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EP0306801B1 - Utilisation de dispersions aqueuses pour le décapage à air comprimé - Google Patents

Utilisation de dispersions aqueuses pour le décapage à air comprimé Download PDF

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Publication number
EP0306801B1
EP0306801B1 EP88114106A EP88114106A EP0306801B1 EP 0306801 B1 EP0306801 B1 EP 0306801B1 EP 88114106 A EP88114106 A EP 88114106A EP 88114106 A EP88114106 A EP 88114106A EP 0306801 B1 EP0306801 B1 EP 0306801B1
Authority
EP
European Patent Office
Prior art keywords
acid
diisocyanate
primer
blasting
und
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
Application number
EP88114106A
Other languages
German (de)
English (en)
Other versions
EP0306801A2 (fr
EP0306801A3 (en
Inventor
Jürgen Dr. Schwindt
Dieter Dipl.-Ing. Kuron
Manfred Schoenborn
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to AT88114106T priority Critical patent/ATE75438T1/de
Publication of EP0306801A2 publication Critical patent/EP0306801A2/fr
Publication of EP0306801A3 publication Critical patent/EP0306801A3/de
Application granted granted Critical
Publication of EP0306801B1 publication Critical patent/EP0306801B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C11/00—Selection of abrasive materials or additives for abrasive blasts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C7/00—Equipment for feeding abrasive material; Controlling the flowability, constitution, or other physical characteristics of abrasive blasts

