AU782284B2 - Aqueous dispersions - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Roiim and Haas Company ADDRESS FOR SERVICE: DAVIIES COLUISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

INVENTION TITLE: Aqueous dispersions The following statement is a full description of this invention, including the best method of performing it known to me/us:receivre 6-QejAVG.t 4

IA

The present invention relates to dispersions or slurries of particulate solids in water; in particular to dispersions of mineral solids which normally tend to aggregate, settle or phase out, and to a method of inhibiting those phenomena in slurries containing such mineral particles so as to improve the viscosity of such slurries making them more workable.

The present invention is suitable to produce slurries of various particulate solids, for example calcium carbonate for the paper industry and clays for use in the ceramic industry, but in fact the invention may be used for producing a workable aqueous dispersion or slurry of any solid particles in high concentration.

Previous attempts at producing such aqueous dispersions are described in, for example, EP-B-0129329. This document discloses pigment slurries containing water soluble polymers of molecular weight from 1,500 to 6,000 formed from one or more ethylenically unsaturated monomers and containing acid groups selected from carboxyl and sulphonic groups. The present invention shows enhanced performance over this prior art.

US-A-4,868,228 discloses grinding agents in aqueous suspensions of mineral materials, and, in particular, the use of such grinding agents to produce low viscosity aqueous suspensions of mineral solids. The grinding agents are described to be acrylic acid polymers and/or copolymers that are completely neutralised by at least one neutralising agent having a monovalent function and at least one neutralising agent having a polyvalent function.

EP-A2-0705892 teaches dispersions or slurries of solid particles in water which also comprise a phosphonocarboxylic acid or a water soluble salt thereof of the following formula, as a dispersing: 5-05:11:46AM:DAVI--S COLLISON CAVE#8/2 2 Fl(CHRCflRJ~n PO3M2/, wherein at least one R group in each unit is a COOM,~ group and the other R group is hydrogen or a COOM11N hydroxyl. phosphono, suiphono, sulphato, 01.7 alkyl group or a carboxylate, phosphono, suiphono, suiphato and/or hydroxy substituted 01L-7 alkyl or CIvz alikenyl group, and each M is a cation such that the phosphonated carboxylate is water soluble and n (the niumber of monomer units in polymerised form in the polymer chain) is from 1 to 6 and preferably less that for example I. to 3. The solid particles dispersed in this prior art preferably have a particle size of less than 1mm, for example less than 0.5mum, preferably to 100 j~m especially 1 to The present invention seeks to provide improved dispersions or slurries of solid particles in water. It is well known that it is especially difficult to achieve stable dispersions of fine materials; thus, it is of particular interest to produce stable dispersions of fine solid particles, such as those which have a significant proportion with a particle size of less than 2 tan.

The present invention, therefore, provides a dispersion of particulate solid in a medium containing water and at least one dispersing agent, characterised in that said dispersing agent comprises a water soluble polymer comprising: 0 A- P-OX Ox wherein X is H, Na, K, Ca, Mg, NH4' or A; and A is a polymer, copolymner or water soluble salt thereof, comprising one or more of the following monomers in polymerised form:- COMS IDNo: SBMI-01 271 673 Received by IP Australia: Time 12:03 Date 2005-05-30 1- 6-05; 9:28AM:DAVIES COLLISON CAVE 4/ 11 -3- R, H

R

3 OC R 2 1I 0 wherein RI is H, OH, Ci to C9 alkyl or alkoxy or acetoxy or acetate

R

2 is H, C, to C 3 alkyl or alkoxy, COOR 3

R

3 is H, Na, K, or Ct to Cio alkyl; hydroxylpropyl acrylate, propyl methacrylate, 2-acrylamido-2-propane sulphonic acid, sodium styrene sulphonate, sodium allylsulphonate, vinyl sulphonic acid, and salts thereof; acrylamide, methacrylamide, tert-butylacrylamide, (meth)acrylonitrile, styrene, vinyl acetate allyloxy-2-hydroxypropyl sulphonate and dialkylacrylamide; wherein A contains at least 10 monomers in polymerised form; and wherein the particulate solid is selected from the group consisting of one or more of calcium carbonate, kaolin clay, talc and metallic oxides; and wherein 70% or more of the particulate solid has a particle size of less than 2pm.

