US20090146107A1

US20090146107A1 - Inorganic/organic dispersant and application thereof

Info

Publication number: US20090146107A1
Application number: US12/146,449
Authority: US
Inventors: Jiang-Jen Lin; Yen-Chi Hsu; Ming-Li Chiang; Chien-Chia Chu
Original assignee: National Taiwan University NTU
Current assignee: National Taiwan University NTU
Priority date: 2007-12-07
Filing date: 2008-06-26
Publication date: 2009-06-11
Also published as: US8653147B2; US20120065053A1; TWI501807B; TW200925133A

Abstract

The present invention discloses an inorganic/organic mixed component (I/O) dispersant and applications thereof, which is primarily applied to dispersing nanoparticles of metal oxides. The I/O dispersant of the present invention can be a composite of inorganic clay and an organic surfactant, a composite of inorganic clay and polyoxyalkylene-amine, or a composite of inorganic clay, polyisobutylene succinic anhydride (PIB-SA) and hydrochloric acid salt or tetraalkyl quaternary salt of polyoxyalkylene-amine, or fatty amines. By mixing with the I/O dispersant of the present invention, nanoparticles of a metal oxide can be uniformly dispersed without aggregation particularly at high solid content. The dispersion has a lower viscosity and is relatively stable in storage even at high temperature.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention
The present invention relates to an I/O (inorganic/organic) dispersant and applications thereof, and particularly to an I/O dispersant which is applied to dispersing nanoparticles of metal oxides, for example, white pigment and photocatalyst made from TiO₂.
2. Related Prior Arts
For application of TiO₂in commercial articles and industrial processes, it's always a technical issue to efficiently disperse TiO₂particles or powders into a solvent. Different sizes of TiO₂can be applied to different fields, for example, nanoparticles of TiO₂can be used as photocatalysts, microparticles of TiO₂can be used as paints.
The well known method for dispersing TiO₂consists in adding a general organic surfactant or a polymeric dispersant. The surfactant or dispersant primarily includes different segments with respective affinities to the solvent and the dispersed particles, so that the dispersant can be effectively attached to surfaces of the TiO₂particles and also dispersed in the solvent. By means of steric hindrance of the dispersant, the TiO₂particles will be stable and no longer aggregate in the solvent.
However, the effect of the dispersant is easily influenced by temperature and time. Once the dispersant is desorbed or isolated from the surfaces of the TiO₂particles, the dispersant will be unstable with aggregation.
To solve the above problem, the present invention provides an I/O dispersant which is suitable for application of TiO₂particles.

SUMMARY OF THE INVENTION

The object of the present invention is to provide an I/O dispersant, which can effectively disperse nanoparticles of a metal oxide.
Another object of the present invention is to provide a method for dispersing nanoparticles of a metal oxide by applying the aforementioned I/O dispersant, so that the nanoparticles can be uniformly dispersed.
To achieve the above objects, the I/O dispersant of the present invention can be a composite of inorganic clay and an organic surfactant; and the I/O dispersant is produced by reacting the inorganic clay with the organic surfactant.
The I/O dispersant of the present invention can also be a composite of inorganic clay and polyoxyalkylene-amine; and the I/O dispersant is produced by reacting the inorganic clay with the polyoxyalkylene-amine.
The I/O dispersant of the present invention can further be a composite of inorganic clay, polyisobutylene succinic anhydride (PIB-SA, Mw=300˜2000 g/mol) and polyoxyalkylene-amine; and the I/O dispersant is produced by reacting the inorganic clay with PIB-SA grafted with polyoxyalkylene-amine.
The I/O dispersant of the present invention can be produced by reacting the inorganic clay with fatty amine quaternary ammonium salt of C12˜C32.
In the present invention, the method for dispersing nanoparticles of a metal oxide comprises mixing the I/O dispersant and the nanoparticles of the metal oxide.
The I/O dispersant of the present invention can be used for dispersing such metal oxides as SiO₂, Fe₂O₃, Al₂O₃, ZrO, Ag₂O, TiO₂, etc.
The above inorganic clay is preferably in the form of layers or sheets, and can be natural clay of silicate and aluminum oxide (for example, natural montmorillonite), organoclay (prepared from organic surfactant intercalated clay through ionic salt exchanging), exfoliated clay (for example, nanosilicate platelets), synthetic fluoride mica, synthetic nanoclay (SNC) or other proper inorganic clays (for example, K10, layered double hydroxides (LDH), kaolin, bentonite, synthetic layered clay, talc, attapulgite clay, laponite, vermiculite, etc.)
The organic surfactant of the present invention can be a cationic surfactant, a nonionic surfactant or an amphoteric surfactant; for example, fatty amine quaternary ammonium salt of C12˜C32, HCl amine salt of C12˜C32, alkylphenol ethoxylate or fatty alcohol ethoxylate. The preferred organic surfactant is octadecyl amine (ODA) or other alkyl amine salts and quaternary salts. For the resultant dispersant, the organic surfactant and the inorganic clay preferably have an organic/inorganic ratio of about 10/90˜90/10.
In the present invention, polyoxyalkylene-amine has a molecular weight of about 200˜10,000. One of this series of products, the Jeffamine® Amine series products, is commercially produced by Huntsman Co. For example, Jeffamine® diamine D-230, D-400, D-2000, D-4000, and ED-2003. Polyoxyalkylene-amine and the inorganic clay preferably have a cation exchanging capacity (CEC) ratio of about 0.1˜1.0. For the resultant dispersant, the polyoxyalkylene-amine and the inorganic clay preferably have an organic/inorganic ratio of about 55/45˜99/1.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the reaction for grafting PIB-SA with polyoxyalkylene-amine.

