Treatment process

200 7S03 -2This invention relates to a treatment process and particularly to the treatment of an inorganic powder with an organic material.

According to the present invention a process for the treatment of an morganic powder comprlses polymerising a reaction ~ lure of an ethylenically s lmc~tllrated monomer in the presence of a dispersed inorganic powder having a cationic charge on the surface of the particles thereof, said monomer being present in an amount not greater than 200~o of the weight of said powder, and subjecting the said monomer and said powder to the effect of ultra onic vibrations during at least a part of the polymerisation of said monomer so that 10 said particles are coated with polymerised monomer.

The present invention is a process for coating particles of an inorganic powder with an organic polymer.

The process reduces to a ~ lm any free polymer produced which does not form part of a coating and seemingly the coating obtained is thicker than that obtained by a process which does not 15 involve the use of ultrasonic vibrations.

The products are well dispersed and aggregation is minimiced.

Generally speaking the process involves the preparation, initially, of a dispersion, usually an aqueous dispersion, of the inorganic powder to be coated,and, if necessary, the modification of the particles thereof so that the surface20 thereof carries a cationic charge.

An ethylenically ~mc~t~lrated monomer usually is then added to the dispersion of the inorganic powder and polymerisation initiated by an appropliate technique.

During at least a part of the polymerisation the dispersion of the inorganic powder is subjected to ultrasonic vibrations which have the advantageous effects hereinbefore 25 specified.

In order to minimice further the production of free polymer the 2~03 -3amount of the monomer should not exceed 200 per cent by weight of the inorganic powder.

The process of the present invention can be used to coat the particles of any inorganic powder but those of more interest are the inorganic pigments, 5 extenders and fillers.

Particularly, inorganic pigments are found to be of most use in the process and such pigments are titanium dioxide pigments, ~lllminium oxide pigments, antimony oxides, barium pigments, calcium pigments, zirconium pigments, chromium pigments, iron pigments and magnesium pigments.

Extenders and/or fillers such as silica, silicates, ~ min~tes and particularly the 10 clays can also be treated by the process of the invention.

Mixtures of pigments and extenders can also be treated as well as non-pigmentary forms of the inorganic powders mentioned as pigments.

In the most preferred process the inorganic powder is titanium dioxide pigment, preferably rutile titanium dioxide.

Desirably the inorganic powder is in a finely divided state prior to coating and, if 15 necessary, can be milled by suitable means to achieve such a state.

In the polymerisation the dispersed inorganic powder particles have a cationic charge on their surfaces.

Usually the inorganic powder will require actual treatment with a suitable compound to produce such a cationic charge but in some types of powders a cationic charge can be produced by lowering the 20 pH of an aqueous dispersion of the powder to a value below pH 7 by adding an acid.

However for many of the inorganic powders actual treatment with a surface charge modifying agent is neces~ry.

Typically a dispersion of the inorganic powder is treated with a suitable cations and examples of such cations are A13+' Zn2+, Th4+, UO22+ and Pd2+.

25 However the use of ~ln"~ "" salts are preferred in view of their cost and thesize of the ion which is small.

Preferably the surface charge modifying agent is 20(~7~ an ~ ",iniu", salt of a mineral acid such as ~h~ llll sulphate or ~lnminillm chloride but preferably the salt is ~hlminillm nitrate.

If desired the inorganicsurface charge modifying agent can be replaced in part or supplemented by the use of an organic compound which is cationic in the particular dispersion.

If 5 desired the organic compound, itself, can be a polymerisable monomer but non polymerisable cationic compounds can be used.

Preferably the organic compound is a polyelectrolyte and suitable compounds are protein colloids, cationic guar gum, certain polymers of methacrylates, vinyl amine and vinyl pyridine.

Methacrylic acid can be added to the powder dispersion, usually prior 10 to the surface modifying agent as an adjunct, if desired.

The amount of the surface charge modifying agent need only be sufficient to achieve the desired cationic charge density and can be determined easily by electrophoretic or other means.

Typical amounts of the surface charge modifying agent will be from 2.5% to 7.5% by weight, of say, an alllmininm salt,15 on weight of inorganic powder depending on the particular inorganic powder to be treated and on the desired cationic charge.

As described the process of the present invention polymerises an ethylenically ~m~t~lrated monomer to coat the inorganic powder particles with a polymer or copolymer as is desired.

Any ethylenically ~ms~tllrated monomer 20 which is polymerisable in an emulsion polymerisation system can be used in the present invention.

Usually the polymer produced desirably is insoluble in water and, if necessary may be cross-linked by a suitable cross-linking agent.

