DE1445857C - Tnsamino s tnazin derivatives, process for their preparation and their use - Google Patents

Description

R ₄

R ₁ and R _{3 are} hydrogen atoms or alkyl or alkenyl radicals with 1 to 20 carbon atoms,

R _{2 is} an alkyl or alkenyl radical with 1 to 20 carbon atoms which is optionally substituted by one or two hydroxyl groups,

R _{4 is} an alkyl or alkenyl radical with 10 to 20 carbon atoms which is optionally substituted by one or two hydroxyl groups,

Q is a divalent alkylene or alkenylene radical having 1 to 20 carbon atoms and
Y denotes a carboxyl or sulfo group and a carboxyl group esterified with an alkanol with a maximum of 18 carbon atoms, 2-hydroxyethylammonium chloride or 1-hydroxy-2-methylpropyl- (2) -ammonium chloride,

20th

25th

30th

as well as the metal and ammonium salts.

2. ll - ^ '^' - bis-n-octadecylamino-s-triazinyl- (6 ') -amino] -undecylic acid and their metal and ammonium salts.

3. 11 - [2 ', 4' - bis - η - octadecenylamino - s - triazinyl (6 ') - amiho] undecylic acid and their metal and ammonium salts.

4. 11 - [2'-Propylamino -4 '-octadecylaminos-triazinyl- (6') -amino] -undecylic acid and their metal and ammonium salts.

5. 11 - r_2 ', 4' - bis - dioctadecylamino - s - triazinyl (6 ') - amino] undecylic acid and their metal and 45 wherein ammonium salts.

6. Process for the preparation of trisaminos-triazine derivatives according to claim 1, characterized in that characterized in that one in a conventional manner cyanuric chloride successively with 1 mol of an amine of the general formulas II, III and IV The present invention relates to trisamino-s-triazine derivatives, a process for the preparation of these compounds and the use of these compounds for the production of coatings.

In the present context, the term "compounds serving to produce coatings" includes Description to understand compounds created by creating a coating for protection and enhancement the physico-chemical properties of all types of surfaces can be used, such as surfaces made of inorganic materials, e.g. B. metal, stone or stoneware, and organic Materials, e.g. B. wood, leather, plastics such as linoleum, textiles and paper.

It has been found that trisamino-s-triazine derivatives of the general formula I.

NH-Q-Y

(I)

N-

R ₄

NH

/
NH

R ₂
R ₃

(Π)

(III)

55

60

NH

R ₄
H

(IV)

Q-Y

R ₁ and R _{3 are} hydrogen atoms or alkyl or alkenyl radicals with 1 to 20 carbon atoms,

R _{2 is} an alkyl or alkenyl radical with 1 to 20 carbon atoms which is optionally substituted by one or two hydroxyl groups,

R _{4 is} an alkyl or alkenyl radical with 10 to 20 carbon atoms which is optionally substituted by one or two hydroxyl groups,
Q is a divalent alkylene or alkenylene radical having 1 to 20 carbon atoms and,
Y denotes a carboxyl or sulfo group and a carboxyl group esterified with an alkanol with a maximum of 18 carbon atoms, 2-hydroxyethylammonium chloride or 1-hydroxy-2-methylpropyl- (2) -ammonium chloride,

as well as the metal and ammonium salts have waxy properties and are excellent for production suitable for coatings.

To prepare the trisaminos-triazine derivatives according to the invention, a method known per se is used Way 2,4,6-trichloro-s-triazine with one mole each Amines of the general formulas II, III and IV

NH

NH

(III)

R ₄

/
NH

(IV)

Q-Y

in which R ₁ , R ₂ , R ₃ , R ₄ , Q and Y have the meanings given above, in any order

(__) follow if necessary in the presence of a proton acceptor and an inert gas, and, if desired, passes the reaction products obtained into their metal and ammonium salts.

