DE102009059149A1 - Composition, useful e.g. as solvent pastes, comprises e.g. diaminediamide long-chain carboxylic acids, diamine monoamide, basic reaction products of e.g. dialkyldiamines, polyamines and/or alkanolamines, and free long chain carboxylic acid - Google Patents

Abstract

Composition comprises: (a) diaminediamide long-chain carboxylic acids (40-90%); (b) diamine monoamide long-chain carboxylic acids (0-10%); (c) basic reaction products of dialkyldiamines, polyamines and/or alkanolamines and long-chain carboxylic acids (0-20%); (d) free long-chain carboxylic acids (0-20%); and (e) optionally partial esters of glycerol and long chain carboxylic acids (0-20%), where the amount of (b) and (c) is sufficiently high to achieve an amine value of 10, and the amount of (d) is sufficiently high to achieve an acid number of >= 10.

Description

Object of the invention:

The The invention relates to a composition of long-chain carboxylic acids and their derivatives for adjusting viscosity and surface properties of coating systems such as aqueous or solvent-based Paints and coatings and bitumen systems for the production of asphalt.

State of the art:

The cationic compounds - fatty amines and fatty amine derivatives, Amidoamines - possess compared to anionic and nonionic Surfactants have a pronounced substantivity opposite almost all solid surfaces. These Substantivity is the special property, by a firmly applying a cationic film to a solid its properties in the desired application technology

• • Korrosionsschutzmitteln für ölige und wässrige Medien, Schmiermittel
• • Wäschenachbehandlungsmitteln, Antistatika
• • Haft- und Netzmitteln für Lacke, Anstrichmittel, Klebstoffe, Dispersionen und Bitumen
• • Textil-, Leder-, Färberei-, Waschhilfsmitteln, Hilfsmitteln für die Gummiindustrie
• • Haarkonditioniermitteln und Desinfektionsmitteln
• • Flotation- und Antibackmitteln etc.

To be able to adjust meaning. This can be very specific performance properties of wool, hair, leather, cotton, synthetic fibers, plastics, pigments, rocks, metals
etc. with the cationic formulations based on fatty amine. The substantivity-based versatile applications are, for example, in

• • Corrosion inhibitors for oily and aqueous media, lubricants
• • Aftertreatment agents, antistatic agents
• • Adhesives and wetting agents for coatings, paints, adhesives, dispersions and bitumen
• • Textile, leather, dyeing, washing aids, auxiliaries for the rubber industry
• Hair conditioners and disinfectants
• • flotation and anti-caking agents etc.

It These are amines or amidoamines, their ethoxylates or Hydrochlorides or acetates, liquid, pasty or low-melting solids, the excellent wetting behavior and in the form of their acetates or hydrochlorides also can be used in aqueous form. she usually form soft flexible films and also act as a plasticizer for binders.

Examples of such applications are in Surfactant Science Series, Volume 34, ISBN 0-8247-8381-6 and references cited therein. For flotation applications z. The monoamide of DETA (diethylenetriamine), or amidoamines of AEP (aminoethylpiperazine) or polyamines in the form of hydrochlorides or acetates, References Br. Pat 578694 ; USSR Patent 1225619 ; Glembotski, in "Flotation, Primary Sources" New York 1972 ; US Patent 4234414 , For use in bitumen or for the production of asphalt are mentioned as references: amidoamines as emulsifiers, condensates of fatty acids and polyamines such as DETA, Chem Abstr. 86: 19162b (1977) ; Patent 1449830 ; Patent patent 1602767 ; Chem Abstract: 82: 75443y (1975) ; DE patent 3313971 ; DE patent 3316906 ; US Patents 4461901 and 4462840 and 4597799 as the dimer fatty acid product US Patent 3259512 ,

Neutral derivatives such as the reaction products of ethylenediamine and tallow fatty acid are higher melting point products used as solids in coatings and paints as surface hardness enhancing particles. In bitumen they are used in addition to FT paraffins and montan wax derivatives to adjust the viscosity and the softening point. References to this EP patent 1452565 and DE patent 10224847 , The polarity is due to the low levels of free functionality, acid number <15 with simultaneously low amine number of <10 in DE 1024847 , SZ <8 and AZ <2 in the commercial products, very low. Web effect is based on these substances only on their viscosity-lowering effect.

It is therefore the task asked, a product or a composition which shows both good network characteristics, but none softening effect on the binder, the softening point of the binder rather still increases and at the same time still lowered the viscosity of the binder in the melt.