The number of monomers in polymerised form can be from 10 to more than 100, but 15 preferably it is from 15 to 85 and most preferably from 25 to 60. The dispersing agents may have a weight average molecular weight of from 1000 to 10,000, and dispersing agents having a weight average molecular weight of from 2000 to 6000 are especially preferred. Although stable dispersions with a low viscosity can be obtained with dispersing agents of a higher molecular weight, there is an increased tendency for gel formation with polymers of molecular weight above 6000 which may be disadvantageous in some applications.

The invention is particularly suited to forming dispersions of very fine particles, that is those in which 70% or more of the particles are below 2pm, and preferably those in which 70% or more are below 1pm. The invention works COMS ID No: SBMI-01276316 Received by IP Australia: Time 09:41 Date 2005-06-01 5-05;11:46AM:DAVIES COLLISON CAVE #10/ 26 -4particularly well with dispersions of fine particles in which 95% or more of the particles are below 1 pm.

The water soluble dispersing agent is preferably a phosphono terminated homo- or copolymer of acrylic acid. The other monomer if the dispersing agent is a copolymer may be maleic acid or maleic anhydride, methacrylic acid, sulfonic unsaturated monomers or any unsaturated polymerisable monomers having a COOH group. Such polymers may be made, for example, according to US 4,046,707, US 5,376,731, US 5,077,361 and US 5,294,686. In an embodiment of the invention the dispersing agent is selected from the group consisting of a phosphonate terminated homopolymer of acrylic acid with a weight average molecular weight of from 2000 to 5800 and a phosphonate terminated copolymer of acrylic acid and malkic anhydride with a weight average molecular weight of 2000 to 5800.

The dispersed or suspended solid is sufficiently chemically inert to be dispersed or suspended in an aqueous medium. The particles are inorganic, and substantially insoluble in water. Preferably, the particulate solid is calcium carbonate.

ll The liquid medium may be water, or a water-containing solution. This medium may 20 also contain alcohols, glycols, surfactants or wetting agents.

The composition of the present invention provides at least two important advantages, namely, a reduction in viscosity of the dispersion and a reduction in the tendency of the dispersion to form a gel particularly in fine particle dispersions. In addition, these benefits are obtained for systems in which the percentage by weight of the solid particles in the dispersion is high, for example greater than 60% and preferably greater than COMS ID No: SBMI-01271673 Received by IP Australia: Time 12:03 Date 2005-05-30 5-05:11:46AMI:DAVIE-S COLLISON CAVE 11/ 2E -4A Finally, the invention also provides a method of reducing the viscosity of a dispersion of solid particulate material in an aqueous medium, comprising contacting the aqueous medium, either before or after forming the dispersion of the solid particulate material, with an effective amount of at least one dispersing agent, wherein said dispersing agent comprises a water soluble polymer comprising- COMS ID No: SBMI-01271673 Received by IP Australia: Time 12:03 Date 2005-05-30 5-05;11:46AMDAVIES COLLISON CAVE 12/ 26 FA M A~ I fg)W A-fP-OX Ox wherein X is H, Na, K, Ca, Mg, N 4 or A; and A is a polymer, copolymer or water soluble salt thereof, comprising one or more of the following monomers in polymerised *5 foirm: R, H

C

:R

3 OC/ 2 0 wherein R 1 is H, OH, C 1 to C 9 alkyl or alkoxy or acetoxy or acetate

R

2 is H4, C 1 I to C 3 alkyl or alkoxy, COOR 3

R

3 is H, Na, K, or C 1 I to C 10 alkyl; hydroxyipropyl acrylate, propyl methacrylate, 2-acrylamido-2-propane sulphonic acid, sodium styrene suiphonate, sodium allylsuiphonate, vinyl suiphonic acid, and salts thereof; acrylamide, mithacrylam'ide, tert-butylacrylainide, (meth)acrylonitrile, styrene, vinyl acetate allyloxy-2-hydroxypropyl suiphonate and dialkylacrylamide; wherein A contains at least 10 monomers in polymerised form; and wherein the particulate solid is selected from the group consistinig of one or more of calcium carbonate, kaolin clay, talc and metallic oxides.

