addition, monoester salt is at Ca (OH) 2Solubleness in the solution is enough.
Even under the temperature of excess NaOH and rising, diester is only hydrolysis and obtain corresponding monoester salt in alkaline medium very lentamente usually.Further hydrolysis and obtain free acid or its salt only carries out very little degree under the described conditions.Itself has corrosion inhibition diester.Usually, the corrosion inhibition of corresponding monoester salt is higher.Monoester salt only discharges gradually by hydrolysis.Diester is the inhibiter of sheltering inhibiter or having delay or long term.
The present invention specifically describes as follows.
Phosphorus-oxygen acids of the present invention contain the diester that alkoxy ester is a following formula:
(A)R 3-NR 4 k-[(CH 2) n-PO(OR 1)(OR 2)] m，
One of them or two phosphorus-oxygen acids groups directly or indirectly are connected on the nitrogen-atoms with at least one other substituting group, or the bridge joint diester of following formula:
(B) [(R 1O) (R 2O) OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[(CH 2) n-PO (OR 1) (OR 2)] m, wherein two nitrogen-atoms are via radicals R 5Interconnect and thereby have one or two phosphorus-oxygen acids group and suitable words also have other substituting group.
Hereinafter, term " diester " is about the ester group quantity of each phosphorus atom and therefore represents that all phosphorus atom that exist in the molecule all have the compound of two ester groups separately.Therefore, term hereinafter " monoesters " is meant that each phosphorus atom wherein all has the compound of ester group or OH or OM group.Diester of the present invention or monoesters be wherein n greater than 0 phosphonate derivative, and they n be 0 o'clock be the derivative of amide group phosphoric acid.
Formula (A) and (B) in symbol n be the integer of 0-10.Preferred n is the integer of 0-3, preferred especially 0 or 1, further preferred especially 1.
Symbol m be 1 or 2 and symbol k be 0 or 1, the summation of m+k is 2.Preferred m and k respectively do for oneself 1, i.e. one-(CH only in each case 2) n-PO (OR 1) (OR 2) group is connected on the nitrogen-atoms.
Radicals R 1, R 2Also has R with suitable words 3In at least one (promptly wherein diester is compound (A)) be alkoxyl group.Suitable alkoxyl group is formula-[CH especially 2-CHR 6-O] lR 7Polyoxyethylene or polyoxypropylene group, wherein l is 2-30 and R 6Be H and/or CH 3R 6Be preferably H, promptly alkoxyl group is a polyoxyethylene group.Preferred l is 3-20, preferred especially 5-15.R 7Be CH group or H.
Known such alkoxyl group of those skilled in the art for example can obtain by hydroxyalkylation or by industrial polyoxyethylene glycol raw material.Therefore the described value of l is mean chain length, and wherein mean value needn't be natural number certainly, but also can be any required rational number.
Be not all the other radicals R of alkoxyl group 1, R 2Also has R with suitable words 3(only for situation (A)) is the alkyl that does not replace or replace of straight chain or branching.The optional substituting group that exists for example can be amino or OH.Substituting group especially can be the OH end group.
R 1And/or R 2Be preferably C 1-C 6Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl or n-hexyl, preferable methyl or ethyl, further preferred especially ethyl.The alkyl that replaces especially can be the 2-methoxy ethyl.
R 3Be preferably C 1-C 20Alkyl or aryl.It is preferably straight chain or branching C 4-C 12Alkyl.The example of proper group comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl.Particularly preferred group comprises n-propyl, normal-butyl, n-octyl and 2-ethylhexyl.The alkyl that replaces especially can be ω-methoxyl group alkyl, for example methoxy ethyl.Aryl can be pure aryl, as the aryl of alkyl replacement, for example-CH 2C 5H 6Group.
If present, R 4Be the alkyl that does not replace or replace of H or straight chain or branching, preferred C 1-C 6Alkyl.Preferred especially R 4Be H or methyl.The alkyl that replaces especially can be the 2-methoxy ethyl.