It was now surprisingly found that the reaction products of long-chain carboxylic acids with suitable mixtures from aliphatic primary diamines, aliphatic NN dialkyldiamines and / or polyamines with a suitable degree of conversion the required Show properties.

The result is products with high hardness, good grindability and good dispersing and wetting power. When used in asphalt production, the viscosity could be lowered, the softening point was raised even at comparatively low dosages of 1.5-2, for commercial products, 3% is recommended and the wetting of the rock and the adhesion of the bitumen with forced storage in water were included the simple storage in water> 60% and also in the bottle rolling test was the adhesion of the bitumen on the rock over the required 60%. These results were achieved with different rock qualities, but especially with acidic rocks. When used with basic basalt could be achieved in the wetting no improvement.

• A) Diamindiamiden langkettiger Carbonsäuren
• B) Diaminmonoamiden langkettiger Carbonsäuren
• C) Amidoaminen von Polyaminen oder Dialkyldiaminen oder Esteramide von Alkanolaminen langkettiger Carbonsäuren und
• D) freien langkettigen Carbonsäuren, gegebenenfalls noch
• E) Partialester von Glycerin und langkettigen Carbonsäuren

weit bessere Performance zeigen als die nach dem Stand der Technik in der Bitumenmodifizierung eingesetzten reinen Zusatzstoffe EBS, FT-Paraffine, Fettamine oder Amidoamine. Als Diamine sind Verbindungen der Struktur H₂N-(CHR₁)_y-(CH₂)_x-NH₂ geeignet wie z. B. Ethylendiamin, 1,3-Propandiamin, 1,2-Propandiamin, Hexamethylendiamin 1,6; Neopentandiamin, Octamethylendiamin 1,8. In der erfindungsgemäßen Zusammensetzung sind als Basiskomponente die Diamindiamide mit 50–94% und die Monoamide mit einem Anteil von 2–15% enthalten.The experiments show that the combination of

• A) Diaminediamides of long-chain carboxylic acids
• B) Diamino monoamides of long-chain carboxylic acids
• C) Amidoamines of polyamines or dialkyldiamines or esteramides of alkanolamines of long-chain carboxylic acids and
• D) free long-chain carboxylic acids, if necessary
• E) partial esters of glycerol and long-chain carboxylic acids

far better performance than the prior art used in the bitumen modification pure additives EBS, FT paraffins, fatty amines or amidoamines. As diamines compounds of the structure H ₂ N- (CHR ₁ ) _y - (CH ₂ ) _x -NH _{2 are} suitable such. Ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine 1.6; Neopentanediamine, octamethylenediamine 1,8. In the composition according to the invention, the basic component is the diaminediamides at 50-94% and the monoamides at 2-15%.

As dialkyldiamines are compounds of structure R ₂ R ₃ N- (CHR ₁ ) _y - (CH ₂ ) _x -NH ₂ such. B. dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine. The composition according to the invention contains the amides of long-chain carboxylic acids at 0-20%. Polyamines are z. B. Compounds of the structure H ₂ N - ((CHR ₁ ) _y - (CH ₂ ) _x -NHR ₁ ) z- (CHR ₁ ) _y - (CH ₂ ) _x -NH ₂ such as. B. diethylenetriamine, dipropylenetriamine, N- (2-aminoethyl) 1,3-propanediamine, N, N bis (aminopropyl) methylamine. In the composition according to the invention, the mono-, di- and triamides and their fatty acid soaps are contained in proportions of 0-20%. Alkanolamines are compounds such. As monoethanolamine, diethanolamine, aminoethylethanolamine, isopropanolamine, 3-aminopropanol-1,2- (2-aminoethoxy) ethanol. In the inventions to the invention composition, the amides and ester amides to 0-15% are included as long-chain carboxylic acids are natural or synthetic carboxylic acids, linear or branched, saturated or unsaturated with or without additional function> C8 suitable such. B. pure fatty acids, fatty acids from natural fats, mixed fatty acids, hydroxy fatty acids, tallow fatty acid, tallow fatty acid hardened, palm stearin, palm oil fatty acid, coconut fatty acid, castor fatty acid, 12-hydroxystearic acid wax acids, oxidized paraffins, oxidized waxes, oxidized polyethylenes. The acids can be used as pure substances, but preferably in mixtures with chain length distribution tailored to the application. They are both bound in the amides and esters before as well as bound in 5-20% proportion as free acids or in amine soaps.

compositions and test results are described in the following Examples listed. The influence was examined softening point, hardness, viscosity, the wetting behavior and the adhesion with simple and forced Storage in water. The properties are compared unmodified bitumen, modifications with EBS, and modifications with the compositions according to the invention.

