Blocked oligomeric isocyanates, their production and use

• US 6,437,077 B1
• Filed: 12/08/2000
• Issued: 08/20/2002
• Est. Priority Date: 04/09/1998
• Status: Active Grant

• Current Assignee: Clariant Finance (Bvi) Limited
• Original Assignee: Clariant Finance (Bvi) Limited
• Inventors: Danner, Bernard
• Primary Examiner(s): Yoon, Tae H.
• Application Number:
  US09/647,957
• Time in Patent Office: 620 Days
• Field of Search: 524/463, 524/590, 524/591, 524/838, 528/73, 528/76, 427/389.9
• US Class Current: 528/73
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/706 the liquid medium being water
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/808 Monoamines
• CPC Class Codes: D06M 15/263 of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/27 of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 15/285 of unsaturated carboxylic acid amides or imides
• CPC Class Codes: D06M 15/568 Reaction products of isocyanates with polyethers
• CPC Class Codes: D06M 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties

Abstract

Self-dispersible mixtures (G) of oligomeric isocyanates (C) reacted in part with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B) are useful as auxiliaries in the finishing of fibrous material with oleophobicizing and/or hydrophobicizing finishes (F) comprising fluorocarbon polymers.

Claims

1. A mixture (G), self-dispersible in water, of oligomeric isocyanates (C) reacted in part with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (I).

2. A mixture (G) according to claim 1, wherein the polyethylene glycol monoalkyl ethers (A), which optionally contain propyleneoxy units, conform to the average formula

 

R—

(O—

CH₂—

CH₂)_n—

OH 

 

(I)

where

R is C_1-4-alkyl-(O-propylene)_m—

,

n is from 5 to 30 and

m is from 0 to 10,

with the proviso that m is ≦

⅓

of n.

3. A mixture (G) according to claim 1, characterized in that (K) is water.

4. A process for the production of mixtures (G) according to claim 1, characterized in that

in a first process step

(a) a minor proportion of the isocyanate groups in the oligomeric isocyanate (C) are reacted in the absence of protogenic solvents with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, to form a product (U1) and this product (U1) is then optionally converted into a product (U2) which has a higher NCO-based equivalent weight and which still contains reactive NCO groups,

and in a second process step

(b) the remaining isocyanate groups are exhaustively blocked with isocyanate-blocking pyrazole (B).

5. A process according to claim 4, characterized in that the equivalents ratio of (A)/(C) is within the range from 1:

2 to 1;

50.

6. A process according to claim 4, characterized in that in process step (a) the treatment of (U1) is carried on at 60-95°

C. until the isocyanate-based equivalent weight of product (U2) has risen beyond that corresponding stoichiometrically to urethane formation in (U1).

7. A process according to claim 6, characterized in that in process step (a) the treatment of (U1) is carried on at 60-95°

C. until the isocyanate-based equivalent weight of product (U2) has risen by 1 to 20% beyond that corresponding stoichiometrically to urethane formation in (U1).

8. A process according to claim 4, characterized in that in process step (a) (U1) is reacted with a chain extender (K) in such a way that the isocyanate-based equivalent weight of product (U2) is 1 to 20% higher than that corresponding stoichiometrically to urethane formation in (U1).

9. The mixtures (G) obtainable by the process of claim 4.

10. An aqueous dispersion (D) of a mixture (G) according to claim 1.

11. An aqueous dispersion (D) according to claim 10, further comprising a non-ionogenic, surface-active stabilizer (E) and/or a solubilizer (L) and/or an additive (Z) to control microbial damage.

12. A process for the production of aqueous dispersions (D) according to claim 10, characterized in that a mixture (G) of oligomeric isocyanates (C) reacted in part with polyethylene, glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B), is mixed with water and optionally admixed with at least one further additive.

16. A process for the finishing of textile material by impregnation methods from an aqueous liquor, optionally together with a synthetic resin finish, with thermofixation, comprising contacting the textile material with the mixture (G) of claim 1.

13. A method for the application of a mixture (G), self-dispersible in water, of oligomeric isocyanates (C) reacted in part with polyethylene, glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B), comprising providing (G) as an auxiliary in the finishing of fibrous material with oleophobicizing and/or hydrophobicizing finishing agents (F) which are fluorocarbon-radicals-containing polymers.

14. The method according to claim 13, characterized in that (G) and (F) are provided in the form of an aqueous composition (P) containing (G) and (F).

15. An aqueous composition (P) comprising (G) and (F), wherein (G) is a mixture, self-dispersible in waters of oligomeric isocyanates (C) reacted in part with polyethylene, glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B), and (F) is an oleophobicizing and/or hydrophobicizing finishing agent which is a fluorocarbon-radicals-containing polymer.

17. A method for the application of an aqueous dispersion (D) of a mixture (G), self-dispersible in water, of oligomeric isocyanates (C) reacted in part with polyethylene, glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B), comprising providing the mixture (G) in said aqueous dispersion (D) as an auxiliary in the finishing of fibrous material with oleophobicizing and/or hydrophobicizing finishing agents (F) which are fluorocarbon-radicals-containing polymers.