In bridge joint compound (B), there is not R 3, preferably have the divalence bridge joint radicals R of at least 2 carbon atoms but exist 5Described group especially can be the group that is derived from aliphatic series, alicyclic or aromatic hydrocarbon.Example comprises also can have heteroatoms or substituent 1,4-xylylene, 1,4-cyclohexylidene or ethylidene.
The bridge joint group is preferably the alkylidene group of 2-20 carbon atom, wherein non-conterminous CH 2Group can also be replaced by O or N atom.Example comprises group-(CH 2) 2-,-(CH 2) 4-,-(CH 2) 6-,-(CH 2) 8-,-(CH 2) 2-O-(CH 2) 2-,-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-,-(CH 2) 3-O-(CH 2) 4-O-(CH 2) 3-,-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 3-,-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-,-(CH 2) 2-O-[(CH 2) 2-O-] j(CH 2) 2-O-(CH 2) 2-,-(CH 2) 2-HN-(CH 2) 2-and-(CH 2) 2-NR 6-(CH 2) 2-NR 6-(CH 2) 2-, wherein j is 1-10 and R 6For alkyl ,-(CH 2) n-PO (OR 1) (OR 2) or-(CH 2) n-PO (OR 1) (OM).
Described group is preferably group-(CH 2) 2-,-(CH 2) 4-,-(CH 2) 6-,-(CH 2) 3-O-(CH 2) 4-O-(CH 2) 3-,-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-or-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-.
In radicals R 1-R 7Various may the combination in, those skilled in the art carry out suitable selection according to the purposes of required character and expection.In order to implement the present invention, radicals R 1And R 2In one be that alkoxyl group is just enough.Yet, preferred R 1And R 2Be alkoxyl group.
Verified useful especially transport property inhibiter is a following compounds:
(2-ethylhexyl)-N (CH 3)-(CH 2)-PO (O-alkoxyl group) (O-alkoxyl group),
(2-ethylhexyl)-N[-(CH 2)-PO (O-alkoxyl group) (O-alkoxyl group)] 2,
Butyl-NH-PO (O-alkoxyl group) (O-alkoxyl group),
Octyl group-NH-PO (O-alkoxyl group) (O-alkoxyl group),
(2-ethylhexyl)-NH-PO (O-alkoxyl group) (O-alkoxyl group),
(2-ethylhexyl)-N (CH 3)-PO (O-alkoxyl group) (O-alkoxyl group),
(alkoxyl group)-NH-PO (O-alkoxyl group) (O-alkoxyl group),
((OP-NH-(the CH of alkoxyl group-O) of alkoxyl group-O) 2) 2-O-(CH 2) 2-O-(CH 2) 2-NH-PO (O-alkoxyl group) (O-alkoxyl group),
(2-methoxy ethyl) 2N-CH 2-PO (O-alkoxyl group) (O-alkoxyl group),
(ethyl) 2N-CH 2-PO (O-alkoxyl group) (O-alkoxyl group),
(CH 2) 5N-CH 2-PO (O-alkoxyl group) (O-alkoxyl group),
(alkoxyl group-and O) (alkoxyl group-O)
Figure C20048001229300091
(O-alkoxyl group) (O-alkoxyl group),
In following ester salt of the present invention:
(C) R 3-NR 4 k-[(CH 2) n-PO (OR 1) (OM)] mAnd
(D) [(MO) (R 1O) OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[(CH 2) n-PO (OR 1) (OM)] mGroup-if present-have the implication of being given in as above the description with symbol to diester.Yet each phosphorus atom of ester salt only has an ester group.Under the situation of (D), R 1Be always alkoxyl group; Under the situation of (C), R 1Or R 3Can be alkoxyl group, or R 1And R 3Be alkoxyl group together.
M is at least a positively charged ion that is selected from basic metal, alkaline-earth metal or ammonium ion.Ammonium ion especially can be NH 4 +The ammonium ion that alkyl replaces or hydroxyalkyl replaces is as (HOCH 2CH 2) 3NH +, (HOCH 2CH 2) 2NH 2 +, HOCH 2CH 2NH 3 +Or HOCH 2CH 2N (CH 3) 2H +Or tetraalkyl ammonium ion such as tetramethyl-ammonium or tetraethyl ammonium.Preferred Na +, K +, Mg ++, Ca ++, Ce +++, Al +++, Zn ++And NH 4 +For the sake of simplicity, following formula is only represented the situation of monovalent cation.Yet those skilled in the art can easily be inferred the correct structural formula of polyvalent cation by it.
The diester of phosphorus-oxygen acids of the present invention for example can be prepared as raw material by commercially available phosphonic acid ester such as diethyl phosphonate.
By making polyoxyethylene glycol required under diethyl phosphonate and the every kind of situation or polypropylene glycol or corresponding monoether reaction, oxyalkylated diester can be made by this marketable material by transesterify.Transesterify can for example be carried out catalysis by basic metal, and steams and remove the ethanol that discharges.
Certainly can also also pass through the known in principle method of those skilled in the art with its hydroxyalkylation as raw material with phosphonic acids itself.In this case, the alkoxyl group that is still had the OH end group.