There are three general methods for making a dispersion of calcium carbonate fines: 1 combine natural calcium carbonate (including marble dust), water and dispersing agent together and mix to form a slurry; COMS ID No: SBMI-01271673 Received by IP Australia: Time 12:03 Date 2005-05-30 5-05:11:46AMIDAVIES COLLISON CAVE #1/2 13/ 26 6 2) precipitate calcium carbonate from an aqueous solution of soda lime (calcium hydroxide) and carbon dioxide, collect the pr~ecipitated material and mix with water and a dispersing agent to form a slurry; and 3) grind calcium carbonate to the desired particle size and mix with water and a dispersing agent to form a slurry.

Embodiments of the present invention will now be described with reference to the following non-limiting Examples.

General Method to Prenare Dispersions of Either Coarse Or Finely Precipitated Calcium Carbonate and Measurement Of Viscosity Thereof.

a) An aqueous solution is formed by dissolving a dispersing agent in water in a bbeaker.

bThe aqueous solution is then agitated and a mineral solid to be dispersed is added thereto; a slow addition rate is needed to avoid agglomeration c) Agitation is maintained for about 10 minutes after the addition of the mineral solid.

d) F~inally, viscosity is measured immediately, and then after 1 hour, 24 hours and 48 hours 'using conventional viscosimeters, such as Bookfield, Ford cup etc.

9 General Method to Prepare Dispersions of Ground Natural Calcium Carbonate and Measiurement Of Viscosity Thereof.

a) Water, dispersing agent and natural calcium which is to be ground are introduced in a vessel containing the grinding agent (balls).

The solution is then shaken or agitated until the desired particle size is obtained.

c) The viscosity of the solution is then measured immediately and then after 1 hour, 24 hours and 48 hours. Viscosity may be measured using conventional viscosirneters, such as Bookfield, Ford cup etc.

COMS ID No: SBMI-01271673 Received by IP Australia: Time 12:03 Date 2005-05-30 7 The dispersing agents used in the above tests are described in Table 1 below: **0 Table 1: Dispersing Agent Compositions Dispersing Agent Composition 1(comp) 100AA (IPA) Mw 5010 solids 43.5 pH (DISPEX DP6) 2 (coinp) 100AA (NaHP) Mw 3500 solids 42.5 pH 3 (comp) 9SAAISHEA Mw 4560 solids 42.4 pH 8.1 4 (comp) 95AAISHPA-Mw 4570 solids 41.8 pH 7.4 (comp) 95AAISEA Mw 4520 solids 42.6 pH 6 (comnp) 100AA (NaHP) Mw 4830 solids 47.7 pH 7 (comp) 100AA (SMBS) Mw 2000 solids 43.0 pH 7.2 8 (comp) 100AA (SMBS) Mw 4500 solids 45.0 pH 9 (comp) 100AA (NaHP) Mw 3500 solids 42.5 pH 10 (comp) (DISPEX 100AA (IPA) Mw 3410 solids 40.0 pH 11 (comip) (DISPEX 100AA (IPA) Mw 4500 solids 42.4 pH 2695) 12 (comp) Preferred phosphonated oligonmaleate of EP-A-705892, prepared according to Example 1 of EP-A-0569731 A (exp) 100AA (H3PO3) Mw 5110 solids 45.8 pH 6.6 B (exp) 100AA (H3PO3) Mw 4880 solids 48.7 pH 7.1 C (exp) 100AA (Hi3PO3) Mw 3600 solids 40.0 pH D (exp) 9OAAI1OMALAC (H3P03) Mw 2000 solids 50.0 pH E (exp) 100AA (113P03) Mw 2000 solids 50.0 pH F (exp) 100AA (H3PO3) Mw 5170 solids 42.0 pH G (exp) 100AA (H3P03) Mw 5170 solids 42.0 pH H (exp) 100AA (H3PO3) Mw 5800 solids 42.0 pH 1 (exp) 100AA (H3PO3) Mw 5800 solids 42.0 pH Key: DISPEX N40, DISPEX DP 6 and DISPEX 2695 are commercial dispersing agents available from Allied Colloids Limited. DISPEX is a trade mark owned by Allied Colloids Limited.

