DE1071335B - Process for the production of water-stable, modified amino resins having cationotropic properties - Google Patents

Description

The invention relates to a process for the production of modified aminoplast resins.

The term " aminoplastic resins" used in the following refers to the known, water-soluble or water-dispersible resins which, when an amino compound containing one or more functional amino groups is condensed with a certain amount of an aldehyde, preferably formaldehyde, with or without a catalyst at temperatures generally above room temperature. The term "aminoplast resin" also refers to a resin produced in the usual way, which contains at least one reactive hydroxyl group in its molecular structure. . '

The disadvantages for the usual use of the above amino resins are their limited stability in water, which is a consequence of the hydroxyl contained therein; is a group or groups that favor condensation or polymerization of the resins in an aqueous medium. The poor stability and the resulting change in the physical and chemical properties of these _; Resins in an aqueous medium make the above-mentioned aminoplast resins unsuitable for use as tanning agents, since they often cause undesirable side effects which can hardly be prevented. It is known that some of these resins do not penetrate deeply enough into the treated leather and make it brittle or considerably reduce its tensile strength. ■

The disadvantages of these known amino resins are avoided by the fact that according to the present Processes exhibiting cationotropic properties, in; Water stable, modified. Aminoplast resins Sales of an aminoplast resin with a water-soluble amino base are produced by at least one reactable aminoplast resin containing methylol group with one to bind all reactable Methylol groups sufficient amount of a water-soluble amino base with at least one functional Amino groups are reacted so that the aminoplast resin does not react in the sirine of methylol groups Groups contains more. The resins produced in this way are soluble or dispersible in water and have the favorable ones Properties of the known aminoplast resins, but have the advantage over them that they behave much more stable in the aqueous medium.

There are already methods known in which Aminoplast resins are reacted with amino bases, however, after this process either only one Some of the methylol groups present in the aminoplast resin are reacted, or they are located after the conversion with the amino base still groups in the form of etherified methylol groups in the resulting aminoplast resin, which are reactable in the sense of methylol groups, so manufacturing processes

of cationotropic properties

exhibiting, stable in water,

modified amino resins

Applicant:

Lucien Seilet,

Saddle River, N.J. (V. St. A.)

Representative: Dr.-Ing. W. Höger, Dr.-Ing. E. Maier

and Dipl.-Ing. M. Sc. W. Stellrecht, patent attorneys,

Stuttgart-O, Uhlandstr. 16

Lucien Seilet, Saddle River, NJ (V. St. Α.);
has been named as the inventor

that in the case of all of these known processes no modified amino resins which are stable in water are obtained but more or less easily condensable products which, if they are at all water-soluble, tend to flocculate.

A particularly convenient method of manufacture a modified aminoplast resin is that at least 1 mole of formaldehyde with an amino base in of the type of urea, thiourea, guanidine, acetylene diurea, melamine or dicyandiamide is condensed. The resulting amino resins contain at least one reactable methylol group, which limits the stability of these resins since they are used in an aqueous medium for polymerization or condensation tend.

By reacting one of the above amino resins with a certain amount of an amino base of the Type of urea, dicyandiamide, guanidine and melamine, condensation occurs in which preferably all reactable methylol groups are switched off, whereby a modified aminoplast resin is produced, which is highly stable in an aqueous medium.

The molar ratio of the amino base used for the reaction with aminoplast resin depends on both the The number of reactive hydroxyl groups in one mole of the aminoplast resin as well as the number of functional ones Amino groups in the amino base. One chooses the molar ratios so that all are viable Hydroxyl groups in the aminoplast resin through reaction with an equal number of functional amino groups the amino base to disappear. The amount

909 689/585

a certain amino base, which reacts with a certain aminoplast resin, can easily be determine.

. The reaction temperatures are preferably between 75 and 110 ° C. It changes depending on the individual case the reaction time, but it is usually between 3 and 10 hours. As is well known, set higher temperatures the reaction times decrease, and vice versa. The reaction medium is preferably slightly acidic, neutral or slightly alkaline. It is advisable to use an alkaline catalyst to accelerate the reaction, for example borax to be used.

Modified aminoplast resins can be produced by the method according to the invention, which have the advantage have that they are water soluble or dispersible in water and retain their stability in water. Since they penetrate well into permeable, permeable or porous materials, they are particularly suitable as pore fillers, For example, for leather, paper, fabric or the like. The porous or permeable material is mixed with an aqueous Solution or dispersion of the resin treated, the resin adhering to the material, filling the pores and closes and gives it a smooth surface.