For n=0, can make gained dialkoxy ester and required amine, for example DEHA reaction.This reaction can be in known mode in principle at CCl 4With as carrying out in the tertiary amine of catalyzer.Use diamines such as quadrol to produce bridge joint diester (B).Use amino polyethylene or polypropylene glycol to produce and have alkoxyl group as R 3Diester.
Wherein the diester of n=1 can obtain by the amino methylization of diethyl phosphonate or corresponding alkoxylate diester.Here make phosphonic acid diester and formaldehyde, required amine and suitable Bronsted acid-respons.
Wherein the diester of n=2 can prepare by amine is added on the vinylphosphonate, and the diester of n＞2 prepares (for example for n=3, adding on the allyl amine) by the free radical addition of phosphonic acid diester at two keys place or prepares by the Arbuzov reaction with the aminoalkyl group bromine.
The preferably preparation of the alkaline hydrolysis by diester of ester salt, for example by in aqueous NaOH, diester being heated to 60-100 ℃ temperature and keeping 2-12 hour, each phosphorus atom ester group of hydrolysis only basically wherein.If suitable only by several experiments, those skilled in the art just can determine the top condition of required compound under every kind of situation.Monoester salt also can form on the spot by hydrolysis in used medium.
Diester of the present invention and monoester salt can be used as inhibiter.They are particularly suitable for alkaline medium such as pH is in the alkaline medium of 8-13.In addition, they are particularly suitable at Ca 2+There is use down in ion.
Diester of the present invention and monoester salt can be directly used in anticorrosion.For example, if suitable after mild heat, can or be poured on the metallic surface suitable derivative spraying.They can also be added in other materials or mixture such as finishing agent, printing-ink, mortar or the concrete, and therefore can be anticorrosion when described material or mixture and metallic contact.
Yet, preferably using diester and monoester salt with suitable prescription form, this prescription comprises at least a diester and/or a kind of monoester salt, suitable solvent and optional other components.
Suitable solvent is water or alcohols especially, as methyl alcohol, ethanol, propyl alcohol, polyoxyethylene glycol or alkyl polyoxyethylene glycol.Certainly can also use the mixture of different solvents.
The preferred prescription that mainly comprises the water-containing solvent mixture.This is interpreted as referring to comprise at least 50 weight %, preferably at least 65 weight %, the especially preferably mixture of at least 80 weight % water.Other components are solvents miscible with water.Example comprises single alcohol as methyl alcohol, ethanol or propyl alcohol, higher alcohols such as ethylene glycol, glycerine or Aethoxy Sklerol, and ether alcohol such as butyl glycol or methoxypropanol.
According to the type and the required purposes of used inhibiter, suitably select in the possible in principle solvent of those skilled in the art.
Particularly preferred solvent is a water.
Those skilled in the art select the pH that fills a prescription according to required purposes.Preferably at alkaline aqueous medium, for example pH uses inhibiter in the alkaline aqueous medium of 8-13.
Those skilled in the art set the concentration of inhibiter according to required purpose.Certainly can also prepare enriched material, before on-the-spot actual the use, just this enriched material is diluted to desired concn.
Only otherwise have a negative impact, can also conduct use other inhibiter with the form of mixtures of inhibiter of the present invention.