AA acrylic acid MALAC maleic acid AMPS 2-acrylamido 2-methyl propane sulphonic acid EA ethyl acrylate HEA hydroxy ethyl acrylate HPA hydroxy propyl acrylate Dispersing agents 1, 10 and 11 were prepared using a method well known to those skilled in the art using isopropyl alcohol (IPA) as the chain transfer agent.

Dispersing agents 2, 6, and 9 were prepared using sodium hypophosphite (NaHP) as the chain transfer agent. Dispersing agents 7, and 8 were prepared using sodium metabisulphite (SMBS) and dispersing agents A-I are phosphonate containing polymers of the present invention and were all prepared using phosphorous acid (H3P03)as the chain transfer agent.

Example 1: Measurement of Viscosity and Gel Tendency for Dispersions of Precipitated Calcium Carbonate of Particle Size 70% 2 Microns Aqueous dispersions of precipitated calcium carbonate with particle size 70%<2 microns were prepared using General Method described above. The Viscosity and gel tendency results are given in Table 2 below.

Table 2: Viscosity and Gel Tendency Results for Dispersions of P a. d Calcium Carbonate of Particle Size 70% 2 Microns 1

S

OS

Disp. dose Solids Brookfield Viscosity Gel Tendency Agent (rpm) 50 100 lhr 24hr 48hr 1 0.80 75.0 2700 876 582 1.0 7.1 2 0.80 75.0 2860 916 604 1.3 7.1 9.1 C 0.80 75.0 1860 652 444 0.7 4.1 D 0.80 75.0 1540 556 390 0.5 2.1 4.2 G 0.80 75.0 1120 456 344 0.3 7.9 11.8 The above results demonstrate that the dispersing agents used in the present invention, i.e. C, D and G, provide dispersions with significantly lower viscosity than dispersing agents 1 and 2. Also, with dispersing agents C and D, in particular, the gel tendency is much lower than that obtained for similar dispersions using non-phosphonate containing polymers as the dispersing agent.

Example 2: Measurement of the Viscosity and Gel Tendency for Ground Natural Calcium Carbonate of Particle Size 79-83% 1 Micron Aqueous dispersions of ground natural calcium carbonate with particle size 79- 83%<1 micron were prepared using General Method described above. The Viscosity and gel tendency results are given in Table 3 below.

Table 3: Viscosity and Gel Tendency Results for Ground Natural of Particle Size 79-83% 1 Micron age* C S 0: *06*0 0 0 o .0 a .5 0-0* Disp. dose Solids Brookfield Gel Tendency Agent 1 pm Viscosity (rpm) %<1pm 10 50 100 2hr 24hr 48hr 1 2.35 78.5 75.7 440 184 136 0.5 2 3 A 2.4 78.6 75.4 520 224 168 1 2 3 3 2.37 78.0 74.7 1360 624 456 8 30 34 4 2.38 77.6 74.8 720 352 268 4 23 28 2.45 78.0 Slurry too viscous 6 2.42 78.5 75.4 1200 380 1.5 8 12.5 As the above results show, dispersing agent A which contains phosphonate groups and is according to the present invention, provides favourable viscosity and gel tendency as compared to the comparative dispersing agents 3, 4, 5 and 6.

S 8 5* S S SO a S.

Example 3 Measurement of the Viscosity and Gel Tendency For Dispersions Of Precipitated Calcium Carbonate of Particle Size 95%< 1Microns Aqueous dispersions of precipitated calcium carbonate with particle size 95%<1 micron were prepared using General Method described above. The Viscosity and gel tendency results are given in Table 4 below.

