Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches

• US 6,420,456 B1
• Filed: 05/21/1998
• Issued: 07/16/2002
• Est. Priority Date: 05/22/1997
• Status: Expired due to Fees

• Current Assignee: Bayer Incorporated (Bayer AG)
• Original Assignee: Bayer Incorporated (Bayer AG)
• Inventors: Koski, Ahti
• Primary Examiner(s): SZEKELY, PETER A
• Application Number:
  US09/082,378
• Time in Patent Office: 1,517 Days
• Field of Search: 524/492, 524/262, 524/445, 524/425, 524/431, 524/188, 524/493, 106/490, 106/475, 106/446, 106/465, 523/213, 523/209, 523/216, 523/351, 428/405
• US Class Current: 523/213
• CPC Class Codes: C01P 2002/02 Amorphous compounds
• CPC Class Codes: C01P 2002/88 by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/50 Agglomerated particles
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/22 Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• CPC Class Codes: C01P 2006/90 Other properties not specified above
• CPC Class Codes: C08K 9/06 with silicon-containing compounds
• CPC Class Codes: C09C 1/3081 Treatment with organo-silicon compounds
• CPC Class Codes: C09C 3/12 Treatment with organosilicon compounds C09C3/006 takes precedence
• CPC Class Codes: Y10T 428/2995 Silane, siloxane or silicone coating

Abstract

Particles are hydrophobicized by treatment with a compound containing amino and silane groups, followed by treatment with a silane compound containing a hydrophobic group. The invention is particularly useful for treating hydrophilic mineral particles. The treated particles can be used, for example, as fillers in polymer masterbatches.

Claims

1. A process for treating particles comprising the steps of:

contacting the particles with a compound of Formula I;

 

or an acid addition or quaternary ammonium salt thereof, in which;

R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₆-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

 

wherein r is an integer from 1 to 6 and d is an integer from 1 to 4;

R⁶ may be any of the groups defined for R⁵, or R⁵ and R⁶ may together form a divalent group of formula;

 

in which A is selected from the group comprising —

CHR or —

NR group in which R is hydrogen or a C_1-40 alkyl or C_2-40 alkenyl group, a C₆-C₄₀ aryl group, an oxygen atom and a sulfur atom, and t and v are each independently 1, 2, 3 or 4;

provided that the sum of t and v does not exceed 6; and

contacting the particles with a compound of the Formula II;

 

in which;

R¹⁵, R¹⁶ and R¹⁷ have the same definitions as R¹, R² and R³; and

R¹² is selected from the group comprising a C_8-40 alkyl group or a C_8-40 mono-, di- or tri-unsaturated alkenyl group, either of which can be interrupted by one or more aryl groups;

a group of formula;

 

or an acid addition or quaternary ammonium salt thereof in which R¹⁸ is a divalent group resistant to hydrolysis at the Si—

R¹⁸ bond, R¹⁹ is selected from the group comprising hydrogen, a C_1-40 alkyl group, a C_2-40 mono-, di- or tri-unsaturated alkenyl group, a substituted aromatic group, the aromatic group being unsubstituted or substituted by a C_1-20 alkyl or C_2-20 mono-, di- or tri-unsaturated alkenyl group; and

R²⁰ may be any of the groups defined for R¹⁹, with the provisos that R¹⁹ and R²⁰ do not have a tertiary carbon atom adjacent to the nitrogen atom and that at least one of R¹⁹ and R²⁰ has a carbon chain at least 8 carbon atoms in length uninterrupted by any heteroatoms.

2. The process defined in claim 1, wherein Steps (a) and (b) are conducted concurrently.

3. The process defined in claim 1, wherein Steps (a) and (b) are conducted sequentially.

4. The process defined in claim 1, wherein Formulae I and II are different compounds.

5. The process defined in claim 1, wherein Step (a) comprises contacting an aqueous slurry of the particles with the compound of Formula I.

6. The process defined in claim 5, wherein the compound of Formula I is a solution comprising a solvent which is substantially water miscible.