The prescription that comprises inhibiter of the present invention with suitable method as being applied on the metallic surface to be protected by coating, spraying, printing or dipping.The metallic surface can be industrial conventional material usually, is selected from the industrial conventional alloy of aluminium alloy and magnesium alloy, iron, steel, copper, zinc, tin, nickel, chromium and these metals.Other examples comprise can be by the industrial common metal coating of chemistry or electrochemical method production, be selected from zinc and alloy thereof, preferable alloy zinc, zinc/iron, zinc/nickel, zinc/manganese or zinc/cobalt-base alloy, tin and alloy thereof, preferable alloy tin, comprise the tin alloy of Cu, Sb, Pb, Ag, Bi and Zn, be preferably used as those of scolder especially, for example the scolder that in the production of circuit card and processing, uses, and copper, the preferably copper of the form of on circuit card and metallized plastic parts, using.
Metallic surface to be protected can also be metallic particles or sheet metal, for example aluminium flake.According to granularity, this metalloid effect pigment is used for purpose very widely.Smaller particles is as the silver bronze look pigment in for example printing-ink or the finishing agent, and larger particles is used as anti-corrosion paint in finishing agent.Diester of the present invention and monoester salt can add in printing-ink or the finishing agent, perhaps handle the metal effect pigment with prescription of the present invention before mixing.
Diester of the present invention and monoester salt are particularly suitable for the anticorrosion of Steel Concrete.On the one hand, they can be added in the novel concrete.They can also be used to improve old concrete, for example handle the reinforcing bar strongthener that exposes.They also are suitable as the transport property inhibiter.
Compound of the present invention can also be used for other field certainly.They also are fit to for example as fireproofing agent.
The following example is described in more detail the present invention:
Raw materials used:
Pluriol A 275E: methyl polyglycol ether, M w275g/mol (BASF AG).
In an embodiment, this compound abbreviates the methoxyl group hexaethylene glycol as.In fact, it is existence-CH 2CH 2O-unit number mean value is the mixture of 5.5 various methyl polyoxyethylene glycol.
For experiment, can also use to have other molecular-weight average M wOther methyl polyglycol ether, for example Pluriol A 350E (M w350g/mol) or Pluriol A 500E (M w500g/mol).
Embodiment 1:
Preparation phosphorous acid two (methyl hexaethylene glycol) ester
Figure C20048001229300121
At first (12.8g, 0.093mol) (50g 0.186mol) places the 500ml flask together with Pluriol A 275 E with diethyl phosphite.Add potassium as catalyzer (20mg, 0.5mmol) after, reaction mixture is heated to 170 ℃ and steam and remove the EtOH that forms under barometric point.Residual EtOH evaporates under 20mmHg.Productive rate is 95-98%.
Have other polyglycol ethers of higher or lower molecular weight by use, can obtain having the phosphonic acid ester of other ester groups.
In another kind of preparation method, phosphorous acid two (methyl hexaethylene glycol) ester also prepares by the direct ethoxylation of phosphonic.
Embodiment 2:
Preparation 2-ethylhexyl phosphamide two (methyl hexaethylene glycol) ester
Figure C20048001229300122
To be dissolved in 1: 1 CCl according to 62.0g (0.092mol) phosphorous acid two (methyl hexaethylene glycol) ester that embodiment 1 obtains 4/ CH 2Cl 2(185ml) in the mixture and add 2-DEHA (11.9g, 0.092mol) (R in following formula 3Be the 2-ethylhexyl).Drip at last triethylamine (9.28g, 0.092mol).Leach white triethylammonium salts hydrochlorate powder and steam and desolventize.Productive rate with 76% obtains transparent liquid shape 2-ethylhexyl phosphamide two (methyl hexaethylene glycol) ester (based on F.R.Atherton, A.R.Todd, J.Am.Chem.Soc., (1947), 674, the same (1945), 660 synthetic method).
Other compounds that can obtain according to the method for embodiment 1 also can be used as phosphonic acid ester.Except the 2-DEHA, can also use other amine.
Embodiment 3:
Preparation (N-methyl-N-2-ethylhexyl amino methyl phosphorous acid) two (methyl hexaethylene glycol) ester
Figure C20048001229300131
In 1 hour, phosphorous acid two (methyl hexaethylene glycol) ester (0.1mol) is added drop-wise to N-methyl-2-DEHA (14.3g simultaneously at～11 ℃ of following refrigerative, 0.1mol), formaldehyde (8.21g, concentration is 36.5% solution, 0.1mol) and ortho-phosphoric acid (4.89g, concentration is 85%, 5 weight %) mixture in.Then this reaction mixture is heated to 90 ℃ and under this temperature, kept 3 hours.