Table 4: Measurement of the Viscosity and Gel Tendency Results Obtained For Dispersions of Precipitated Calcium Carbonate of Particle Size 95% 1 Microns Disp. dose pH Solids Brookfield Viscosity Gel Tendency Agent (rpm) 50 100 1hr 24hr 48hr 1 0.8 12.3 75.0 2900 920 582 1.9 10.9 15.2 2 0.8 12.4 75.0 7740 2012 1158 5.3 13.9 15.7 7 0.8 11.7 75.0 17360 NM NM 10.7 18.2 21.7 8 0.8 12.2 75.0 6740 1840 1072 4.6 19.7 20.9 9 0.8 11.7 75.0 5340 1448 850 3.4 13.1 13.9 0.8 12.3 75.0 3060 944 586 2.3 12.5 14.6 11 0.8 11.6 75.0 3120 964 602 1.8 11.5 13.1 C 0.8 11.2 75.0 3360 1000 614 2.6 9.1 10.3 D 0.8 12.7 75.0 2840 852 526 2 7.3 8.7 E 0.8 10.8 75.0 7160 1888 1086 4.8 8.6 B 0.8 12 75.0 1980 764 512 1.2 17 17.9 F 0.8 10.9 75.0 1280 550 394 0.9 15.1 19.3 G 0.8 12.9 75.0 840 448 344 0.3 17.9 21 H 0.8 12.4 75.0 1600 668 466 0.4 21.1 27.7 I 0.8 12.9 75.0 1360 604 430 0.2 20.5 23.4 From the results in Table 4, it is to be noted that phosphonopolycarboxylic acids provide a significant improvement in the viscosity and gel tendency of dispersed of calcium carbonate with 95% of the particles being less than 1 micron in size.

Example 4: Comparison of the Viscosity of Dispersing Agent C Against the Viscosity of Dispersing Agent 12 (the preferred phosphonated oligonmaleate of EP-A-705892 which was prepared according to Example 1 of EP-A-0569731).

Aqueous dispersions of precipitated calcium carbonate with particle size 90%<1 micron were prepared using General Method described above. 0.8% dispersing agents were used. The viscosity was measured using a Brookfield viscosimeter RV model (spindle 4) at 10, 20, 50 and 100rpm. The results are given in Table 5 below.

Table 5: Viscosity for Dispersing Agent C Against Dispersing Agent 12 Dispersing Agent C (exp.) Dispersing Agent 12 (comp.) Spindle Viscosity Torque Viscosity Torque Speed (mPa.s) (mPa.s) 7260 36.3 Not measureable, too viscous 4030 40.3 Not measureable, too viscous 1884 47.1 Not measureable, too viscous 100rpm 1078 53.9 Not measureable, too viscous Example Comparison of the Torque of Dispersing Agent C Against the Torque of Dispersing Agent 12 (the preferred phosphonated oligonmaleate of EP- A-705892 which was prepared according to Example 1 of EP-A-0569731).

Aqueous dispersions of precipitated calcium carbonate with particle size 90%<1 micron were prepared using General Method described above. 0.8% dispersing polymers were used. This time the Torque was measured at time zero, and after 1, 2 and 7 days using a Brookfield viscosimeter RV III model and a helipath spindle (lrpm/25s spindle The results are given in Table 6 below. Torque is related to the gelation behaviour of calcium carbonate slurries.

Table 6: A Comparison of the Gel Tendency Results Obtained For Dispersing Agent C Compared Against Dispersing Agent 12.

Dispersing Agent C (exp.) Dispersing Agent 12 (comp.) Time (days) Viscosity Torque Viscosity Torque (mPa.s) (mPa.s) 0 57000 5.7 735000 73.5 1 134000 13.4 730000 73.0 2 142000 14.2 742000 74.2 187000 18.7 813000 81.3 As the results in Tables 5 and 6 above demonstrate, the phosphonated dispersing agents of the present invention provide significantly improved performance over the dispersing agents of prior art document EP-A-0705892, providing stable dispersions with a lower viscosity, even after standing for several days.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Claims (5)