Typicalethylenically lln~tmated monomers are aliphatic or aromatic compounds cont~ining a polymerisable ~m.c~t~lrated group such as the ~m~tllrated carboxylic 25 acids or lm~turated carboxylic acid esters.

One of the carbon atoms forming the double bond can preferably carry two hydrogen atoms and such compounds ~007503 _.

would be named vinyl monomers.

Typical monomers useful are acidic monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or its anhydride, fumaric acid, crotonic acid.

Esters of acid monomers can be used such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate and5 ethyl methacrylate.

Other monomers which can be polymerised to form coatings are styrene, vinyl toluene, alpha methylstyrene, ethylene, vinyl acetate, vinyl chloride, acrylonitrile, and the like.

If desired two or more of the polymerisable monomers can be copolymerised.

Also a cross-linking agent can be present and typical agents are di10 or poly-functional ethylenically lln~ rated monomers, for example ethylene glycol dimethacrylate, ethylene glycol diacrylate, allyl methacrylate, allyl acrylate, 1,3-butanediol diacrylate, divinyl benzene or 1,3-butanediol dimethacrylate.

The amount of such cross-linking agent can be within the range of 10% to 50% by weight of said agent on weight of total monomer employed.

As described hereinbefore the amount of said polymerisable ethylenically lln~ lrated monomer is not greater than 200% by weight of the inorganic powder and plefe-ably the amount is not greater than 100~o by weight.

In the most desirable process the amount of said polymerisable ethylenically lln~ lrated monomer is within the range 2% to 25% by weight of 20 the inorganic powder.

The inorganic powder usually will be formed into an aqueous dispersion initially, if necessary, with the aid of a dispersing agent.

This dispersion can be milled, if desired, and then to the dispersion there is added any necessary surface-modifying agent, followed by, or preceded by, any desired organic 25 polyelectrolyte or other adjunct.

When the adjunct is an organic acid such as _ 2007503 -6methacrylic acid an amount of a cross-linking agent such as ethylene glycol dimethacrylate can also be added.

In the process of the invention the chosen monomer usually, prior to mixing with the inorganic powder, is formed into an aqueous emulsion 5 employing, as is necessary, a nonionic or anionic emulsifier or a mixture thereof to assist the emulsification.

Typical emulsifying agents are sodium dodecyl benzene sulphonate and ethoxylated alkyl phenols such as those in which the alkyl group is a nonyl, octyl or decyl group.

Other known emulsifying agents canbe employed.

Where the polymerisation is to be effected in the presence of a crosslinking agent for the chosen ethylenically lln~t~lrated monomer or monomers then this usually but not always will be added to the inorganic powder separately from the emulsion of the monomer.

Usually the polymerisation is initiated with a water-soluble initiator such 15 as a peroxy compound, a persulphate, a peracetate or a redox initiator, e.g. a salt of a persulphuric acid or an organic hydroperoxide or peroxide in combination with a sulphite, bisulphite, hydrosulphite or metal formaldehyde sulphoxylate.

The initiator is added at any suitable stage? e.g. prior to the addition of the monomer to the inorganic powder.

Only a part of the required amount of the 20 initiator can be added initially followed by the rem~ining necessary amount or amounts at one or more later stages.

The polymerisation of the added monomers is usually carried out at an elevated temperature, and depending on the ambient tempel~lure within the range 25C to 80C, usually from 30C to 50C.

The polymerisation normally 25 but not always is effected in an inert atmosphere, for example, under a protective atmosphere of an inert gas, e.g. nitrogen.

- 2007503 -7In the process of the present invention at least part of the polymerisation is effected while subjecting the ~ ule of the monomer and inorganic powder to the effect of ultrasonic vibrations.

Usually this is achieved by immersing anultrasonic vibrator in the aqueous ~ ure being polymerised and preferably the ~ lule is treated with the vibrations from the commencement of polymerisation.

The ultrasonic vibrations are those known as power ultrasound usually employing frequencies in the range 20 to S0 kHz.

The actual power delivered to the mLxture depends on that desired and on the volume of mLxture being treated and it has been found that most advantageous results are obtained by employing relatively low powers of ultrasonic vibrations.

Preferably, the power output into the polymerisation lllixl~lre is within the range lS to 60 watts per litre of ll~ ure and most desirably 20 to 30 watts per litre.

Typically the amount of inorganic powder in the ~ ure is within the range lS0 to 300 gms per litre, preferably 200 to 240 grams per litre.

lS The use of lower amounts of power of the ultrasonic vibrations produces a more uniform coating insofar as the degree of coverage is concerned.

Higher amounts of power provide a beKer dispersion of the particles of the inorganic powder.

The use of lower concentrations of inorganic powder in the aqueous dispersion also hllploves the thickness and u"~rolmity of the coating coverage.