Examples approach for the preparation of the invention Compositions Process description for the preparation of the above described compositions of the invention

The carboxylic acid / triglyceride mixture is melted, into the melt, the amine components are metered and the reaction mixture is stirred at 150-180 ° C until reaching the specified characteristics in acid number and amine number. The water of reaction is separated off. The final reaction mixture is then cooled and made up. For use as ultrafine powder is still ground to the predetermined particle distribution. Table 1 Comparative Example EBS components substance mol diamine ethylenediamine 1.00 carboxylic acid tallow 2.00

Product characteristics:

• Dropping point: 140 ° C
• Acid value: 5 mg KOH / g
• Amine number: 2 mg KOH / g

table 2 Example 1a components substance mol diamine ethylenediamine 1 N-Dialkylaminodiamin dimethylaminopropylamine 0.13 carboxylic acid tallow 2.15

Product characteristics:

• Dropping point: 138 ° C
• Acid value: 13 mg KOH / g
• Amine number: 18 mg KOH / g

Table 3 Example 1b components substance mol diamine ethylenediamine 1 N-Dialkylaminodiamin dimethylaminopropylamine 0.13 Carboxylic acid 1 C16 / C18 acid 1: 1 2.15

Product characteristics:

• Dropping point: 138 ° C
• Acid value: 13 mg KOH / g
• Amine number: 18 mg KOH / g

Table 4 Example 1c components substance mol diamine ethylenediamine 1 N-Dialkylaminodiamin dimethylaminopropylamine 0.13 Carboxylic acid 1 palm stearic 2.15

Product characteristics:

• Dropping point: 138 ° C
• Acid number: 14 mg KOH / g
• Amine number: 18 mg KOH / g

Table 5 Example 1d components substance mol diamine ethylenediamine 1.00 carboxylic acid tallow 1 Glycerinester palm stearin 0.5

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 9 mg KOH / g
• Amine number: 15 mg KOH / g

table 6 Example 2 components substance mol diamine ethylenediamine 1 N-Dialkylaminodiamin dimethylaminopropylamine 0.13 carboxylic acid 1 C16 / C18 Acid 1: 1 2 carboxylic acid 2 dimer fatty acid 0.06

Product characteristics:

• Dropping point: 125 ° C
• Acid value: 12 mg KOH / g
• Amine number: 17 mg KOH / g

Table 7 Example 3a components substance mol diamine ethylenediamine 0.9 polyamine diethylenetriamine 0.15 Carboxylic acid 1 C16 / C18 acid 1: 1 2.15

Product characteristics:

• Dropping point: 135 ° C
• Acid value: 11 mg KOH / g
• Amine number: 18 mg KOH / g

Table 8 Example 3b components substance mol diamine ethylenediamine 1 polyamine diethylenetriamine 0.12 Carboxylic acid 1 palm stearic 0.6 Glycerinester Tallow hardened 1

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 10 mg KOH / g
• Amine number: 14 mg KOH / g

Table 9 Example 4a components substance mol diamine ethylenediamine 0.9 polyamine dipropylenetriamine 0.13 carboxylic acid C16 / C18 acid 1: 1 2.1

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 12 mg KOH / g
• Amine number: 17 mg KOH / g

table 10 Example 4b components substance mol diamine ethylenediamine 0.9 N-Dialkylaminodiamin dimethylaminopropylamine 0.13 carboxylic acid 1 tallow hardened 2.1 carboxylic acid 2 dimer fatty acid 0.06

Product characteristics:

• Dropping point: 125 ° C
• Acid value: 12 mg KOH / g
• Amine number: 17 mg KOH / g

Table 11 Example 4c components substance mol diamine ethylenediamine 1 polyamine diethylenetriamine 0.12 Carboxylic acid 1 palm fatty acid 0.6 Glycerinester Tallow hardened 1

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 12 mg KOH / g
• Amine number: 17 mg KOH / g

Table 12 Example 5 components substance mol diamine ethylenediamine 0.9 alkyl polyamine N, N-dimethylaminopro-pandiamine 1,3 0.13 Carboxylic acid 1 C16 / C18 acid 1: 1 2.1

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 12 mg KOH / g
• Amine number: 17 mg KOH / g