Except ortho-phosphoric acid, can also be being that the amount of 1 weight % uses acid ion exchangers such as Amberlyst 36Dry as catalyzer based on total amount.Can also can be used as phosphonic acid ester according to other compounds that embodiment 1 obtains.Except the 2-DEHA, can also use other amine.If the use primary amine then also forms corresponding dimer except above-mentioned product.This is as follows by the example that uses octylame.
Figure C20048001229300132
Embodiment 4:
Preparation (N-methyl-N-2-ethylhexyl amino methyl phosphorous acid) two (hydroxyl hexaethylene glycol) ester
Figure C20048001229300133
The 1st step: synthetic phosphonic acids
In first reactions steps according to above reaction formula based on K.Moedritzer, R.R.Irani, J.Org.Chem. (1966), the synthetic method of 1603-1607 is synthesized phosphonic acids.
The 2nd step: phosphonic ethoxylation
With N-methyl-N-2-ethylhexyl aminomethylphosphonic acid (238g 1mol) is suspended in the 2l toluene, and under 50 ℃ and 1-1.5 crust, slowly be metered into 14 normal ethylene oxides (616g, 14mol).Under reduced pressure solvent is separated with product (B).
The hydrolysis diester is to obtain the general method of monoesters
At first (dialkyl amino ylmethyl phosphorous acid) two (methyl polyoxyethylene glycol) esters or alkyl phosphamide two (methyl polyoxyethylene glycol) ester (0.05mol) are placed the 100ml four neck flasks that have thermopair, thermoswitch, coil condenser and bubble counter.Product dilutes with softening (37.0g).Then in about 10 minutes dropping sodium solution (50%, 8g, 0.1mol), temperature is increased to and is no more than 32 ℃.After reinforced fully, slowly be heated to 100-105 ℃ reflux temperature and reaction mixture was kept 8 hours under this temperature.Product is used 31P, 1H and 13C-NMR characterizes.
Under these conditions, only can detect single hydrolysate.
The compounds of this invention is used as the purposes of inhibiter in alkaline medium:
The general operation method:
By degreasing of negative electrode alkalescence and electrolytic derusting and metal pretreated test piece (2cm * 5cm, steel 1.0037) subsequently.
Sample was covered 7 days with test soln, measure the mass loss of metal testing plate then.The inhibiter of correspondence is added in this test soln.Use identical tinsel with identical test soln but do not add inhibiter and compare experiment in each case.
Preservative efficiency obtains by the mass loss of the tinsel that relatively adds and do not add inhibiter and test.
Efficient [%]=[(Δ M 0-Δ M)/(Δ M 0)] 100
Δ M 0: the mass loss of tinsel when not adding inhibiter
Δ M: the mass loss of tinsel when adding inhibiter.
Test soln: softening water, 0.03mol/l NaCl transfers to 10 with KOH with pH
The concentration of inhibiter in solution: be 1 weight % in each case.
Table 1 has illustrated the preservative efficiency of different inhibiter of the present invention.Nulling sample and the sample that contains conventional inhibiter monoethanolamine have also been tested in experiment as a comparison.
The performance of inhibiter of the present invention in concrete:
The general operation method:
In order to test the migration performance of inhibiter of the present invention, use the concrete sheet of long 75mm, wide 20mm and thick 4mm.As under the situation of tlc, the concrete sheet vertically is positioned in the test soln that contains 10 weight % inhibiter of the present invention in each case in water, so that they immerse about 1cm this solution from bottom margin.In order to prevent the test soln evaporation, in closed container, test, for example in having the suitable dimension glass jar of snap close lid.After 1 day, this test soln is upwards moved to the top edge of this sheet.
In order to analyze, phosphorus content is analyzed then as sample and with its grinding in the top 1/3 of smashing this concrete sheet after 1 day.Deduct the phosphorus content of untreated concrete sheet in each case.
Use 3 kinds of The compounds of this invention to experimentize.The results are shown in Table 2 and show that The compounds of this invention has good migration performance.
Figure C20048001229300161