FIG. 2 shows the status of the TiO2 particles dispersed in a solvent with D2000/MMT as the dispersant (b), ODA/NSP as the dispersant (c), and without any dispersant (a).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The intercalated inorganic clay of the present invention can be prepared by referring to R.O.C. (Taiwan) Patent No. 254064 and Pub. Nos. 550246 and 577904. The nanosilicate platelets of the present invention can be prepared by referring to R.O.C. Patent Nos. 280261, 284138 and 270529, and Pub. Nos. 577904 and 593480. The other materials used in the preferred embodiments (Examples) include:
1. Montmorillonite: Na⁺-MMT, a product of Nanocor Ind. Co. (CEC=1.2 mequiv/g) and a product of Kunimine Ind. Co. (Kunipia-F, CEC=1.15 mequiv/g).
2. Synthetic Nanoclay: SNC, a product of CO-OP Chemical Co., LTD (CEC=0.7˜1.2 mequiv/g).
3. Polyoxyalkylene-amine: Jeffamine® series products of Huntsman Chemical Co., for example, D-2000, T-403, T-5000; wherein D-2000 (poly(propylene glycol) bis(2-aminopropyl ether), Mw=2000) has a structural formula:
4. TiO₂: nanoparticles, a product of BASF and Aldrich Chemical Co.

EXAMPLE 1

Step (a): Na⁺-montmorillonite (MMT) (10 g) is first dispersed in water (1 L) at 80° C. and then vigorously stirred for 4 hours to obtain a stable earth-colored dispersion.
Step (b): The polyoxypropylene diamine of Mw 2000 (D2000) (24 g, 12 mmol, CEC ratio of D2000/MMT=1.0) is dissolved in ethanol (100 ml), and equivalent moles of hydrochloric acid is added therein for acidification for 30 minutes. The acidified intercalation solution is added to the Na⁺-MMT dispersion slowly and stirred at 60˜70° C. for 6 hours for a cation exchanging reaction. Then the resultant reaction solution is separated into two phases. After filtration, the residual is washed with water for several times to remove the unreacted organics and the inorganic clay. The synthesized product (D2000/MMT hybrid) was analyzed to have an organic/inorganic weight ratio 74/26 and can be further dried in a vacuum oven at high temperature for 24 hours.

EXAMPLES 2˜3, COMPARATIVE EXAMPLES 1˜2

Repeat the steps of Example 1, but the dosage of D2000 is changed so that CEC=0.8, CEC=0.6, CEC=0.4, and CEC=0.2, respectively. The products (D2000/MMT) with organic/inorganic weight ratios 69/31, 63/37, 53/47, and 36/64 are obtained.