Table 13 Example 6 components substance mol diamine ethylenediamine 0.9 polyamine dipropylenetriamine 0,075 N-Dialkylaminodiamin dimethylaminopropylamine 0,075 carboxylic acid Tallow fatty acid cured 2.45

Product characteristics:

• Dropping point: 121 ° C
• Acid value: 15 mg KOH / g
• Amine number: 21 mg KOH / g

table 14 Example 7 components substance mol diamine ethylenediamine 1 N-Dialkylaminodiamin dimethylaminopropylamine 0.1 alkanolamine diethanolamine 0.1 carboxylic acid palm stearic 0.6 Glycerinester tallow hardened 1

Product characteristics:

• Dropping point: 115 ° C
• Acid value: 8 mg KOH / g
• Amine number: 14 mg KOH / g

Table 15 Example 8a components substance mol diamine ethylenediamine 1 Carboxylic acid 1 Sebum / palm fatty acid 1: 1 2.1

Product characteristics:

• Dropping point: 139 ° C
• Acid value: 12 mg KOH / g
• Amine number: 13 mg KOH / g

Table 16 Example 8b components substance mol diamine ethylenediamine 0.9 carboxylic acid Tallow fatty acid cured 0.2 Glycerinester Hardened tallow fat 0.9

Product characteristics:

• Dropping point: 121 ° C
• Acid number: 14 mg KOH / g
• Amine number: 15 mg KOH / g

Table 13 Example 6 components substance mol diamine ethylenediamine 1 alkanolamine dipropylenetriamine 0.2 carboxylic acid palm stearic 2.6

Product characteristics:

• Dropping point: 115 ° C
• Acid value: 8 mg KOH / g
• Amine number: 14 mg KOH / g

Application testing

bitumen tests

commercial Bitumen 50/70 is mixed with the test substance at 180 ° C mixed for 15 minutes to form a homogeneous mixture is. The viscosity is measured with the fresh mixture and the specimens for the determination of the needle penetration number and the softening point.

• Asphaltprüfungen, Affinität (Flaschenrollprüfung): DIN EN 12697-11 bzw. TP Asphalt-Stb Teil 11

The test included commercially available EBS viscosity regulators and dimethylaminopropyl stearamide wetting agents.
Bitumen Preparation: DIN EN 12594 ; Needle penetration: DIN EN 1426 ; softening point: DIN EN 1427 Table 14 Characteristics of modified bitumen modifiers NPZ 1% NPZ 3% EP 1% EP 3% EBS 37 38 56 95.5 Example 1b 40 37 52 94 Example 2 40 41 52 83.5 Example 3a 41 42 52.4 89.5 Example 4a 43 45 52 74.2 Example 8b 39 38 52 94 Dimethylaminopropylstearamid 45 - 52 - unmodified 43 - 52 - Table 15 Bitumen characteristics with increasing additive quantity modifiers NPZ 1% NPZ 3% EP 1% EP 3% EBS 37 38 56 95.5 Example 1b 40 37 52 94 Example 2 40 41 52 83.5 Example 3a 41 42 52.4 89.5 Example 4a 43 45 52 74.2 Example 8b 39 38 52 94 Dimethylaminopropylstearamid 45 - 52 -

• Asphalt tests, affinity (bottle rolling test): DIN EN 12697-11 or TP Asphalt-Stb Part 11

In all examples show the inventive Compositions a high wetting of the rocks and in contrast to the EBS, the effect remains even after a long test period receive.

Asphalt tests with the pure wetting agent additive were not included in the investigations because, although an excellent network effect is achieved, the required softening point increase can not be realized. Dispersion Preparation: Approach: Example 1b 25 g Grinding powder with d90 <50 μm water 75 g acetic acid 2 g

The powder is stirred with a propeller stirrer into the acidified water. The dispersion is stable and can be well combined with aqueous binder systems. For comparison, pure EBS can not be incorporated into water without a high use of emulsifiers and wetting agents. Solvent paste: batch Example 1b 20 g toluene 80 g

The Composition of the invention is in toluene stirred, the mixture is heated and after dissolving the solid cooled again. It creates a fine uniform paste with solvent-based paints and printing inks can be combined.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - GB 578694 [0005]
• - RU 1225619 [0005]
• - US 4234414 [0005]
• FR 1449830 [0005]
• - FR 1602767 [0005]
• - DE 3313971 [0005]
• - DE 3316906 [0005]
• US 4461901 [0005]
• US 4462840 [0005]
• - US 4597799 [0005]
• - US 3259512 [0005]
• EP 1452565 [0006]
• - DE 10224847 [0006]
• - DE 1024847 [0006]