7. The process defined in claim 1, wherein the particles are mineral particles that are hydrophilic and have surface hydroxyl groups.

8. The process defined in claim 1, wherein the particles are silica particles.

9. The process defined in claim 1, wherein:

R¹ is selected from the group consisting of hydroxyl groups, groups of formula OC_pH_2p+1, where p has a value from 1 to 10 and the alkyl chain may be interrupted by one or more oxygen atoms, phenoxy, acetoxy, chloro, bromo, iodo, ONa, OLi, OK, amino and mono- and dialkylamino,

R² is selected from the group consisting of hydroxy) groups, groups of formula OC_pH_2p+1 where p has a value from 1 to 10 and the alkyl chain may be interrupted by one or more oxygen atoms, phenoxy, acetoxy, ONa, OLi, OTC, amino mono- and dialkylamino, C_1-10, alkyl, C_2-10 mono- and di-unsaturated alkenyl, phenyl and groups of the formula;

10. The process defined in claim 1, wherein:

R¹⁵ is selected from the group consisting of hydroxyl groups, groups of formula OC_pH_2p+1, where p has a value from 1 to 10 and the alkyl chain may be interrupted by one or more oxygen atoms, phenoxy, acetoxy, chloro, bromo, iodo, ONa, OLi, OK, amino and mono- and dialkylamino,

R¹⁶ is selected from the group consisting of hydroxyl groups, groups of formula OC_pH_2p+1 where p has a value from 1 to 10 and the alkyl chain may be interrupted by one or more oxygen atoms, phenoxy, acetoxy, ONa, OLi, OK, amino, mono- and dialkylamino, C_1-10 alkyl, C_2-10 mono- and di-unsaturated alkenyl, phenyl and groups of formula;

11. The process defined in claim 1, wherein the particulate material comprises mineral particles.

12. The process defined in claim 11, wherein the mineral particles are selected from the group consisting of silicates, silicas, clay, titanium dioxide, alumina, calcium carbonate, zinc oxide and mixtures thereof.

13. The process defined in claim 11, wherein the mineral particles comprise silica made by carbon dioxide precipitation of sodium silicate.

14. Particulate material which has been produced by the process defined in claim 1.

27. The process defined in claim 1, wherein two of R¹, R² and R³ are selected from a hydroxyl group and a hydrolysable group.

28. The process defined in claim 1, wherein each of R¹, R² and R³ are selected from a hydroxyl group and a hydrolysable group.

29. The process defined in claim 1, wherein the sum of t and v is 4.

30. The process defined in claim 1, wherein R¹² is selected from the group comprising a C_8-40 alkyl group or a C_8-40 mono-, di- or tri-unsaturated alkenyl group, either of which can be interrupted by one or more phenyl groups.

15. A particulate material comprising particles having bound thereto an aminohydrocarbonsilane moiety having the formula

in which:

R^a, R^b and R^c are the same or different and each is selected from —

O— and

—

C_pH_2p—

, optionally substituted by one or more oxygen atoms and wherein p is an integer of from 1 to 10; and

R¹² is a C_8-40 alkyl group;

a C_8-40 mono-, di- or tri-unsaturated alkenyl group;

a group of formula

 

or an acid addition or quaternary ammonium salt thereof in which R⁴ is a divalent group resistant to hydrolysis at the Si—

R⁴ bond, R⁵ is hydrogen, C_1-40 alkyl, C_2-40 mono-, di- or tri- unsaturated alkenyl;

a group of formula

22. The particulate material defined in claim 15, wherein the particulate material comprises mineral particles.

23. The particulate material defined in claim 22, wherein the mineral particles are selected from the group consisting of silicates, silicas, clay, titanium dioxide, alumina, calcium carbonate, zinc oxide and mixtures thereof.

24. The particulate material defined in claim 22, wherein the mineral particles comprise silica made by carbon dioxide precipitation of sodium silicate.