EXAMPLE 4

Step (a): Na⁺-MMT (10 g) is first dispersed in water (10 L) at 80° C. and then vigorously stirred for 4 hours to obtain a stable earth-colored dispersion.
Step (b): P-cresol (27.2 g) and D2000 (757.6 g) are weighted with a molar ratio 2:3 and circulated in toluene at 90° C. for 3 hours. Then a formaldehyde solution (37 wt %, 61.4 g) is added and the temperature is raised to 130° C. for reaction for 5 hours. When a gel is formed, the reaction is stopped and the product, an intercalating agent AMO (Amine-termination Mannich Oligomer), can be obtained. The AMO is analyzed with GPC and three peaks are found at Mw=3,142, 6,221 and 9,246, respectively. Results of amino titration are that primary amine=0.4 meq/g, secondary amine=0.56 meq/g, and no tertiary amine is found. Then the AMO is dissolved into water (575 g) and mixed with concentrated hydrochloric acid (35 wt %, 36 g) at 80° C. for 30 minutes to acidify the AMO. The acidified AMO is poured into the above Na⁺-MMT dispersion and vigorously stirred at 80° C. for 5 hours. After the intercalation reaction is completed, a mixture solution of AMO/Clay is obtained.
Step (c): A buffer solution of water at various pH values is added into the mixture solution of AMO/Clay which then becomes a yellowish emulsification slurry.
Step (d): Ethanol (7.5 L) is added into the slurry. After filtration, the residual is added into ethanol (10 L) and stirred. After filtration, a semi-opaque yellowish mixture of AMO/MMT platelet silicates is obtained with an organic/inorganic (O/I) ratio of about 40/60.
Step (e): The AMO/MMT mixture is added into ethanol (10 L) and stirred well. After water (10 L) is added and stirred well and then toluene (10 L) is then added and stirred well. After it is left to stand for one day, the mixture solution is separated into three phases, wherein the upper phase includes toluene and AMO, the middle phase includes ethanol, and the lower phase includes the product, a water solution of NSP.
Step (f): Octadecyl amine (ODA) and a water solution of NSP are mixed with an organic/inorganic weight ratio of 70/30 for modification of the nanosilicate platelets. After drying, an I/O dispersant (ODA/NSP) is obtained.

COMPARATIVE EXAMPLE 3

Repeat the steps of Example 4, but ODA and the water solution of NSP are mixed with an organic/inorganic weight ratio of 30/70 in Step (f).

EXAMPLE 5

Repeat Step (a) and Step (f) of Example 4, but NSP is replaced with MMT in Step (f). Then the product (ODA/MMT) with an organic/inorganic weight ratio 70/30 is obtained.

EXAMPLE 6

Repeat Step (a) and Step (f) of Example 4, but MMT of Step (a) and NSP of Step (f) are replaced with synthetic nanoclay (SNC). Then the product (ODA/SNC) with an organic/inorganic weight ratio 70/30 is obtained.

EXAMPLE 7

Repeat Step (a) and Step (f) of Example 4, but MMT of Step (a) and NSP of Step (f) are replaced with synthetic mica. Then the product (ODA/Mica) with an organic/inorganic weight ratio 70/30 is obtained.

EXAMPLES 8˜12

Repeat the procedure in the R.O.C. (Taiwan) Patent No.574370 “Combined Antifoulant of Derivative Disperser From Polyetheramine And PIBSA”, so that PIB-SA-POP or PIB-SA-POE can be obtained by grafting hydrophobic polyisobutylene succinic anhydride (PIB-SA) with Jeffamine® diamine D-230 (or POP230), D-400 (or POP400), D-2000 (or POP2000), D-4000 (or POP4000), and ED-2003 (or POE2000). The reaction is shown in FIG. 1. The I/O dispersants are obtained by respectively mixing these PIB-SA-POP or PIB-SA-POE with clay.

Evaluation of Dispersants and Dispersions

1. Dispersions of Examples 17 and Comparative Examples 13

The modified clay is uniformly dispersed in heptane to have a concentration of 1˜30 wt. %. Then TiO₂(10 wt. % or 50 wt. %) are added for dispersion. Effects of the dispersants are evaluated by observing or measuring the mobility and the uniformity of the dispersions with a viscometer, SEM, TEM, AFM, and an interfacial tension meter are provided. Results are listed in Table 1.

TABLE 1

Example/		Organic/	Effect for
Comparative	CEC	inorganic	dispersing TiO₂

Example	Dispersant	ratio	Weight ratio	10 wt. %	50 wt. %

Examples 1	D2000/MMT	1.0	74/26	+	−
Examples 2	D2000/MMT	0.8	69/31	+	−
Examples 3	D2000/MMT	0.6	63/37	+	−
Comparative	D2000/MMT	0.4	53/47	−	−
Examples 1
Comparative	D2000/MMT	0.2	36/64	−	−
Examples 2
Examples 4	ODA/NSP	—	70/30	+	+
Comparative	ODA/NSP	—	30/70	−	−
Examples 3
Examples 5	ODA/MMT	—	70/30	+	+
Examples 6	ODA/SNC	—	70/30	+	−
Examples 7	ODA/Mica	—	70/30	+	−