Cited non-patent literature

• - Surfactant Science Series, Volume 34, ISBN 0-8247-8381-6 [0005]
• - Glembotski, in "Flotation, Primary Sources" New York 1972 [0005]
• DETA, Chem Abstr. 86: 19162b (1977) [0005]
• - Chem Abstract: 82: 75443y (1975) [0005]
• - DIN EN 12594 [0032]
• - DIN EN 1426 [0032]
• - DIN EN 1427 [0032]
• - DIN EN 12697-11 [0032]

Claims (12)

Composition of long-chain carboxylic acids and their derivatives for adjusting the viscosity and surface properties of coating systems, such as aqueous or solvent-based paints and coatings and bitumen systems for the production of asphalt, characterized in that they are contained in the composition A) Diaminediamides of long-chain carboxylic acids 40-90% B) Diamine monoamides of long-chain carboxylic acids 0-10% C) basic reaction products of dialkyldiamines and / or Polyamines and / or alkanolamines and long-chain carboxylic acids 0-20% D) free long-chain carboxylic acids, 0-20% E) optionally also partial esters of glycerol and long-chain carboxylic acids 0-20% which give 100% in the addition, and that the content of component B and C is sufficiently high to reach an amine value> / = 10, and the content of D is sufficiently high to reach an acid value> / = 10. A composition according to claim 1, characterized in that are used as diamines compounds of the structure H ₂ N- (CHR ₁ ) _y - (CHR ₁ ) _x -NH ₂ , where R ₁ = short-chain alkyl such as methyl, ethyl, propyl, butyl, cyclohexyl or H, and y and x are values of 1 to 8 and do not exceed 10 in the addition. Composition according to claim 2, characterized in that that as diamines ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, Hexamethylenediamine 1.6; Neopentanediamine, octamethylenediamine 1.8 serve. Composition according to claim 2, characterized in that that the diaminediamides in a proportion of 40 to 90% and the monoamides contained in a proportion of 0-10%. A composition according to claim 1, characterized in that as dialkyldiamines compounds of the structure R ₂ R ₃ N- (CHR ₁ ) _y - (CH ₂ ) _x -NH ₂ are used, wherein R ₁ , R ₂ , R ₃ = short-chain alkyl such Methyl, ethyl, propyl, butyl, cyclohexyl or H, and y and x are from 1 to 8 and in the addition do not exceed 10. Composition according to claim 5, characterized in that in that the dialkyldiamines are dimethylaminopropylamine, diethylaminoethylamine, or diethylaminopropylamine. A composition according to claim 1, characterized in that as polyamines compounds of the structure H ₂ N - ((CHR ₁ ) y- (CH ₂ ) _x -NR ₁ ) z- (CHR ₁ ) _v - (CH ₂ ) _w -NR ₂ R ₃ , wherein R ₁ , R ₂ , R ₃ = short-chain alkyl such as methyl, ethyl, propyl, butyl, cyclohexyl or H, and y, x, v, z and w are from 1 to 8 and in the addition of 15 do not exceed. Composition according to claim 7, characterized in that that as polyamines diethylenetriamine, dipropylenetriamine, N- (2-aminoethyl) 1,3-propanediamine, N, N bis (aminopropyl) methylamine, or N, N-dimethyldipropylenetriamine serve. Composition according to claim 1, characterized in that that as alkanolamines compounds monoethanolamine, diethanolamine, Aminoethylethanolamine, isopropanolamine, 3-aminopropanol-1,2- (2-aminoethoxy) ethanol be used. Composition according to Claim 1 in that as long-chain carboxylic acids natural or synthetic carboxylic acids, linear or branched, saturated or unsaturated with or without additional Function> C8 as pure substances or mixtures thereof adapted to the application Chain length distribution can be set. Composition according to Claim 10, characterized in that pure fatty acids, fatty acids from natural fats, mixed fatty acids, hydroxyfatty acids, tallow fatty acid, tallow are used as long-chain carboxylic acids fatty acid cured, palm fatty acid, coconut fatty acid, castor fatty acid, 12-hydroxystearic acid, wax acids, oxidized paraffins, oxidized waxes, and / or oxidized polyethylenes. Use of a composition according to one of Claims 1 to 11 in bitumen, asphalt, aqueous Dispersions and / or solvent pastes.