2,4,6-Trichloro-s-triazine is preferably used first with an amine of the general formula II or III at 0 to 5 ° C. (exothermic reaction), then with an amine of the general formula III or II at 40 to 60 ° C and finally with an amine of the general formula IV at 150 to 175 ° C, the replacement of the third chlorine atom with an amine of the general formula IV preferably in the presence of a higher-boiling aliphatic hydrocarbon, e.g. B. a petroleum fraction from boiling point 160 to 175 ⁰ C, takes place as a solvent. Solvents used for the first and second stage are the solvents customary for the reactions of cyanuric chloride with amines, such as water, chloroform, mixtures of acetone and water and other mixtures of organic solvents with water.
The represented by Q in the general formula I

ζ ~ \ presented alkylene or alkenylene groups are preferential

^^ wise straight-chain.

The trisamino-s-triazine derivatives of the general formula I, in which Y is a carboxyl or sulfo group represents, can in the form of their metal and ammonium salts, preferably their alkali metal salts, isolated will.

The trisamino-s-triazine derivatives of the general formula I have well-defined, relatively high melting points; they can therefore be used instead of natural waxes or together with the latter to produce the ίο physico-chemical properties of surfaces all types of enhancing coatings can be used. They have those characteristic of natural waxes Properties such as solubility in fat solvents, miscibility with natural and synthetic waxes, formation of pastes and gels with organic solvents, in particular with light gasoline, gloss formation after light rubbing, etc. The new compounds result in relative hard waxes with excellent gloss and are resistant to chemicals, especially good alkali-resistant. In their excellent suitability as waxes, they are similar to the montanic acid esters.

To produce coatings, the inventive Trisamino-s-triazine derivatives of the general formula I with others for treatment common substances suitable for surfaces are mixed. Such substances are for example natural and synthetic waxes, resins or silicones that change the physical properties improve, as well as solvents, also inorganic and organic fillers, z. B. Silicates, ground Plastics, anionic, cationic or nonionic dispersants, cleaning agents, such as natural ones and synthetic soaps, tensio-active substances, pigments, agents to improve light resistance, Stabilizers of all kinds, such as corrosion inhibitors, odorants, dyes, biocidal agents, such as insecticides, fungicides or bactericides.

Such agents can be in the form of aerosols, solutions, emulsions, semi-solid and solid pastes are available and applied.

For the production of coatings and for the production of such coatings-producing agents the following trisamino-s-triazine derivatives of the formula I are used:

No. Q-Y R ₁ R ₂ R ₃ HC ₁₈ H ₃₇ M.p. ⁰ ° C 1 -CH ₂ COOH H UC ₁₈ H ₃₇ H nC ₁₈ H ₃₇ 147 to 148. 2 - CH ₂ COONa H nC ₁₈ H ₃₇ H HC ₁₈ H ₃₇ , 268 3 - C ₅ H ₁₀ COOH H HC ₆ H ₁₃ H U-Cj ₈ H ₃₇ 94 to 96 4th - - C ₅ H ₁₀ COOk H HC ₆ H ₁₃ H 11-C ₁₈ H ₃₇ 150 to 152 5 -C ₅ H ₁₀ COOH ''"'' H UC ₁₈ H ₃₇ H UC ₁₈ H ₃₇ 136 6th - C ₅ H ₁₀ COONa H nC ₁₈ H ₃₇ H HC ₁₈ H ₃₇ 148 to 150 7th -C ₁₀ H ₂₀ COONa 11-C3H7 nC ₃ H ₇ H UC ₁₈ H ₃₇ ' 166 to 168 8th -C ₁₀ H ₂₀ COOH II-C4H9 UC ₄ ed . H HC ₁₈ H ₃₇ 50 to 52 9 - C ₁₀ H ₂₀ COONa nC ₄ H ₉ nC ₄ H ₉ H HC ₁₈ H ₃₇ 154 to 156 10 -C ₁₀ H ₂₀ COOK II-C4H9 n-QH ₉ H nC ₁₈ H ₃₇ 164 to 166 11th - C ₁₀ H ₂₀ COOH H nC ₁₂ H ₂₅ H HC ₁₈ H ₃₇ 82 to 83 12th - C ₁₀ H ₂₀ COONa H nC ₁₂ H ₂₅ H , HC ₁₈ H ₃₇ - ¹ 132 to 134 13th -C ₁₀ H ₂₀ COOH UC ₁₂ H ₂₅ HQ ₂ H ₂₅ H nC ₁₈ H ₃₇ 54 to 56 14th -C ₁₀ H ₂₀ COONa nC | ₂ H ₂₅ HC ₁₂ H ₂₅ H 11-C ₁₂ H ₂₅ 78 to 80 15th - C ₁₀ H ₂₀ COOH nC ₁₂ H ₂₅ HC ₁₂ H ₂₅ 11-Q ₂ H ₂₅ H-Ci ₂ H ₂₅ 65 16 - C ₁₀ H ₂₀ COONa UC ₁₂ H ₂₅ nC ₁₂ H ₂₅ HQ ₂ H ₂₅ H-Cj ₈ H ₃₇ 92 to 94 17th -C ₁₀ H ₂₀ COOH H HQ ₆ H ₃₃ ^{: H} nQ ₈ H ₃ , 82 to 83 18th - C ₁₀ H ₂₀ COONa H HC ₁₆ H ₃₃ H UC ₁₈ H ₃₇ 124 to 126 19th -C ₁₀ H ₂₀ COONa H UC ₁₈ H ₃₇ H HC ₁₈ H ₃₇ 188 to 190 20th - C ₁₀ H ₂₀ COOK H 11-C ₁₈ H ₃₇ H 162 to 164