25. The particulate material defined claim 15, wherein the particulate material comprises non-mineral particles.

26. The particulate material defined in claim 25, wherein the non-mineral particles comprise carbon black.

16. A particulate material comprising particles having:

(i) bound thereto an aminohydrocarbonsilane moiety, and (ii) a contact angle with water of at least about 100°

.

17. The particulate material defined in claim 16, wherein the contact angle of at least about 110°

.

18. The particulate material defined in claim 16, wherein the contact angle is in the range of from about 115°

to about 160°

.

19. The particulate material defined in claim 16, wherein the contact angle is in the range of from about 120°

to about 150°

.

20. The particulate material defined in claim 16, wherein the contact angle is in the range of from about 120°

to about 140°

.

21. The particulate material defined in claim 16, wherein the aminohydrocarbonsilane moeity has the formula

in which:

R^a, R^b and R^c are the same or different and each is selected from —

O— and

—

C_pH_2p—

, optionally substituted by one or more oxygen atoms and wherein p is an integer of from 1 to 10; and

R¹² is a C_8-40 alkyl group;

a C_8-40 mono-, di- or tri-unsaturated alkenyl group;

a group of formula

 

or an acid addition or quaternary ammonium salt thereof in which R⁴ is a divalent group resistant to hydrolysis at the Si—

R⁴ bond, R⁵ is hydrogen, C_1-40 alkyl, C_2-40 mono-, di- or tri-unsaturated alkenyl;

a group of formula

31. A process for treating particles to render them hydrophobic, the process comprising the following steps in sequence of:

(a) contacting the particles with a compound of Formula I;

 

or an acid addition or quaternary ammonium salt thereof, in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

32. A process for treating particles to render them hydrophobic, the process comprising the steps of:

(a) contacting the particles with a compound of Formula 1;

 

or an acid addition or quaternary ammonium salt thereof, in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

33. A process for treating particles to render them hydrophobic, the process comprising the steps of:

(a) contacting the particles with a compound of Formula I;

 

or an acid addition or quaternary ammonium salt thereof, in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴₁ which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

34. The process according to claim 33, wherein the coupling agent is selected from the group consisting of bis[3-(triethoxysilyl)propyl]tetrasulfane, bis[3-(triethoxysilyl)propyl]tetrasulfane, bis[2-(trimethoxysilyl)ethyl]tetrasulfane and mixtures thereof.

35. A process for treating particles to render them hydrophobic, the process comprising the steps of:

(a) contacting the particles with an acid addition or quaternary ammonium salt of a compound of Formula I;

 

in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

36. A process according to claim 35, wherein compound of Formula I is N-oleyl-N-(3-trimethoxysilyl)propyl ammonium dichloride or an acid addition or quaternary ammonium salt thereof.

37. A process for treating particles to render them hydrophobic, the process comprising the steps of:

(a) contacting the particles with a compound of Formula I;

 

or an acid addition or quaternary ammonium salt thereof, in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 a mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

38. A process for treating particles to render them hydrophobic, the process comprising the steps of:

(a) contacting the particles with a compound of Formula I;

 

or an acid addition or quaternary ammonium salt thereof, in which;

at least one of R¹, R² and R³ is selected from a hydroxyl group and a hydrolysable group;

R⁴ is a divalent group that is resistant to hydrolysis at the Si—

R⁴ bond;

R⁵ is selected from the group comprising;

hydrogen;

a C_1-40 alkyl;

a C₅-C₄₀ aryl group;

a C_2-40 mono-, di- or tri-unsaturated alkenyl group;

a group of the formula;

 

in which x is an integer from 2 to 10, R¹³ and R¹⁴, which may be the same or different, are each hydrogen;

C_1-18 alkyl;

C_2-18 mono-, di- or tri-unsaturated alkenyl;

phenyl;

a group of formula;

 

wherein b is an integer from 1 to 10;

a group of formula;

 

wherein c is an integer from 1 to 10 and R²² and R²³, which may be the same or different, are each hydrogen, C_1-10 alkyl group or C_2-10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom;

a group of formula;

39. A process according to claim 38, wherein said non-mineral particles comprise carbon black.