METHOD FOR PRODUCING DISPERSANT ADDITIVES

• US 20140194537A1
• Filed: 05/05/2012
• Published: 07/10/2014
• Est. Priority Date: 06/22/2011
• Status: Active Grant

• Current Assignee: BYK-Chemie GmbH (Susanne Klatten, MBA)
• Original Assignee: BYK-Chemie GmbH (Susanne Klatten, MBA)
• Inventors: Gbelt, Bernd, Nagelsdiek, Ren, Omeis, Jrgen, Piestert, Frederik, Pritschins, Wolfgang, Tiegs, Werner, Meznaric, Natasa, Schrder, Daniela
• Granted Patent: US 9,573,103 B2
• Time in Patent Office: Days
• US Class Current: 514/788
• CPC Class Codes: C08G 18/0814 containing ammonium groups or groups forming them
• CPC Class Codes: C08G 18/0819 containing anionic or anionogenic groups
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/282 Alkanols, cycloalkanols or arylalkanols including terpenealcohols
• CPC Class Codes: C08G 18/2825 having at least 6 carbon atoms
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/284 Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
• CPC Class Codes: C08G 18/2865 Compounds having only one primary or secondary amino group; Ammonia
• CPC Class Codes: C08G 18/2875 Monohydroxy compounds containing tertiary amino groups
• CPC Class Codes: C08G 18/3275 containing two hydroxy groups
• CPC Class Codes: C08G 18/3281 containing three hydroxy groups
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/615 containing carboxylic acid groups
• CPC Class Codes: C08G 18/7621 being toluene diisocyanate including isomer mixtures
• CPC Class Codes: C08G 18/8064 with monohydroxy compounds
• CPC Class Codes: C08G 18/836 by phosphorus containing compounds
• CPC Class Codes: C08K 5/5455 containing at least one group
• CPC Class Codes: C09D 7/45 Anti-settling agents
• CPC Class Codes: C09K 23/018 Mixtures of two or more different organic oxygen-containing compounds
• CPC Class Codes: C09K 23/14 : Derivatives of phosphoric acid
• CPC Class Codes: C09K 23/16 : Amines or polyamines

Abstract

The present invention relates to a method for producing an additive composition which in particular contains specific urea urethanes. The additive composition is extremely suitable as a wetting agent and dispersant.

Claims

1. A method for producing an additive composition, comprising the steps i) to iii), wherein

in step i) a hydroxy component of the general formula (I)

Y(—

OH)_q 

 

(I)

wherein

Y is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms,

q is the same or different and represented by an integer from 1 to 10

is reacted with a diisocyanate of the general formula (II) having NCO groups of different reactivity

R¹(NCO)₂ 

 

(II)

wherein

R¹ is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms,

wherein the diisocyanate of the general formula (II) is used with respect to the hydroxy component of the general formula (I) in a molar ratio of at least (1.1*arithmetic mean of q);

1.0, so that an isocyanate adduct of the general formula (III)

Y(—

O—

CO—

NH—

R¹—

NCO)_q 

 

(III)

wherein

Y, q and R¹ are each as described above,

and unreacted diisocyanate of the general formula (II) containing reaction mixture is formed,

in step ii) at least 50 mol % of the unreacted portion of the diisocyanate of the general formula (II) is removed from the reaction mixture,

in step iii) a compound of the general formula (IV) having at least one head group radical Z¹

Y(—

O—

CO—

NH—

R¹—

NH—

CO—

X—

Z¹)_q 

 

(IV)

wherein

Y, q and R¹ are each as described above,

X is the same or different and is represented by 0, NH and/or NZ²

wherein

Z² is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical,

Z¹ is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms having at least one head group which is present in salifiable or salified form, and is selected from the group consisting of tertiary amino functions, quaternary ammonium functions, phosphoric acid ester functions, and carboxylic acid functions,

wherein step iii) is carried out in a single stage iii-a) or a sequence of steps iii-b),

in step iii-a) the isocyanate adduct of the general formula (III) present in the reaction mixture is reacted with an isocyanate-reactive compound of general formula (V) having said head group radical Z¹,

HX—

Z¹ 

 

(V)

wherein

X and Z¹ are each as described above,

and in the sequence of steps iii-b), first, the isocyanate adduct of the formula (III) which is present in the reaction mixture is reacted with a compound having a isocyanate-reactive group HX and at least one further functional group Q, wherein then Q is reacted with a reagent involved in the generation of the head group radical Z¹ to form the head group radical Z¹.