continuation

No. Q-Y R, R ₂ R ₃ R ₄ M.p. ⁰ ° C 21 -C ₁₀ H ₂₀ COOCaOH H "-C ₁₈ H ₃₇ H 1-Q ₈ H ₃₇ 230 22nd (- C ₁₀ H ₂₀ COO) ₂ AlCl (H) ₂ (nC ₁₈ H ₃₇ ) ₂ (H) ₂ (UC ₁₈ H ₃₇ ), 104 to 106 23 - C ₁₀ H ₂₀ COOC ₂ H ₄ NH ₂ HC] H "1-Q ₈ H ₃₇ H 1-C ₁₈ H ₃₇ 78 to 79 NH ₂ 24 - C ₁₀ H ₂₀ COOCH ₂ - C - CH ₃ HCl H UC ₁₈ H ₃₇ H nC ₁₈ H ₃₇ 125 to 127 25th CH ₃
- C ₁₀ H ₂₀ COOH CH ₃ nC ₁₈ H ₃₇ CH ₃ 1-C ₁₈ H ₃₇ 84 to 86 26th - C ₁₀ H ₂₀ COONa CH ₃ . "-C ₁₈ H ₃₇ CH ₃ 1-C ₁₈ H ₃₇ ' 148 to 152 27 - C ₁₀ H ₂₀ COOH 11-C ₁₈ H ₃₇ ■ nC _I8 H ₃₇ H 1-C ₁₈ H ₃₇ 72 to 74 28 - C ₁₀ H ₂₀ COONa nC ₁₈ H ₃₇ UC ₁₈ H ₃₇ H 1-C ₁₈ H ₃₇ 98 to 100 29 -C ₁₀ H ₂₀ COOH H UC ₁₈ H ₃₅ H 1-C ₁₈ H ₃₇ 78 (8-en) 30th - C ₁₀ H ₂₀ COONa H "-C ₁₈ H ₃₅
(8-en)
nC ₁₈ H ₃₅ H 1-C ₁₈ H ₃₇ 128 to 130 31 -C ₁₀ H ₂₀ COOH H HC ₁₈ H ₃₅ H 1-C ₁₈ H ₃₅ 52 to 54 32 - C ₁₀ H ₂₀ COONa H nC ₆ H ₁₃ H 1-C ₁₈ H ₃₅ 184 to 186 33 - C ₁₀ H ₂₀ COOH H nC ₆ H ₁₃ H 1-C ₁₈ H ₃₇ 70 to 72 34 -C ₁₀ H ₂₀ COONa H UC ₁₈ H ₃₇ H nC ₁₈ H ₃₇ 156 to 158 35 - C ₁₀ H ₂₀ COOH H nC ₁₈ H ₃₇ H 1-C ₁₈ H ₃₇ 104 36 ■ -C ₁₀ H ₂₀ COONa nC ₁₈ H ₃₇ HC ₁₈ H ₃₆ OH nC ₁₈ H ₃₇ 1-C ₁₈ H ₃₇ 50 to 52 37 - C ₁₀ H ₂₀ COOH H HC ₁₈ H ₃₅ (OH) ₂ H nC ₁₈ H ₃₆ OH 90 to 94 38 - C ₁₀ H ₂₀ COOH H nC _{! 8} H ₃₇ H HC ₁₈ H ₃₅ (OH) ₂ 80 to 82 39 -C ₁₀ H ₂₀ COOC ₂ H ₅ H Ji-Q ₈ H ₃₅ H 1-C ₁₈ H ₃₇ 70 to 72 40 -C ₁₀ H ₂₀ COOK H nC ₁₈ H ₃₇ H nC ₁₈ H ₃₇ 165 to 166 41 -C ₁₀ H ₂₀ COOC ₁₈ H ₃₇ H DC ₁₂ H ₂₅ H UC ₁₈ H ₃₇ ¹ 72 42 - C ₅ H ₁₀ COONa H nC ₁₂ H ₂₅ H 1-C ₁₈ H ₃₇ 150 to 152 43 - C ₅ H ₁₀ COOH . H nC ₁₈ H ₃₇ H 1-C ₁₈ H ₃₇ ■ 114 44 - C ₂ H ₄ - SO ₃ H H H 1-Ci ₈ H ₃₇ 196 to 198