Claims (10)

  1. Following formula (A) or phosphorus-oxygen acids (B) contain alkoxy ester and/or following formula (C) or phosphorus-oxygen acids (D) contain the purposes of alkoxy ester salt as inhibiter:
    (A)R 3-NR 4 k-[(CH 2) n-PO(OR 1)(OR 2)] m，
    (B)[(R 1O)(R 2O)OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[-(CH 2) n-PO(OR 1)(OR 2)] m
    (C)R 3-NR 4 k-[(CH 2) n-PO(OR 1)(OM)] m，
    (D)[(MO)(R 1O)OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[-(CH 2) n-PO(OR 1)(OM)] m
    Wherein
    N is 0 or 1,
    M+k=2, m be 1 or 2 and k be 0 or 1,
    Radicals R 1, R 2And R 3In at least one be formula-[CH 2-CHR 6-O] 1R 7Alkoxyl group, wherein l is 2-30 and R 6Be H, R 7Be H or CH 3,
    And work as R 1And R 2When being not alkoxyl group, it is the C of straight or branched 1-C 6Alkyl,
    And work as R 3When being not alkoxyl group, it is the C of straight or branched 1-C 20Alkyl,
    R 4C for H or straight or branched 1-C 6Alkyl,
    R 5For alkylidene group with 2-20 carbon atom and
    M is at least a positively charged ion that is selected from basic metal, alkaline-earth metal or ammonium ion.
  2. 2. according to the purposes of claim 1, wherein this inhibiter is used for alkaline medium.
  3. 3. according to the purposes of claim 2, wherein this medium is a water-bearing media.
  4. 4. according to any one purposes among the claim 1-3, wherein work as R 1And R 2When being not alkoxyl group, it is a methyl;
    Work as R 3When being not alkoxyl group, it is the C of straight or branched 4-C 12Alkyl;
    R 4Be H or methyl.
  5. 5. according to any one purposes among the claim 1-3, wherein k and m respectively do for oneself 1.
  6. 6. according to any one purposes among the claim 1-3, wherein l is 3-20.
  7. The phosphorus-oxygen acids of following formula contain alkoxy ester salt:
    (C) R 3-NR 4 k-[(CH 2) n-PO (OR 1) (OM)] m, or
    (D)[(MO)(R 1O)OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[-(CH 2) n-PO(OR 1)(OM)] m
    Wherein
    N is 0 or 1,
    M+k=2, m be 1 or 2 and k be 0 or 1,
    Radicals R 1And R 3In at least one be formula-[CH 2-CHR 6-O] 1R 7Alkoxyl group, wherein l is 2-30 and R 6Be H, R 7Be H or CH 3,
    And work as R 1When being not alkoxyl group, it is the C of straight or branched 1-C 6Alkyl,
    And work as R 3When being not alkoxyl group, it is the C of straight or branched 1-C 20Alkyl,
    R 4C for H or straight or branched 1-C 6Alkyl and
    R 5For alkylidene group with 2-20 carbon atom and
    M is at least a positively charged ion that is selected from basic metal, alkaline-earth metal or ammonium ion.
  8. According to the phosphorus-oxygen acids of claim 7 contain alkoxy ester salt, wherein work as R 1When being not alkoxyl group, it is a methyl;
    Work as R 3When being not alkoxyl group, it is the C of straight or branched 4-C 12Alkyl;
    R 4Be H or methyl.
  9. The phosphorus-oxygen acids of following formula contain alkoxy ester:
    (A) R 3-NR 4 k-[(CH 2) n-PO (OR 1) (OR 2)] m, or
    (B)[(R 1O)(R 2O)OP-(CH 2) n-] m-NR 4 k-R 5-NR 4 k-[-(CH 2) n-PO(OR 1)(OR 2)] m
    Wherein
    N is 0 or 1,
    M+k=2, m be 1 or 2 and k be 0 or 1,
    Radicals R 1, R 2And R 3In at least one be formula-[CH 2-CHR 6-O] 1CH 3Alkoxyl group, wherein l is 2-30 and R 6Be H,
    And work as R 1And R 2When being not alkoxyl group, it is the C of straight or branched 1-C 6Alkyl,
    And work as R 3When being not alkoxyl group, it is the C of straight or branched 1-C 20Alkyl,
    R 4C for H or straight or branched 1-C 6Alkyl and
    R 5For having the alkylidene group of 2-20 carbon atom.
  10. 10. according to the alkoxy ester that contains of the phosphorus-oxygen acids of claim 9, wherein work as R 1And R 2When being not alkoxyl group, it is a methyl;
    Work as R 3When being not alkoxyl group, it is the C of straight or branched 4-C 12Alkyl;
    R 4Be H or methyl.
CNB200480012293XA 2003-05-05 2004-05-03 Esters of phosphorus-oxygen acids, these esters comprising alkoxy groups, and their use as corrosion inhibitors and flameproofing agents Expired - Fee Related CN100365003C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10320071.1 2003-05-05
DE10320071A DE10320071A1 (en) 2003-05-05 2003-05-05 Esters of phosphorus-oxygen acids containing alkoxy groups and their use as corrosion inhibitors