Definitions

  • the invention relates to the use of aqueous dispersions based on a carboxyl group-containing binder, the carboxyl groups of which are at least partially neutralized, for compressed air blasting.
  • wet blasting This process, referred to as "wet blasting", has been improved by introducing the liquid in the form of a mist into the air flow so that the necessary amount of liquid could be reduced (“wet blasting", DE-OS 2 724 318).
  • the object of the invention was therefore to find additives for compressed air jets which should combine a good binding of the resulting dusts with good disposal options with a simultaneously highly effective provisional corrosion protection.
  • organic binders containing carboxyl groups the carboxyl groups of which have been at least partially neutralized with certain amines, solve the problem described.
  • the invention relates to the use of an aqueous dispersion based on organic binder, the carboxyl groups (before neutralization) correspond to an acid number of 40 to 70 and at least 60, preferably at least 70%, in particular at least 80% by a tertiary amine formula NR1R2R3, wherein R1, R2, R3 independently of one another C1-C6-alkyl, C6-C12-aryl, hydroxy-C2-C3-alkyl mean, are neutralized for compressed air blasting.
  • aqueous dispersions to be used according to the invention in addition to the primarily desired binding of the dust by the permanent dust binding, permit unproblematic disposal, offer surprisingly good temporary corrosion protection and are compatible with subsequent corrosion protection coatings.
  • Suitable organic binders for the dispersions to be used according to the invention are preferably (1) oil-free polyesters, (2) alkyd resins, (3) acrylate resins and (4) polyurethanes.
  • Oil-free polyesters (1) and alkyd resins (2) are understood to be polycondensates of the type produced from alcohols and carboxylic acids by polycondensation by known processes, of the type described, for example, in Römpp's Chemielexikon, Vol. 1, p. 202, Frankh'sche Verlagbuch Stuttgart, 1966 or described in DH Solomon, The Chemistry of Organic Filmformers, pp. 75-101, John Wiley & Sons Inc., New York, 1967.
  • alkyd resins are understood to mean fatty acid- or oil-modified polyesters.
  • Preferred acid components for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids, with 2 to 14, preferably 4 to 12 C- Atoms per molecule or their esterifiable derivatives (for example anhydrides or esters), for example phthalic anhydride, isophthalic acid, tetrahydro- and hexahydrophthalic anhydride, endomethylene tetrahydrophthalic acid, succinic acid, glutaric acid, trimellitic acid, trimellitic acid, trimellitic acid Phthalic anhydride is the most common acid component.
  • Preferred alcohols for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic and / or araliphatic alcohols with 1-15, preferably 2-6 C atoms, and 1-6, preferably 1-4, of non-aromatic C-bonded OH groups per molecule, e.g.
  • Glycols such as ethylene glycol, 1,2-propanediol and -1,3, 1,2-butanediol, 1,3 and -1,4, 1,3-2-ethylpropane, 1,3-2-ethylhexane, neopentyl glycol, 2,2-trimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1,4, 1,2- and 1,4-bis (hydroxymethyl) cyclohexane, adipic acid bis (ethylene glycol ester) ); Ether alcohols such as di- and triethylene glycol, dipropylene glycol; Dimethylolpropionic acid, oxalkylated bisphenols with 2 C2-C3-oxalkyl groups per molecule, perhydrogenated bisphenols; 1,2-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, trimethyl
  • Monocarboxylic acids preferred for the preparation of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 3-24 carbon atoms per molecule, such as benzoic acid, p-tert-butylbenzoic acid, tolylic acid, hexahydrobenzoic acid , Abietic acid and lactic acid.
  • the alkyd resins (2) or polyester (1) can also monohydric alcohols with 1 to 8 carbon atoms such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts up to 15 wt .-%, based on alkyd resin (2) or polyester (1), condensed in. It is also possible to replace up to 25% of the ester bonds with urethane bonds.
  • Polyisocyanates preferably diisocyanates, are suitable for introducing these urethane bonds.
  • Preferred diisocyanates for this purpose are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates, as described, for example, by W.
  • the length of the oil in the alkyd resins (2) is generally 5 to 50, preferably 20 to 40,% by weight.
  • the drying or non-drying fatty acids which generally contain 6 to 24 carbon atoms, can be used either as such or in the form of their glycerol esters (triglycerides).
  • Vegetable and animal oils, fats or fatty acids such as e.g. Coconut, peanut, castor, wood, olive, soybean, linseed, cottonseed oil, safflower oil or oil fatty acids, dehydrated castor oil or fatty acid, monounsaturated fatty acids, lard, tallow and tears, tall oil fatty acid and synthetic fatty acids, which can be made from natural unsaturated oils or fatty acids by conjugation or isomerization.
  • Preferred saturated fatty acids are e.g. Coconut oil fatty acids, 2-ethylhexanoic acid, isononanoic acid (3,4,4-trimethylhexanoic acid) as well as palmitic and stearic acid.
  • the number average molecular weight of the polyester (1) or alkyd resin (2) is 2000 - 10,000 (up to molecular weights of 5000 determined by vapor pressure osmometry in dioxane and acetone, whereby the lower value is considered correct if the values differ; for molecular weights over 5000 membrane osmometric determined in acetone).
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ("isophorone diisocyanate"), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanate dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4- and 2,6-diisocyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-diphenylpropane - (2,2), p-xylylene diisocyanate and ⁇ , ⁇ ,
  • polyfunctional polyisocyanates known per se in polyurethane chemistry or else modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
  • polyisocyanates examples include tris (6-isocyanatohexyl) biuret, optionally in a mixture with its higher homologues, tris (6-isocyanatohexyl) isocyanurate, optionally in a mixture with its higher homologues, as described, for example, in DE-OS 28 39 133 is accessible by trimerizing hexamethylene diisocyanate, and further by trimerizing aliphatic and / or aromatic diisocyanates, such as.
  • "Isophorone diisocyanate" diisocyanatotoluene and hexamethylene diisocyanate available, isocyanurate group-containing polyisocyanates as they belong to the known prior art.