Examples of typical application forms are given below. Parts mean in it Parts by weight.

example 1

5.25 parts of 11 - [2 ', 4' - bis - η - octadecylamino - s - triazinyl (6 ') - amino] undecylic acid sodium salt,

0.75 parts of vinyl octadecyl ether polymer (melting point: 49 ° C),

1.50 parts of microwax (melting point: 74/76 ° C;
Penetration ASTM 30),

7.50 parts paraffin (melting point: 50/52 ° C),

5.00 parts 1,4-dioxane,
80.00 parts of petroleum fraction (boiling limits: 150/180 ° C.).

The components are brought into solution at 120 ° C. and the clear solution rapidly with stirring cooled, resulting in a homogeneous gel-like liquid, which is a liquid floor wax with high gloss can be used.

B e i s ρ i e 1 2

3.15 parts of 6 - [2 ', 4' - bis - η - octadecylamino - s - triazinyl- (6 ') - amino] -caproic acid, sodium salt,

0.45 parts of polyvinyl stearate (melting point: 46/48 ° C), 0.90 part of microwax (melting point: 74/76 ° C;

Penetration ASTM 30),
4.50 parts paraffin (melting point: 50/52 ° C),
3.00 parts of diethylene glycol monoethyl ether,
48.00 parts of petroleum fraction (boiling range: 180 / 22O ⁰ C), 40.00 parts of dichlorodifluoromethane.

The solid or liquid components at normal temperature are ^{brought into solution at 120 °} C. and the solution is rapidly cooled while stirring. The resulting mixture is mixed with the propellant gas in a pressure vessel with a spray valve. The resulting sprayable mixture is ideally suited as a floor wax with good gloss and excellent shelf life.

Example 3

1.25 parts 11 - [2 ', 4' - bis - η - didodecylamino - s - tri-

azinyl- (6 ') -amino] -undecylic acid,
5.00 parts of dimethylpolysiloxane (viscosity: 300 cps / 2O ⁰ C),
1.25 parts of sorbitan monolaurate,

1.25 parts of polyoxyethylene sorbitan monolaurate,
43.75 parts of petroleum fraction (boiling limits: 180/220 ° C.), 47.50 parts of water.

The organic components are at 100 ⁰ C

brought into solution and added the boiling water to this hot solution while stirring vigorously.

The mixture is cooled while stirring, a homogeneous, white liquid being formed which is

. ideal for the care of furniture.