Publications (2)

Publication Number Publication Date
CN1784413A CN1784413A (en) 2006-06-07
CN100365003C true CN100365003C (en) 2008-01-30

Family

ID=33394156

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200480012293XA Expired - Fee Related CN100365003C (en) 2003-05-05 2004-05-03 Esters of phosphorus-oxygen acids, these esters comprising alkoxy groups, and their use as corrosion inhibitors and flameproofing agents

Country Status (7)

Country Link
EP (1) EP1622917A1 (en)
JP (1) JP2006525423A (en)
KR (1) KR20060013527A (en)
CN (1) CN100365003C (en)
CA (1) CA2524052A1 (en)
DE (1) DE10320071A1 (en)
WO (1) WO2004099222A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1681295A1 (en) * 2005-01-17 2006-07-19 Solutia Europe N.V./S.A. Process for the manufacture of aminoakylenephosphonic acid compounds in the presence of a heterogeneous catalyst
CN102002716A (en) * 2010-12-10 2011-04-06 上海电力学院 Corrosion inhibitor auxiliary electrochemical re-alkalization repairing technology for carbonized reinforced concrete structure
WO2013033438A2 (en) * 2011-08-31 2013-03-07 Mallinckrodt Llc Nanoparticle peg modification with h-phosphonates
JP6066701B2 (en) * 2012-12-04 2017-01-25 学校法人東京理科大学 Method for producing diphosphorous acid (polyoxyethylene ether)
KR102341327B1 (en) * 2015-04-13 2021-12-21 정용주 Method for manufacturing hygroscopicity rust Inhibitor and the hygroscopicity rust Inhibitor manufactured by the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314957A (en) * 1963-05-21 1967-04-18 Union Carbide Corp Aminomethyl-phosphonates
GB1604657A (en) * 1978-05-30 1981-12-16 Lankro Chem Ltd Phenolic resins and products prepared therefrom