  • polyisocyanates are the polyisocyanates known per se, such as those obtained by reacting excess amounts of 2,4-diisocyanatotoluene or "isophorone diisocyanate" with simple polyhydric alcohols in the molecular weight range 62 to 300, in particular with trimethylolpropane, and subsequent distillatives Removal of the unreacted excess diisocyanate can be obtained.
  • the hydroxyl-containing polyesters are z. B. Reaction products of preferably polyhydric, particularly preferably dihydric and optionally additionally trihydric alcohols with preferably polybasic, particularly preferably dibasic carboxylic acids. Instead of the free carboxylic acids, the corresponding carboxylic acid anhydrides or corresponding carboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • the alcohols to be used as the polyester construction component are e.g. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butanediol (1,4), hexanediol (1,6), neopentyl glycol, octanediol (1,8), 2-ethyl-hexanediol - (1,3), 1,4-bishydroxymethylcyclohexane, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerin and pentaerythritol.
  • B ethylene glycol, propylene glycol (1,2) and - (1,3)
  • butanediol (1,4) hexanediol (1,6), neopentyl glycol, octanediol (1,8), 2-ethyl-hexanediol - (1,3), 1,4-bishydroxymethylcycl
  • the blocking agents can be used alone or as mixtures.
  • Preferred blocking agents are ⁇ -caprolactam, butanone oxime and diethyl malonate.
  • polyurethane prepolymers (component I) suitable as polyisocyanates I can be prepared by customary methods be prepared in accordance with the prior art, for example by reacting polyisocyanates (i) with higher molecular weight polyols (ii) and low molecular weight polyols (iii), the molar ratio of the isocyanate groups of the polyisocyanate (i) to the hydroxyl groups of the polyols (ii) and ( iii) can be from 1.5 to 3.0.
  • the resulting polyurethane prepolymers with free isocyanate groups are then reversibly blocked with suitable monofunctional compounds (iv) to block the isocyanate groups.
  • the structure of polyurethane prepolymers (I) is described, for example, in German Pat. No. 1,644,813.
  • Component I comprises both reaction products of the polyisocyanates (I) and blocking agents (iv) and blocked polyisocyanate prepolymers based on the above-mentioned compounds (i) and (ii) and / or (iii).
  • the polymers (component II) containing H atoms which are reactive with isocyanate groups are polyester or polyether polyols, polyhydric low molecular weight alcohols, polyamines, polyepoxypolyols, polyhydroxy acrylates or any mixtures of the products mentioned.
  • the polyester polyols and polyether polyols are compounds of the type known per se in polyurethane chemistry with number average molecular weights M n from 300 to 10,000, preferably 300 to 5,000. they are preferably formed from the structural components (ii) of the polyurethane prepolymers (I) described above.
  • the low molecular weight alcohols are polyalcohols of the known type with at least 2 hydroxyl groups per molecule and molecular weights between 62 and 300.
  • the polyamines in question are preferably di- or polyfunctional aliphatic or cycloaliphatic amines such as 1,2-diaminoethane, tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine, 1,4-diaminocyclohexane, 1,4-bis-aminomethyl-cyclohexane, "isophorone” diamine, 4,4'-diamino-dicyclohexylmethane, 2,2-bis (4-amino-cyclohexyl) propane or m- or p-xylylenediamine. 4,4'-Diamino-3,3'-dimethyl-dicyclohexylmethane is particularly preferred.
  • Components (I) and (II) are preferably used in amounts such that the molar ratio of blocked isocyanate groups to hydroxyl and / or amino groups is 0.5 to 2, preferably 0.8 to 1.5.
  • dimethylolpropionic acid is preferably used in the preparation of the polyurethanes (4).
  • the organic binders suitable for the aqueous dispersions to be used according to the invention are preferably selected so that they are at least temporarily sticky. In other words, you should Have the property of binding them to their surface under practical conditions when they collide with the abrasive used as "sand" and the particle blasted off the substrate.
  • a droplet of binder would be completely surrounded by dust particles.
  • Tertiary aines preferred for neutralizing the carboxyl groups of the organic binders include, for example, triethyl, tripropyl and tributylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, methyldipropanolamine, dimethylpropanolamine, tripropanolamine, N, N-dimethylaniline. Tripropylamine and dimethylethanolamine are particularly preferred amines.
  • the water content of the aqueous dispersions to be used according to the invention is 60 to 95, preferably 85 to 93,% by weight, based on the aqueous dispersion.
  • the dispersions to be used according to the invention are preferably introduced in countercurrent to the blasting material, so that an optimal distribution is ensured and they reach the surface to be blasted with the blasting material in the finest distribution.
  • Salt spray test Condensation test ⁇ 190 x 106 mm Salt dissolving station 330 x 165 mm.
  • 256 g of precondensate from 0.077 mol of soybean oil fatty acid, 0.43 mol of trimethylolpropane, 0.87 mol of 1,6-hexanediol, 0.5 mol of adipic acid and 0.5 mol of isophthalic acid are mixed with 21.7 g of dimethylolpropionic acid, 72 g of isophorone diisocyanate, 52.5 g N-methylpyrrolidone, 10.3 g dimethylethanolamine and water processed to an aqueous dispersion with a solids content of 7 wt .-%.
  • the resulting dust consisting of rust and old coating, was irreversibly bound together with the blasting slag.
  • the material could be swept up and removed with the broom without raising dust.
  • test panels were coated according to the following criteria:
  • the subsequent coatings were applied every 24 hours.
  • the paints were applied in such a way that the behavior of the coatings on one, two and three layers can be assessed.
  • the paints were processed by spray application.
  • the table above shows that the invention leads to at least the same coating quality as the prior art (the advantage being the problem-free removal of rust, old coating and blasting agent).
  • a comparison of the last two columns in the table shows the corrosion protection surprisingly obtained by the binder used.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Sealing Material Composition (AREA)
  • Prevention Of Fouling (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Special Spraying Apparatus (AREA)
  • Toys (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (4)