1. 5-05:11:46AM:OAVIES COLLISON CAVE 14/ 26 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. Dispersion of particulate solid in a medium containing water and at least one dispersing agent, characterised in that said dispersing agent comprises: a water soluble polymer comprising: A Pf -OX Ox wherein X isH,Na, K, Ca, Mg, N144~ or A; and A is a polymer, copolymer or water soluble salt thereof, comprising one or more of the following monomers in polymnerised form: R H C R 3 OC R 2 0 wherein R is H, OH, C 1 to C 9 akyl or alkoxy or actoxy or acetate R 2 is H, C, to C 3 alkyl or alkoxy, COOR 3 R 3 is 1H, Na, K, or CI to CIO alkyl; hydroxyipropyl acrylate, propyl. methacrylate, 2-acrylamido-2-propane suiphonic acid, sodium styrene sulphonatc, sodium allylsuiphonate, vinyl suiphonic acid, and salts thereof; aerylamide, methacrylamide, tert-butylacrylamide, (meth)acrylonitrile, styrene, vinyl acetate allyloxy-2-hydroxypropyl suiphonate and dialkylacrylamide; COMS ID No: SBMI-01271673 Received by IP Australia: Time 12:03 Date 2005-05-30 1- 6-05; 9!28AtI:DAVIE-S COLLISON CAVE 5/ 11 -16- wherein A contains at least 10 monomers in polymerised form; wherein the particulate solid is selected from the group consisting of one or more of calcium carbonate, kaolin clay, talc and metallic oxides; and wherein 70% or more of the particulate solid has a particle size of less than 2pu. 2. Dispersion according to claim 1 or claim 2, comprising at least 60% by weight of thle dispersion of lahe particulate solid. 3. Dispersion according to claim I or claim 2, wherein the weight average molecular weight of the dispersing agent is from 1000 to 10,000. 4. Dispersion according to claim 3, wherein the weight average molecular weight of the dispersing agent is from 2000 to 6000. 5. Dispersion according to any one of the preceding claims, wherein the dispersing agent is selected from the group consisting of a phosphonate terminated homopolymer of acrylic acid with a weight average molecular weight of from 2000 to 3800 and a phosphonate terminated copolymer of acrylic acid and maleic anhydride with a weight average molecular weight of 2000 to 5800.
2. 6. Dispersion according to any one of the preceding claims, wherein the particulate solid is calcium carbonate.
3. 7. Method of reducing the viscosity of a dispersion of a solid particulate material in an aqueous medium comprising contacting the aqueous medium, either before or after forming the dispersion of the solid particulate material, with an effective amount of at least one dispersing agent, wherein said dispersing agent comprises: a water soluble polymer comprising: COMS ID No: SBMI-01276316 Received by IP Australia: Time 09:41 Date 2005-06-01 1- 6-05; 9:28AM:DAVIES COLLISON CAVE 6/ 11 17 A- f-OX Ox wherein X is H) Na, K, Ca, Mg, NI- 4 or A; and A is a polymer, copolymer or water soluble salt thereof, comprising one or more of the following monomers in polymerised form: R, H C R 3 OC R 2 wherein R I is H, OH, C 1 I to C 9 alkyl or alkoxy or acetoxy or acetate R 2 is H, C, to C 3 alkyl or alkoxy, COOR 3 R3 is H, Na, K, or C 1 I to C 10 ailkyl; hydroxyipropyl acrylate, propyl inethacrylate, 2-acrylamido-2-propane suiphonic acid,+ *:sodium styrene suiphonate, sodium allylsuiphonate, vinyl suiphonic acid, and salts thereof; acrylamide, inethacrylamide, tert-butylacrylamide, (meth)acrylonitrile, styrene, vinyl acetate allyloxy-2-hydroxypropyl suiphonate and dialkylacrylamide; wherein A contains at least 10 monomers in polymerised form; and wherein the particulate solid is selected from the group consisting of one or more of calcium carbonate, kaolin clay, talc and metallic oxides.
4. 8. Method according to claim 7, wherein the dispersion comprises at least 60% by weight of the particulate solid. COMS ID No: SBMI-01276316 Received by IP Australia: ime 09:41 Date 2005-06-01 1- 6-05: 9:28AM:DAVIES COLLISON CAVE 7/ 1 1
5. 9. Dispersion according to claim 1 substantially as hereinbefore described with reference to the Examples. A method according to claimn 7 substantially as hereinbefore described with reference to the Examples. DATED this 1" day of June, 2005 Rohm and Haas Company By DAVIES COLLISON CAVE Patent Attorneys for the Applicant COMS ID No: SBMI-01276316 Received by P1 Australia: Time 09:41 Date 2005-06-01