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297796A (en) * 1963-09-27 1967-01-10 Dow Chemical Co Hydroxyalkyl-aminomethyl phosphonates
FR1470166A (en) * 1965-03-01 1967-02-17 Lankro Chem Ltd Improvements with hydroxy-alkyl diesters of dialkylolamino-alkylphosphonic acid
ZA721530B (en) * 1971-03-18 1972-11-29 Interstab Ltd Curing agents for epoxy resins
DE3409935C1 (en) * 1983-11-11 1985-04-18 Hoesch Ag, 4600 Dortmund Method and device for hot-galvanising ribbed tubes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314957A (en) * 1963-05-21 1967-04-18 Union Carbide Corp Aminomethyl-phosphonates
GB1604657A (en) * 1978-05-30 1981-12-16 Lankro Chem Ltd Phenolic resins and products prepared therefrom

Also Published As

Publication number Publication date
WO2004099222A1 (en) 2004-11-18
DE10320071A1 (en) 2004-12-02
EP1622917A1 (en) 2006-02-08
JP2006525423A (en) 2006-11-09
CN1784413A (en) 2006-06-07
KR20060013527A (en) 2006-02-10
CA2524052A1 (en) 2004-11-18

Similar Documents

Publication Publication Date Title
CN102674571B (en) Method of scale inhibition
CA2672237C (en) Functionalized amine-based corrosion inhibitors for galvanized metal surfaces and method of using same
CA2718242A1 (en) Process for coating metal surfaces with a passivating agent, the passivating agent and its use
CN100365003C (en) Esters of phosphorus-oxygen acids, these esters comprising alkoxy groups, and their use as corrosion inhibitors and flameproofing agents
US20250109343A1 (en) Corrosion inhibitor
DE2621606A1 (en) PROPANE-1,3-DIPHOSPHONIC ACIDS FOR WATER CONDITIONING
JP2006524749A (en) Use of phosphorus-oxyacid esters containing alkoxy groups as corrosion inhibitors for reinforced concrete
EP0846690B1 (en) Melamin polycarboxylic amides and their use as corrosion inhibitor
EP0934948B1 (en) Phosphorus containing compounds based on 1-hydroxy-1,3-diphosphonic acid
CA1090818A (en) 2,2,2-tris (hydroxymethyl) ethylphosphonic acid and method for its preparation
US6607610B1 (en) Polyphenolamine composition and method of use
CA1315085C (en) Corrosion inhibiting aqueous compositions comprising metal-chelating diphenolamine compounds
JP2852758B2 (en) Lubricating rust preventive oil composition
EP0368155B1 (en) Inhibiting corrosion in aqueous systems
RU2430997C2 (en) Corrosion inhibitor
CN110144146A (en) A kind of synthetic method of band rust antirust styrene-acrylic emulsion
JP4154564B2 (en) Aqueous anticorrosive and method for producing the same
US4911887A (en) Phosphonic acid compounds and the preparation and use thereof
US4018700A (en) Chromated alkaline earth salts of bis(s-diphenylguanidinium benzenephosphonate) for the corrosion-inhibition of aluminum and ferrous alloys
Shumatbaev et al. Novel α-Aminophosphonates Based on Syntanols: Synthesis and Anti-Corrosion Activity
CA1174451A (en) Low level zinc corrosion inhibitors
US4061589A (en) Corrosion inhibitor for cooling water systems
CN1231346A (en) Novel corrosion inhibitor for inhibiting iron and steel corrosion in running water
US4438013A (en) Phosphorylated and thiophosphorylated poly(oxyalkylated) hydrazines and selected adducts and their use as corrosion inhibitors
CN103261337A (en) Anti-corrosive compositions

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080130