  1. Utilisation d'une dispersion aqueuse à base d'un liant organique dont les groupes carboxyle (avant la neutralisation) correspondent à un indice d'acide de 40 à 70 et sont neutralisés au moins à 60 % par une amine tertiaire de formule



            NR¹R²R³,



    dans laquelle
       R¹, R², R³ représentent, indépendamment les uns des autres, un groupe alkyle en C₁ à C₆, aryle en C₆ à C₁₂, hydroxyalkyle en C₂ ou C₃,
       pour le décapage à l'air comprimé.
  2. Utilisation suivant la revendication 1, caractérisée en ce que les groupes carboxyle sont neutralises à 70 % au moins.
  3. Utilisation suivant la revendication 1, caractérisée en ce que les groupes carboxyle sont neutralisés à 80 % au moins.
  4. Utilisation suivant les revendications 1 à 3, caractérisée en ce que l'amine tertiaire est choisie dans le groupe comprenant la tripropylamine et la diméthyléthanolamine.
EP88114106A 1987-09-10 1988-08-30 Utilisation de dispersions aqueuses pour le décapage à air comprimé Expired - Lifetime EP0306801B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88114106T ATE75438T1 (de) 1987-09-10 1988-08-30 Verwendung waessriger dispersionen fuer das druckluftstrahlen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3730320 1987-09-10
DE19873730320 DE3730320A1 (de) 1987-09-10 1987-09-10 Verwendung waessriger dispersionen fuer das druckluftstrahlen

Publications (3)

Publication Number Publication Date
EP0306801A2 EP0306801A2 (fr) 1989-03-15
EP0306801A3 EP0306801A3 (en) 1990-10-24
EP0306801B1 true EP0306801B1 (fr) 1992-04-29

Family

ID=6335651

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88114106A Expired - Lifetime EP0306801B1 (fr) 1987-09-10 1988-08-30 Utilisation de dispersions aqueuses pour le décapage à air comprimé

Country Status (4)

Country Link
EP (1) EP0306801B1 (fr)
AT (1) ATE75438T1 (fr)
DE (2) DE3730320A1 (fr)
ES (1) ES2036637T3 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460296A (en) * 1966-10-24 1969-08-12 Xerox Corp Metalworking
DE2724318C2 (de) * 1977-05-28 1984-09-20 Ernst Peiniger GmbH Unternehmen für Bautenschutz, 4300 Essen Verfahren zum Befeuchten des Strahlmittels beim Druckluftstrahlen
DE3127035A1 (de) * 1981-07-09 1983-01-27 Ernst Peiniger GmbH Unternehmen für Bautenschutz, 4300 Essen "verfahren zum druckluftstrahlen"
DE3415174A1 (de) * 1984-04-21 1985-10-31 Ernst Peiniger GmbH Unternehmen für Bautenschutz, 4300 Essen Verfahren zum druckluftstrahlen
GB8425539D0 (en) * 1984-10-10 1984-11-14 Brent Chemicals Int Abrading surfaces

Also Published As

Publication number Publication date
EP0306801A2 (fr) 1989-03-15
DE3730320A1 (de) 1989-03-30
DE3870554D1 (de) 1992-06-04
EP0306801A3 (en) 1990-10-24
ATE75438T1 (de) 1992-05-15
ES2036637T3 (es) 1996-07-16

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