The coated particles produced by the process of the invention can be used as opacifiers in paints and other media such as in plastics and inks.

The coating provides an improvement of the dispersion of the inorganic material in organic media and also tends to reduce the abrasivity of the powder on m~nllf~ctllring equipment for plastics cont~ining the powders.

The invention is illustrated in the following Examples.

~007~3 -8EXAMPLE 1 The general process for the production of coated inorganic powders is described in the following numbered stages during which an atmosphere of dry nitrogen was m~int~ined in the reaction vessel.

S st~Pe 1.

Inorganic powder (19Og) was weighed into a 1 l. kettle and 750 ml of N2 purged (30-60 mins, dry N2) distilled water added.

The slurry was mechanically stirred at 20C for 5-10 mimltes.

st~e 2.

Methacrylic acid (MA) (1.9 g) was added and stirring continued for 15 minlltes at 20C.

St~e 3.

Al(NO3)3 (2.8 g) (AIN) was added and stirring conlillued for 10 minutes.

S~ge 4.

Ethylene glycol dimethacrylate (EDMA, 0.525 g) was added and the temperature raised to 40C (20-30 mins).

Stirring was conLh~ued at 40C for 15 minutes.

st~e 5.

Fresh solutions of 1% pot~c~ium persulphate (0.25 g/25 ml, solution A) and 1% sodium bisulphite (0.25 g/25 ml, solution B) were prepared. 1.8 g of solution A and O.9g of solution B were added to the kettle and stirring colllhlued for 15 minlltes.

St~e 6.

Methyl methacrylate (MMA, 7.5 g) was emulsified in water (100 ml) with an emulsifying agent (EA) (0.38 g) using an ultrasonic probe (5 mimltes).

The emulsion was added (5 ml aliquots), with stirring, over a period of 15 mimltes.

~ 2Q07503 g st~e 7.

Ethylene glycol dimethacrylate (0.41 g) was added and the temperature raised to 70C (45-65 mins).

St~e 8.

S ` Further aliquots of solution A (7.2 g) and solution B (3.6 g) were added and the polyrnerisation left for 4 hours at 7~C.

st~pe 9.

After 4 hours the product was filtered, washed with water and dried overnight at 70C.

The emulsifying agent was isooctylpheno~l,olyethoxy ethanol and was available comrnercially under the Trade Mark'~riton - xn.

In carrying out specific experiments as detailed here~arler ultrasound was applied to the re~ction vessel employed in experiment 2 by an ultrasound bath (1~15/cm2 watts) and for the re...~ini.~g eA~e~ lcnts by ultrasonic probes - 15 of dirrerellt basic power oul~ub, one of a m~;-------- rated output of 225 watts (probe X) and one of a m~ .----.. rated output of 375 watts (probe Y).

The ultrasound was used according to three dirrere.lt srlle~ les i.e.

Schedule I - during stages 1 to 5 inclusive E - during stages 1 to 7 indusive P - during stages 5 to 7 inclusive Twenty six ,~.i~ents were carried out as described below with the conditions as shown in Table 1. l~e watts shown was the actual ~mollnt of power delivered to the re~ct~nt~ during operation of the probe.

In Experiments 3 to 8, 11 to 18 and 21 to 26 the chosen probe was operated at 30% rated output and in the other experiments at 60% of rated output.

The amount of reagents ` ~007503 -10shown is that given in the general description (i.e. 1 = same; Y2 = Y2 of the general description etc.) TABLE 1 EXP ULTRASOUND POWDER MA AIN EDMA EA MMA PROBE/WATTS/ DURATION NONE 1 Ba2SO4 2 BATH/WATTS/E 1 Ba2SO4 3 Y/47/P 1 TiO2 4 X/28/P 1 TiO2 Y/47/E 1 TiO2 6 X/28/E 1 TiO2 7 X/28/I 1TiO2 8 Y/47/I lTiO2 9 X/55/E 1 TiO2 Y/41/E 1 TiO2 11 Y/22/E 1 TiO2 1 1 1 Y2 12 X/28/E 1 TiO2 1 1 1 Y2 13 Y/22/I Y2 TiO2 Y2 Y2 Y2 Y2 Y2 14 X/28/I Y2 TiO2 Y2 Y2 Y2 Y2 l/2 Y/22/I Y2 TiO2 1 1 1 Y2 16 X/28/I Y2 TiO2 1 1 1 Y2 17 Y/22/I 1 TiO2 18 X/28/I 1TiO2 19 Y/41/I Y2 TiO2 1 1 1 Y2 ~007503 X/SS/I Y2 TiO2 1 1 1 Y2 21 Y/22/I 1 TiO2 2 2 2 1 2 22 X/28/I 1 TiO2 2 2 2 1 2 23 Y/22/I 1 TiO2 1 1 1 1 2 24 X/28/I 1 TiO2 1 1 1 1 2 2S Y/22/I 1 TiO2 2 1 1(DVB) Y2 26 X/28/I 1 TiO2 2 1 1(DVB) Y2 DVB = divinyl benzene instead of EDMA The products obtained were çY~mined by electron microscopy and 10 micrographs visually assessed.