2. The method according to claim 1, characterized in that q is the same or different and is represented by an integer from 1 to 5.

3. A method for the preparation of an additive composition according to claim 1, characterized in that q=1, so that in the method including steps i) to iii)

in step i) as a hydroxy component a monohydroxy compound of the general formula (Ia)

Y—

OH 

 

(Ia)

wherein

Y is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms

is reacted with a diisocyanate of the general formula (II) having NCO groups of different reactivity

R¹(NCO)₂ 

 

(II)

wherein

R¹ is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms,

wherein the diisocyanate of the general formula (II) is used with respect to the monohydroxy component of the general formula (Ia) in a molar ratio of at least 1.1;

1.0, so that a monoisocyanate adduct of the general formula (IIIa)

Y—

O—

CO—

NH—

R¹—

NCO 

 

(IIIa)

wherein

Y and R¹ are each as described above,

and unreacted diisocyanate of the general formula (II) containing reaction mixture is formed,

in step ii) at least 50 mol % of the unreacted portion of the diisocyanate of the general formula (II) is removed from the reaction mixture,

in step iii) a compound of the general formula (IVa) having at least one head group radical Z¹

Y—

O—

CO—

NH—

R¹—

NH—

CO—

X—

Z¹ 

 

(IVa)

wherein

Y and R¹ are each as described above,

X is the same or different and is represented by O, NH and/or NZ²

wherein

Z² is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical,

Z¹ is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms having at least one head group which is present in salifiable or salified form, and is selected from the group consisting of tertiary amino functions, quaternary ammonium functions, phosphoric acid ester functions, and carboxylic acid functions,

wherein step iii) is carried out in a single stage iii-a) or a sequence of steps iii-b),

in step iii-a) the monoisocyanate adduct of the general formula (IIIa) present in the reaction mixture is reacted with an isocyanate-reactive compound of general formula (V) having said head group radical Z′

,

HX—

Z¹ 

 

(V)

wherein

X and Z¹ are each as described above,

and in the sequence of steps iii-b), first, the monoisocyanate adduct of the formula (IIIa) which is present in the reaction mixture is reacted with a compound having a isocyanate-reactive group HX and at least one further functional group Q, wherein then Q is reacted with a reagent involved in the generation of the head group radical Z¹ to form the head group radical Z¹.

4. The method according to claim 1, characterized in that Y contains at least one polyether radical, polyester radical, hydrocarbon radical, and/or polysiloxane radical.

5. The method according to claim 1, characterized in that Y in total contains 1 to 450 ether oxygen atoms, which optionally are contained in ether oxygen-containing groups, which are derived from polytetrahydrofuran, polyoxethanes and/or polyoxiranes.

6. The method according to claim 1, characterized in that Y in total contains 3 to 400 ether oxygen atoms, wherein at least 50 mol % of the ether oxygen atoms are present in ethylene oxide and/or propylene structural units.

7. The method according to claim 1, characterized in that R¹ is the same or different and is present in the form of a hydrocarbon radical, optionally as an arylene group, as a branched or unbranched alkylarylene group, and/or as an acyclic, cyclic, branched or unbranched alkylene group.

8. The method according to claim 1, characterized in that the diisocyanate of the general formula (II) is present as toluene-2,4-diisocyanate and/or isophorone diisocyanate, optionally as toluene-2,4-diisocyanate.

9. The method according to claim 1, characterized in that the head group of the head group radical Z¹ is present in the form of a phosphoric acid ester function, step iii) is carried out in the form of a sequence of steps iii-b), wherein the further functional group Q is present in the form of a hydroxyl group and the reagent involved in the generation of the head group moiety Z¹ optionally is present as a phosphorylization agent.