The process is particularly important for leather treatment, with the new, cationotropic modified Aminoplast resins together with an anionotropic, water-soluble or water-dispersible, one or more sulfo group-containing high molecular organic compounds can be used can.

Examples 1 to 16 illustrate the preparation of modified aminoplast resins according to the invention. Possibly these can also be prepared in the presence of an anionotropic sulfo compound (Examples 17 to 22).

For the exemplary embodiments 1 to 22, the substances mentioned in column (a) are used, possibly in the presence of a catalyst, mixed in a vessel with reflux cooling. The respective reaction temperatures and

ίο times are listed in column (b). Then, the column referred to in (c) additive is added, the whole mixture again, as mentioned under (d), refluxed, so that finally yield the p _H values indicated in column (e). Special treatments are listed at the end of the table.

To facilitate understanding, embodiment 1 contained in the table below is intended will be explained in more detail.

Embodiment 1

180 g of guanidine carbonate and 243 g of 37% formaldehyde are mixed in a vessel with reflux cooling and refluxed at 80 ° C. for 1 hour.

168 g of dicyandiamide are then added and the mixture is refluxed at 80 ° C. for 6 hours. The _pH value of the reaction product is then about 10.5. The product thus obtained is a water-soluble cationotropic resin which is suitable as a tanning aid.

Serial
No. ; Reaction partner
weight
concentration Reaction temperature
and duration additive
weight Reaction temperature
and duration. Approximately
achieved
p _H value (a) ° (b) (C) (d) (e) 1 Guanidine carbonate
180 g ■
formaldehyde
243 g 37% 80 ⁰ C
1 hour Dicyandiamide
168 g 80 ° C
6 hours 10.5 2 like 1 80 to 90 ° C
1 hour melamine
126 g 95 ⁰ C
4 hours . 10.3 3 like 1 80 to 90 ° C
1 hour Thiourea
228 g 90 ° C
4 hours 9.8 4th like 1 80 to 90 ° C
1 hour urea
180g 90 ° C
4 hours 9.9 5 melamine
126g.
formaldehyde
489 g 37% 8O ⁰ C
¹ J ₂ hours Guanidine carbonate
360g 95 ⁰ C
5 hours 9.5 6th Urea '.
60 g:.
formaldehyde
162 g 37% - 80 ° C
1 ¹ I ₂ hours Guanidine carbonate
360g
-f water 200 cm ³ 8O ⁰ C
5 hours 10.2 7th Urea '
120 g
formaldehyde
648 g 37% 80 ⁰ C
! ^ Hours Dicyandiamide
84g 80 ° C
3 hours
(Product not
cationotropic) -> 9.0 - catalyst
Borax. 38 g ^ Dicyandiamide
84g 95 ⁰ C
4 hours

1 071 336

5 Reaction temperature
and duration
(b) additive
weight
(C) 6th Approximately
achieved
p _n value
(e) Serial
No. ' Reaction partner
weight
concentration
in "/".
(a) 95 ⁰ C
4 hours Guanidine carbonate
180 g Reaction temperature
and duration
(d) 10.3 8th Acetylenediurea
142 g
formaldehyde
324 g 37% *)
85 ° C
4 hours
while stirring melamine
63 g 95 ° C
2 hours 9.0 9 catalyst
Borax 1.4 g
Acetylenediurea
142 g
formaldehyde
324 g 37% 95 ⁰ C
4 hours Dicyandiamide
168 g
Dicyandiamide
168 g to 470 g
of the resulting
Product 95 ° C
2 hours -> Additive
Caustic soda
2 g 40 ° Beaume
Acetylenediurea
284g
formaldehyde
652 g 37% 95 ° C
3V ₂ hours Diacetylene
urea powder
142g 95 ⁰ C
2 hours
95 ⁰ C
11 hours 8.1 10 catalyst
Borax 1.25 g
Dicyandiamide
84 g (1 mole)
formaldehyde
324 g (4MoI) 37% 95 ° C
Cool for 4 hours Dicyandiamide
336 g 95 ⁰ C
10 hours 8.5 11 catalyst
Borax 1.2 g
Dicyandiamide
168 g
formaldehyde
648 g 37% 95 ° C
3 hours
(achieved
p _H value 8.5). ' Guanidine carbonate
180g
+ Water 208 g 90 to 95 ° C
9 hours 9.7 12th catalyst
Borax 3.6 g
Dicyandiamide
84g
formaldehyde
324 g 37% 95 ° C
** \
25 to 30 minutes 'Urea
240 g 95 ° C
3 hours 10.0 13th catalyst
Borax 1.6 g
Dicyandiamide
84 g
formaldehyde
324 g 37% urea
120 g 95 ° C
5 hours 9.9 14th catalyst
Borax 1.2 g
Dicyandiamide
84g
formaldehyde
162 g 37% ^ Formaldehyde
324 g 37% 95 ⁰ C
2 hours - 1 8.0 15th catalyst
Borax 1.2 g 95 ⁰ C
4 hours

*) The _pH value of the mixture is 10 to 12. The product is clear.

