Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-06-30
2001-07-24
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06265589
ABSTRACT:
This application is a 371 of PCT/EP97/07318 filed Dec. 30, 1997.
The present invention relates to mixtures of mixed-alkylated methylolated 4,5-dihydroxyimidazolidin-2-ones. The invention also relates to a process for preparing the mixtures mentioned, to finishing baths thereof and to their use.
Methylolated 4,5-dihydroxyimidazolidin-2-ones are used in textile finishing as low-formaldehyde textile crosslinkers. They are also described as DMDHEU compounds (cf. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 26, pages 227 to 350]. These textile crosslinkers are effective for good crease recovery and reduced textile shrinkage. And DMDHEU derivatives reacted with methanol provide good easy-care effects. At the same time, the formaldehyde contents of the textiles treated with such DMDHEU derivatives are low. Yet there are disadvantages in the form of high emissions in use, i.e. in textile finishing, due to residual methanol or partly detached methanol.
U.S. Pat. No. 4,396,391 discloses the treatment of cellulosic textiles with polyol-derivatized DMDHEU. The DMDHEU reacted with polyols or their mixtures leads to low formaldehyde values in the treatment of textiles. However, the disadvantage of these hydroxyalkoxyalkylated DMDHEU derivatives is that their easy-care effects are inferior to methanol-derivatized DMDHEU compounds.
It is an object of the present invention to provide a low-formaldehyde textile crosslinker which provides good finishing effects with low formaldehyde values on the textile coupled with low emissions in textile finishing use. It shall impair the breaking strength of the fiber as little as possible, if at all, and confer good smoothness on it. In addition, it shall provide good easy-care effects.
This object is achieved by mixtures of mixed-alkylated methylolated 4,5-dihydroxyimidazolidin-2-ones, which are preparable by reaction of methylolated 4,5-dihydroxyimidazolidin-2-one (DMDHEU) with a monohydric C
1-5
alcohol and a polyol selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO(CH
2
CH
2
O)
n
H where 3=n=20, the monohydric C
1-5
alcohol and the polyol each being used in an amount of from 0.1 to 2.0 mol equivalents, based on DMDHEU, and the reaction being carried out at temperatures from 20° C. to 70° C. and at a pH of from 1 to 2.5, and the pH being set to a value of from 4 to 8 after the reaction.
The invention further provides a corresponding process for preparing these mixtures. The invention additionally provides an aqueous finishing bath for cellulosic textile materials, which comprises the said mixtures of the invention.
In the mixtures provided according to the invention, DMDHEU preferably has asymmetric substitution on the two nitrogen atoms of the imidazolidine ring. It is preferred for one of the two methylol groups of DMDHEU to be etherified with a methyl radical and the other methylol group to be derivatized by reaction with a polyol selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO(CH
2
CH
2
O)
n
H where 3≦n≦20, preferably diethylene glycol.
The mixtures of such asymmetrically substituted DMDHEU derivatives and their aqueous solutions are useful in textile finishing as low-fornaldehyde textile crosslinkers because they have very low formaldehyde values. At the same time, the emissions in textile finishing are likewise reduced. In addition, the strength of the cellulosic textile materials treated therewith is distinctly improved as well. Another aspect is that the Monsanto smoothness image shows improved values.
The novel process for preparing the mixtures has both a single-stage and a two-stage variant. In the two-stage variant, an aqueous solution of DMDHEU is initially reacted with a monohydric C
1
-C
5
-alkohol, preferably methanol. From 0.1 to 2.0 mol equivalents of the alcohol are used. The pH during the reaction is within the range from 1 to 2.5. The temperature is from 20° C. to 70° C. The DMDHEU solution used has a solids content of typically 40-85% by weight. The reaction takes place in the presence of mineral acids, mixtures thereof or organic acids. Preferred acids are phosphoric acid or its mixtures with other mineral acids. The reaction times are within the range from 0.5 to 6 hours.
After this first reaction step, the aqueous solution is reacted in a second step with again from 0.1 to 2.0 mol equivalents of a polyol selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO(CH
2
CH
2
O)
n
H where 3≦n≦20. Preferably, the monohydric C
1-5
alcohol is used in an amount of from 0.7 to 2.0 mol equivalents and the polyol in an amount of from 0.8 to 1.4 mol equivalents, each based on DMDHEU. Preferably, the monohydric C
1-5
alcohol and the polyol are altogether used in an amount of from 1.7 to 2.9 mol equivalents, based on DMDHEU. The pH and the temperature of the reaction of the second step are within the ranges already mentioned in connection with the first step. Diethylene glycol is the preferred polyol. The order of the first process step and the second process step are advantageously changed. After the reaction has ended, the pH is adjusted to 4-8 by means of a customary base, for example sodium hydroxide or potassium hydroxide. The resulting solutions are adjusted to a desired solids content within the range from 40 to 85% by weight.
The novel mixtures can also be prepared in a single-stage process by reaction of aqueous solutions of DMDHEU with alcohol mixtures. Here alcohol mixtures are mixtures of the abovementioned alcohol components, namely of the monohydric C
1
-C
5
-alcohols and the polyols mentioned. The mixtures mentioned contain the monohydric C
1
-C
5
-alcohols and the polyols which are used according to the invention in ratios of 0.1-2.0:2.0-0.1 mol equivalents. The reaction takes place at a pH of from 1 to 2.5 and at from 20 to 70° C., preferably 20 to 50° C., in the presence of mineral acids, mixtures thereof or organic acids. The single-stage reaction is preferably carried out in the presence of phosphoric acid or its mixtures with other mineral acids. As with the two-stage reaction, the pH is adjusted to 4-8 by means of a customary base, for example sodium hydroxide or potassium hydroxide, after the reaction has ended. The preferred C
1
-C
5
-alcohol for the single-stage process is again methanol. And the preferred polyol is again diethylene glycol.
As already mentioned, the mixtures according to the invention are used for finishing cellulosic textile materials. Cellulosic textile materials are finished using a finishing bath which contains the mixtures according to the invention together with other, customary constituents, e.g. catalysts such as magnesium chloride, for example.
The Examples which follow illustrate the invention.
REFERENCES:
patent: 3079279 (1963-02-01), Van Loo, Jr.
patent: 3091617 (1963-05-01), Burris
patent: 4396391 (1983-08-01), North
Hois Pia
Lippert Ferdinand
Reichert Jurgen
BASF - Aktiengesellschaft
McKane Joseph K.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wright Sonya N
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