As shown in Table 1, the products D2000/MMT of Examples 1˜3 can effectively disperse TiO₂(10 wt. %), but those of Comparative Examples 1˜2 can not. As for high solid content of TiO₂(50 wt. %), none of the products D2000/MMT can disperse them well.
In Example 4, the product ODA/NSP with an organic/inorganic weight ratio 70/30 can effectively disperse TiO₂(both 10 wt. % and 50 wt. %). However, when the organic/inorganic weight ratio is 30/70 as in Comparative Example 3, even TiO₂(10 wt. %) can not be dispersed well.
In Example 5, the product ODA/MMT exhibits effect for dispersing TiO₂as good as in Example 4. Both TiO₂of 10 wt. % and 50 wt. % can be dispersed well.
In Comparative Examples 6 and 7, though the products ODA/SNC and ODA/Mica have higher organic/inorganic weight ratio 70/30, only TiO2 (10 wt. %) can be dispersed well.
FIG. 2 compares dispersions of TiO₂(20 wt. % in hexane) with and without dispersant, and with different dispersants. Picture (B) shows the bottles of picture (A) upside down, wherein no dispersant is added in the bottle (a), D2000/MMT (10 wt. %) is added in the bottle (b), and ODA/NSP (10 wt. %) is added in the bottle (c). the results show that ODA/NSP (10 wt. %) results in the best mobility and uniformity, that is, the dispersion has a lowest viscosity. The dispersion including D2000/MMT (10 wt. %) is not as good as that of bottle (c), but much better than that of bottle (a) without adding the dispersant.

2. Dispersions of Examples 8˜12

The I/O dispersants including PIB-SA-POP and PIB-SA-POE are first uniformly dispersed in methyl cyclohexane to have a concentration of 10 wt. %. Then different concentrations of TiO₂(10 wt. % and 50 wt. %) are added for dispersion. Effects of the dispersants are evaluated by observing or measuring the mobility and the uniformity of the dispersions. Results shows that both PIB-SA-POP and PIB-SA-POE (10 wt. %) perform well in dispersion and are suitable for processes with a low dosage.
In the present invention, the organic layered clay greatly facilitates dispersion of TiO₂in organic solvents when modified with organic surfactants or polyoxyalkylene-amine. By means of steric hindrance, different nanoparticles with different geometric shapes can reduce or countervail the energy thereof. For example, white TiO₂pigment particles or photocatalysts can be dispersed by the natural clay having a layered structure. Such mechanism using a geometric principle is not related to adsorption or desorption, and thus thermal stability of dispersions will be improved.
In the present invention, the layered clay is modified to have a hydrophobic end, and therefore can serve as a dispersant without aggregation. The modified clay can promote mobility and stability of high-concentration dispersions of TiO₂, wherein the nanosilicate platelets (NSP) with a high aspect ratio (average 100×100×1 nm dimension), high surface area (700˜800 m²/g) and high charge density (20,000 ions/platelet) is particularly preferred. Accordingly, properties or characteristics of the dispersion, for example, lower viscosity, better thermal, UW and pH stability, are improved and thus suitable for many applications.

Claims

1. An inorganic/organic (I/O) dispersant for dispersing a metal oxide, comprising a composite of an inorganic clay and an organic surfactant, or a composite of inorganic clay and polyoxyalkylene-amine,

wherein the organic surfactant is a cationic surfactant, a nonionic surfactant or an amphoteric surfactant; the inorganic clay is in the form of layers or sheets; and polyoxyalkylene-amine has a molecular weight of 200˜10,000.

2. The I/O dispersant as claimed in claim 1, wherein the metal oxide is selected from the group consisting of SiO₂, Fe₂O₃, Al₂O₃, ZrO, Ag₂O and TiO₂.

3. The I/O dispersant as claimed in claim 1, wherein the organic surfactant is a fatty amine quaternary ammonium salt of C12˜C32, an HCl amine salt of C12˜C32, a tetraalkyl quaternary salt of C12˜C32, alkylphenol ethoxylate or fatty alcohol ethoxylate.

4. The I/O dispersant as claimed in claim 1, wherein the organic surfactant and the inorganic clay has an organic/inorganic weight ratio of 10/90˜90/10.

5. The I/O dispersant as claimed in claim 1, wherein the inorganic clay is natural clay of silicate and aluminum oxide, exfoliated clay, synthetic mica or synthetic nanoclay.

6. The I/O dispersant as claimed in claim 1, wherein the polyoxyalkylene-amine is a Jeffamine® Amine series product of Huntsman Chemical Co.

7. The I/O dispersant as claimed in claim 1, wherein the polyoxyalkylene-amine and the inorganic clay have a cation exchanging capacity ratio of 0.1˜1.0.

8. The I/O dispersant as claimed in claim 1, wherein the polyoxyalkylene-amine and the inorganic clay have an organic/inorganic weight ratio of 55/45˜99/1.