Stirred an hour until the solution at 50 to 6O ⁰ C

**) The reaction is checked by adding 1 cm ^{3 of} the reaction liquid to 100 cm ^{3 of cold water.} First of all, the test gives a completely clear solution. As the reaction proceeds, it becomes cloudy and after 25 to 30 minutes the solution becomes cloudy.

7th Reaction temperature ί. • 95 ° C additive 8th 95 ° C Approximately Reaction partner and duration 4 hours weight 4 hours achieved weight (b) (C) Reaction temperature 95 ⁰ C p _H value 'No.' concentration 95 ° C urea and duration 6 hours (e) (a) ° *) 120 g (d) 8.8 16 Dicyandiamide OC "Kic ^ n TVTi-m-i-för» 95 ⁰ C 84 g ώο DlS oU lVllIiULcTl ^ Formaldehyde 2 hours -, I j ι— ■ - | -i ^- i Λ I ^ -J / ■ * V% ΥΤ / "ί 162 g 37% I. r ormaiuenyQ
162 g 37% 80 ⁰ C Dicyandiamide 1 hour 80 ° C 168g 10.5 17th Guanidine carbonate 1 ¹ Z ₂ hours 180 g ; 95 ° C formaldehyde 8 hours 243 g 37% Sodium salt by disulfo- dinaphthylmethane 80 ° C 1580 g in 35% 1 hour Diacetylene urea Water solution 142g 8.5 48 Sodium salt by disulfo- 8O ⁰ C dinaphthylmethane 4 hours 1580 g in 35% _: Water solution formaldehyde 324 g 37% 95 ° C Dicyandiamide 4 hours melamine 84g 63 g 80 ° C 19th urea Sodium salt 4 hours 90g by disulfo- formaldehyde dinaphthylmethane 243 g 37% 500 g in 35% catalyst Water solution Borax 15 g urea 95 ° C. : 180 g 20th melamine 4 hours [ 63 g 95 ⁰ C formaldehyde 9 hours 243 g 37% Sodium salt by disulfo- dinaphthylmethane 790 g in 35% Dicyandiamide Water solution 84g 21 Dicyandiamide 42g 95 ° C formaldehyde 1 hour 162 g 37% Sodium salt of 95 ° C
A f \ C + hviJats Disulfodihydroxy IU btunden diphenylpropane: 500 g in 50% Diacetylene urea ' Water solution ^{[ :} 142 g - ■ ': 22nd Dicyandiamide 84g I. formaldehyde * Sodium salt of ■ 3.24 g 37% Disulfodihydroxy
diphenyl sulfone catalyst
"Borax 18? 1000 g dissolved in 5O ° / _O '' "'Water solution'

*) The reaction is tested by adding 1 cm ^{3 of} the reaction liquid to 100 cm ^{3 of cold water.} First of all, the test gives a completely clear solution. As the reaction progresses, it becomes cloudy and after 25 to 30 minutes the solution becomes cloudy.

Claims (3)

Patent claims: 1. Process for the production of cationotropic properties, stable in water, modified aminoplast resins by reacting an aminoplast resin with a water-soluble amino base, characterized in that one containing at least one reactive methylol group Aminoplast resin with an amount sufficient to bind all of the reactive methylol groups a water-soluble amino base is reacted with at least one functional amino group, so that the aminoplast resin no longer contains any reactive groups in the sense of methylol groups. 2. The method according to claim 1, characterized in that a by condensation of formaldehyde with urea, thiourea, guanidine, acetylenediurea, melamine, dicyandiamide or their derivatives formed aminoplast resin and as the amino base urea, dicyandiamide, guanidine or Melamine is used. 3. The method according to claim 1 and 2, characterized in that the reaction in the presence of anionotropic sulfo compounds takes place. Considered publications:
German Patent Nos. 499 710, 517 251,
626;
U.S. Patent No. 2,662,872. © 909 6S9 / 585 12.59