10. The method according to claim 1, characterized in that the head group radical Z¹ has a phosphoric acid ester function as a head group, wherein Z′

is the same or different and is represented by the general formula (VII)

R²—

O—

PO(OR³)_n(OH)_2-n 

 

(VII)

wherein

R² is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms,

R³ is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical; and

n is the same or different and is represented by 0 and/or 1.

11. The method according to claim 10, characterized in that n is equal to 0 and R² optionally is the same or different and is represented by a saturated, linear C₂-C₄₀-alkylene radical.

12. The method according to claim 1, characterized in that the head group of the head group radical Z¹ is the same or different and is present as tertiary amino function or quaternary ammonium function.

13. The method according to claim 1, characterized in that Z² is the same or different and is represented by a C₁-C₅₀-hydrocarbon radical having optionally ether oxygen atoms, and/or includes the equivalent of Z¹, with the proviso that Z¹ and Z² each are represented independently from one another.

14. The method according to claim 1, characterized in that X is the same or different and is represented by NH and/or NZ².

15. The method according to claim 1, characterized in that Z¹ and Z² each are represented independently from one another by radicals which in each case are either only relatively weakly reactive or optionally inert towards isocyanates.

16. The method according to claim 1, characterized in that in step i) the diisocyanate of the general formula (II) is used with respect to the hydroxy component of the general formula (I) in a molar ratio of at least (1.5*arithmetic mean of q):

1.0.

17. The method according to claim 1, characterized in that in step ii) at least 75 mol % of the unreacted portion of the diisocyanate of the general formula (II) is removed from the reaction mixture.

18. The method according to claim 3, characterized in that the molar ratio of the monohydroxy compounds of the general formula (Ia) reacted in total in step i) to the sum of the compounds of general formula (V) reacted in step iii) and the compounds reacted in step iii) containing a isocyanate-reactive group HX and at least one further functional group Q, is 0.9 to 1.1.

19. The method according to claim 3, characterized in that in step iii) as much compounds of the general formula (Va) and/or as much compounds having one isocyanate-reactive group HX and at least one further functional group Q, is used, that at least 90 mol % of the monoisocyanate adduct of the general formula (IIIa) formed in step i) is reacted.

20. The method according to claim 3, characterized in that in step i) the diisocyanate of the general formula (II) with respect to the monohydroxy compound of the general formula (Ia) is used in a molar ratio of at least 1.5:

1.0, optionally to 20;

1.

21. An additive composition prepared by the method according to claim 1.

22. The additive composition of claim 21, containing

i) 10 to 99.98% by weight of the compound according to the general formula (IVa) Y—

O—

CO—

NH—

R¹—

NH—

CO—

X—

Z¹,

ii) 0.01 to 10% by weight diurethane according to the general formula Y—

O—

CO—

NH—

R¹—

NH—

CO—

O—

Y, wherein Y is the same or different,

iii) 0.01 to 10% by weight diurea of the general formula Z¹—

X—

CO—

NH—

R¹—

NH—

CO—

X—

Z¹, wherein Z¹ is the same or different; and

iv) 0 to 8% by weight urethane of the general formula Y—

O—

CO—

NH—

R¹—

NCO.

23. A process comprising utilizing an additive composition according to claim 21 as an additive, optionally as a wetting agent and dispersant in coatings, paints, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, casting compounds, fillers, printing colors and inks.

24. A solid mixture containing particles and/or fibers that have been treated with an additive composition according to claim 21.

25. Paint and/or plastic, containing an additive composition according to claim 21.

26. A process comprising utilizing an additive composition according to claim 22 as an additive, optionally as a wetting agent and dispersant in coatings, paints, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, casting compounds, fillers, printing colors and inks.

27. A solid mixture containing particles and/or fibers that have been treated with an additive composition according to claim 22.

28. Paint and/or plastic, containing an additive composition according to claim 22.