9. The I/O dispersant as claimed in claim 1, wherein the polyoxyalkylene-amine is selected from the group consisting of Jeffamine® diamine D-230, D-400, D-2000, D-4000 and ED-2003.

10. The I/O dispersant as claimed in claim 1, wherein the composite of inorganic clay and polyoxyalkylene-amine further comprises polyisobutylene succinic anhydride (PIB-SA).

11. A method for producing an inorganic/organic (I/O) dispersant for dispersing a metal oxide, comprising a step of reacting inorganic clay with an organic surfactant, or reacting inorganic clay with polyoxyalkylene-amine,

wherein the organic surfactant is a cationic surfactant, a nonionic surfactant or an amphoteric surfactant; the inorganic clay is in the form of layers or sheets; and the polyoxyalkylene-amine has a molecular weight of 200˜10,000.

12. The method as claimed in claim 11, wherein the metal oxide is selected from the group consisting of SiO₂, Fe₂O₃, Al₂O₃, ZrO, Ag₂O and TiO₂.

13. The method as claimed in claim 11, wherein the organic surfactant is a fatty amine quaternary ammonium salt of C12˜C32, an HCl amine salt of C12˜C32, a tetraalkyl quaternary salt of C12˜C32, alkylphenol ethoxylate or fatty alcohol ethoxylate.

14. The method as claimed in claim 11, wherein the organic surfactant and the inorganic clay have an organic/inorganic weight ratio of 10/90˜90/10.

15. The method as claimed in claim 11, wherein the inorganic clay is natural clay of silicate and aluminum oxide, exfoliated clay, synthetic mica or synthetic nanoclay.

16. The method as claimed in claim 11, wherein the polyoxyalkylene-amine is a Jeffamine® Amine series product of Huntsman Chemical Co.

17. The method as claimed in claim 11, wherein the polyoxyalkylene-amine and the inorganic clay have a cation exchanging capacity ratio of 0.1˜1.0.

18. The method as claimed in claim 11, wherein the polyoxyalkylene-amine and the inorganic clay have an organic/inorganic weight ratio of 55/45˜99/1.

19. The method as claimed in claim 11, wherein the polyoxyalkylene-amine is Jeffamine® diamine D-230, D-400, D-2000, D-4000 or ED-2003 of Huntsman Chemical Co.

20. The method as claimed in claim 11, wherein polyisobutylene succinic anhydride (PIB-SA) is mixed with inorganic clay and polyoxyalkylene-amine in the step of reacting inorganic clay with polyoxyalkylene-amine.

21. A method for dispersing nanoparticles of a metal oxide, comprising a step of mixing an inorganic/organic (I/O) dispersant and nanoparticles of the metal oxide,

wherein the I/O dispersant is a composite of inorganic clay and an organic surfactant, or a composite of inorganic clay and polyoxyalkylene-amine,

wherein the organic surfactant is a cationic surfactant, a nonionic surfactant or an amphoteric surfactant; the inorganic clay is in the form of layers or sheets, and polyoxyalkylene-amine has a molecular weight of 200˜10,000.

22. The method as claimed in claim 21, wherein the metal oxide is selected from the group consisting of SiO₂, Fe₂O₃, Al₂O₃, ZrO, Ag₂O, TiO₂.

23. The method as claimed in claim 21, wherein the organic surfactant is a fatty amine quaternary ammonium salt of C12˜C32, an HCl amine salt of C12˜C32, a tetraalkyl quaternary salt of C12˜C32, alkylphenol ethoxylate or fatty alcohol ethoxylate.

24. The method as claimed in claim 21, wherein the organic surfactant and the inorganic clay have an organic/inorganic weight ratio of 10/90˜90/10.

25. The method as claimed in claim 21, wherein the inorganic clay is natural clay of silicate and aluminum oxide, exfoliated clay, synthetic mica or synthetic nanoclay.

26. The method as claimed in claim 21, wherein the polyoxyalkylene-amine is a Jeffamine® Amine series product of Huntsman Chemical Co.

27. The method as claimed in claim 21, wherein the polyoxyalkylene-amine and the inorganic clay have a cation exchanging capacity ratio of 0.1˜1.0.

28. The method as claimed in claim 21, wherein the polyoxyalkylene-amine and the inorganic clay have an organic/inorganic weight ratio of 55/45˜99/1.

29. The method as claimed in claim 21, wherein the polyoxyalkylene-amine is Jeffamine® diamine D-230, D-400, D-2000, D-4000 or ED-2003 of Huntsman Chemical Co.

30. The method as claimed in claim 21, wherein the composite of inorganic clay and polyoxyalkylene-amine is further mixed with polyisobutylene succinic anhydride (PIB-SA).