B e i s ρ i e 1 4

5.00 parts of II- [2'-n-octadecylamino-4'-di-n-octadecylamino - s - triazinyl - (6 ') - amino] undecylic acid,

15.00 parts perchlorethylene,
40.00 parts of trichlorofluoromethane,
40.00 parts dichlorodifluoromethane.

11 - [2 '- η - Octadecylamino - 4' - di - η - octadecylamino-s-triazinyl- (6 ') - amino] undecylic acid is dissolved in the perchlorethylene and this solution in a pressure vessel with a spray valve with the propellant gases (Trichlorofluoromethane and dichlorodifluoromethane) added. The resulting, sprayable mixture is ideal for achieving a beading effect on textiles, especially if the resulting, invisible covering is still being ironed.

Example 5

1.00 part microwax, partially oxidized (melting point: 82 ° C), penetration ASTM 7; Saponification number: 75/85),
2.00 parts 11 - [2 ', 4' - bis - didodecylamino - s - tri-

azinyl- (6 ') -amino] -undecylic acid,
2.00 parts of dimethylpolysiloxane (viscosity: 500 cps /

2O ⁰ C),

1.00 part sorbitan monolaurate,
1.00 part polyoxyethylene sorbitan monolaurate,
35.00 parts petroleum fraction (boiling point: 180/220 ° C), 38.00 parts water,
4.00 parts propane,
16.00 parts of butane.

20th

40

The solid and liquid organic components at normal temperature become in Brought solution and added the boiling water to this hot solution while stirring vigorously.

The mixture is cooled with stirring, placed in a pressure vessel with a spray valve and there with the propellant gases (propane and butane). The resulting sprayable mixture is suitable excellent for car body care and other shiny paintwork on metal.

Example 6

42.00 parts 11 - [2 '- η - Octadecylamino - 4' - η - octadecen- (8 ") - ylamino-triazinyl- (6 ') - amino] - undecylic acid,

5.00 parts of petroleum jelly,
26.00 parts spindle oil,

5.00 parts wool fat,

1.2 parts Viktoriablaubase,

0.6 parts methyl violet,

2.2 parts olein,

6.00 parts Milori blue,
12.00 parts of carbon black.

Carbon black, Milori blue and spindle oil are finely rubbed off on the pulp mill. About this mixture the other components are added and the mixture is heated to 120 ° C. with stirring until the preparation is homogeneous originated. With a heatable calender, this mixture becomes even and thin applied to one side of a suitable paper, thereby creating a suitable paper for making copies Carbon paper is created.

1.53 parts emulsifier of the fatty alcohol type

polyglycol ether,
67.66 parts of water,

b) 2.25 parts of phenol-formaldehyde resin, alkali-soluble,

0.67 parts of concentrated ammonia, 12.07 parts of water.

The components of mixture a), with the exception of the water, are melted at 150.degree and stirred to a homogeneous mixture. This mass is then cooled to 100 to 110 ° C, you the boiling water is added, and then it is cooled to room temperature. Man receives an emulsion to which mixture b) is added. The resulting emulsion is excellent for the care of modern floors.

Example 8

A floor wax consisting of 5.25 parts of gloss wax and 0.75 parts was applied to linoleum panels Vinyl octadecyl ether polymer, 1.50 parts of microwax, 7.50 parts of paraffin, 5.00 parts of 1,4-dioxane and 80.00 parts petrol, applied and blotted. After the bioching, the gloss measurement was carried out with 45 ° reflection in the device determined according to Lange and that of a mixture of gloss waxes of the montanic acid ester series (types OM and F).

B e i s ρ i e 1 7

a) 3.19 parts of 11 - [2 ', 4' - bis - η - octadecylaminos - triazinyl (6 ') - amino] - undecylic acid,' 3.19 parts of paraffin (melting point: 50/52 ° C),
6.38 parts wax of the montanic acid ester type

(Melting point: 80/83 ° C, acid number: 20/30, saponification number: 135/150),
1.70 parts olein,
1.36 parts aminomethylpropanol, gloss wax

Gloss in% of the gloss of the comparison wax (= 100%)