Generally speaking the P~min~tion showed that the use of ultrasound hllploved the degree of coverage of the product of experiment 2 as compared with experiment 1.

It was seen that the most beneffcial effect was obtained when ultrasound was used only in the initial stage of the reaction i.e. I was better than P which 15 was better than E.

Also the use of lower power levels hlll)roved the coverage as compared to higher power but higher power levels produced better dispersion of the coated particles.

An increase in the ratio of em~ ing agent/powder illlproved the 20 coverage. A decrease in the content of TiO2 slightly iml)loved the thickness and u~ifollllily of the coating.

Also increasing the monomer concentration increased the coverage and un.ror,nily of the coating.

In the experiments the tit~nillm dioxide used was the reactor discharge obtained in the vapour phase oxidation of titanium tetrachloride.

; Z~]075~3 -12Example 2 The general process as detailed in Example 1 was repeated with certain variations as detailed in the description of the Experiments described below.

The probe was probe Y and the power was supplied at an input of 22 watts 5 during stages 1 to 5 inclusive unless specified otherwise.

The powder used was the same ti~nillm dioxide as in Experiments 3 to 26.

Experiment 27 In stage 2 acrylic acid (1.9g) was added instead of the methacrylic acid.

The product was polymer coated titanium dioxide.

Experiment 28 Three different amounts of the emulsifying agent (EA) were employed equivalent to 5%, 3% and 12% by weight of monomer.

All produced similar degrees of coating on the powder but the optimum level was about 10% by weight of monomer.

Experiment 29 Butyl acrylate was used instead of methyl methacrylate.

The powder was coated with polymer.

Experiment 30 St.,vrene was used in place of methyl methacrylate.

The product had a 20 ullirollll coating of polymer.

Experiment 31 A ll~i~lure of equal weights of methyl methacrylate and butyl acrylate was used instead of methyl methacrylate alone.

The product was Ill~irollllly coated with polymer.

-13- 2~07503 Experiment 32 Methyl methacrylate was replaced by butyl methacrylate.

An encapsulated product was obtained.

Experiment 33 The emulsifying agent (EA) used was sodium dodecyl benzene sulphonate. A coated product was obtained but the co~ting was not as thick as that obtained using the emulsifying agent used in Experiments 1 to 24.

Experiment 34 Cetyl trimethyl ammonium bromide was used as the emulsifying agent.

A product similar to that of Experiment 33 was obtained.

Experiment 35 The emulsifying agent used was sodium dodecyl benzene sulphonate and butyl acrylate was used in~te~l of methyl methacrylate. A uniformly coated product was obtained.

Experiment 36 Amounts of methyl methacrylate were chosen to be equivalent to 1%, 3%, 5%, 7%, 9~o, 11%, 13%, 15%, 17%, l9~o, 21%, 23% and 25% of polymer on powder weight.

All produced coated products.

Experiment 37 Amounts of pot~csium persulphate of 1%, 2%, 3%, 4%, 5~o, 6~o and 6.5% on weight of powder were used and amounts of sodium metabisulphite of 1%, 2%, 3% and 3.25% on powder were used in stages 5 and 8.

All produced polymer coated products with an optimum co~ting being obtained using pot~ccium persulphate in amounts of 1.44% and 6.5~o in stages 5 and 8 respectively and sodium metabisulphite in amounts of 0.72~o and 3.25~o in stages S and 8 respectively.

~07503 -14Experiment 38 A mixture of 2 parts by weight styrene and one part by weight of methyl methacrylate was used instead of methyl methacrylate.

The product was polymer coated powder.

Experiment 39 The sonic vibrations were applied throughout all the reaction stages but in a pulsed manner (at approYi",~tely 30 second intervals) instead of in a continuous manner.

Again a polymer coated product was obtained.

Experiment 40 The process of Example 1 was carried out except that the power input in stage 1 was S0 watts. A polymer coated powder was produced.

In Experiments 27 to 40 where a re~ct~nt (or mixture) replaced another re~ct~nt described in Example 1 then unless specified otherwise an equal weight of the replacement was used.

All products were analysed visually by tr~n~mi~sion electron micrographs.