105 120

6- [2 ', 4'-bis-n-octadecylamino-s-ti ¹ razinyl- (6')] aminocaproic acid

11- [2 ', 4'-bis-n-octadecylamino-triazinyl- (6')] -amino-undecylic acid

Example 9

The following emulsion was applied to PVC floor slabs, Emulsion A consisting of:

45 4.250 parts of 11 - [2 ', 4' - bis - η - octadecenylaminos - triazinyl - (6 ') - amino] - undecylic acid,

4,250 parts of carnauba wax,

4.250 parts of petroleum wax (melting point 86 to 90 ° C; acid number 13 to 16, saponification number 45 to 55, penetration 4 to 6 at 100g / 25 ° C / 5sec),

0.850 parts olein,

0.765 parts of a fatty alcohol polyglycol ether emulsifier,

0.680 parts of aminomethylpropanol,

2,250 parts synthetic resin (of the rosin-modified phenolic resin type),

0.675 parts concentrated ammonia and 82.030 parts water and

Emulsion B the same composition as Emulsion A, except for the triazine derivative which ^v type Montansäureester by a commercially available wax (melting point 80 to 83 ⁰ C;. Saponification value 135-150, acid value 20 to 30) was replaced. The PVC floor panels treated with emulsions A and B were punched to determine the gloss and the adhesive strength.

209 537/575

Results

emulsion Gloss in%
that of a black one
Mirror (= 100%) Static friction in
Gram A.
B. 26th
27 50 to 60
30 to 40

Conclusion

IO

From the above results it can be seen that with the same gloss, the triazine wax according to the invention is a Significantly better static friction on PVC floor slabs than montan wax, which is essential equates to a lower risk of accidents due to slipping when walking on the surface.

Example 10

On PVC floor panels wax formulations were applied, consisting of 90% (weight percent) consisted of the following at 150 to 18O ⁰ C boiling petroleum fraction, and 10% wax types:

1. 11 - [2 '- Propylamino - 4' - octadecylamino - s - triazinyl - (6 ')] - amino undecyl acid Sodium,

2. 11 - (2 ', 4' - bis - dioctadecylamino - s - triazinyl - (6 ')] - amino undecyl acid Sodium,

3. montanic acid ester,

4. petroleum waxes,

5. carnauba wax;

6. synthetic hard paraffin.

The treated PVC flooring panels were left to dry and the self-luster of the was not braided

Wax type Gloss in% that one
black mirror) = 100%) .3. * ■ '·
4th
- 5th
6th OOOO

The triazine waxes 1 and 2 which can be used according to the invention give up on application PVC floor tiles without biting, high gloss values, while the commercially available waxes do not Show brilliance.

Example 11

Linoleum plates wax formulations were applied, consisting of 90% (weight percent) consisted of the following at 150 to 18O ⁰ C boiling petroleum fraction, and 10% wax types:

1. 11 - [2 ', 4' - bis - octadecylamino - s - triazinyl - (6 ')] - amino undecyl acid Sodium,

2. 11 - r_2 ', 4' - bis - 8 (9) - hydroxy - octadecylaminos-triazinyl- (6 ')] - amino-undecylic acid,

3. Carnauba wax.

The treated linoleum sheets were allowed to dry and punched. The shine was in the device determined by Lange and with that of the carnauba wax formulation (= 100%) compared.

Deposits in the device determined by Lange.
Results 35 Wax type Results 1
2
3 Wax type 40 Gloss in% that one
black mirror (= 100%) Gloss in% that of the
Carnauba wax 1
2 27
25th 220
140
100

Claims (1)

Patent claims: 1. Trisamino-s-triazine derivatives of the general formula I. NH-Q-Y (I) N N , A _n A ν N ^ N in which R ₁ , R ₂ , R ₃ , R ₄ , Q and Y have the meanings given in claim 1, in any order in the presence of a solvent or diluent which is inert to the reactants and optionally in the presence of a proton acceptor and an inert gas , and converting the reaction products to their metal and ammonium salts, if desired. ; ■■■■■ · '■ -': ·· "- ^ · ■■ '-: ■ ■ · ■ ■■ ·; ..". 7. Use of trisamino-s-triazine derivatives of the general defined in claim 1 Formula for the production of coatings.