CA1110504A - Polymer coated inorganic fillers - Google Patents
Polymer coated inorganic fillersInfo
- Publication number
- CA1110504A CA1110504A CA304,247A CA304247A CA1110504A CA 1110504 A CA1110504 A CA 1110504A CA 304247 A CA304247 A CA 304247A CA 1110504 A CA1110504 A CA 1110504A
- Authority
- CA
- Canada
- Prior art keywords
- filler
- organic polymer
- polymer
- acidic group
- basic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/028—Compounds containing only magnesium as metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A coated particulate filler which comprises an acidic group-containing organic polymer containing at least one unsaturated group and which has a molecular weight of not greater than 100,000 bound to the surface of a basic particulate, for example, calcium carbonate, a process for producing the coated particulate filler, and compositions comprising a matrix organic polymer and the coated particulate filler.
A coated particulate filler which comprises an acidic group-containing organic polymer containing at least one unsaturated group and which has a molecular weight of not greater than 100,000 bound to the surface of a basic particulate, for example, calcium carbonate, a process for producing the coated particulate filler, and compositions comprising a matrix organic polymer and the coated particulate filler.
Description
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This invention relates to novel fillers and to a process for producing the fillers, and in particular to fillers which are useful in organic polymer compositions.
It is well known to modify the properties of a wide variety of organic polymers by incorporating into such polymers one or more inorganic materials in finely divided ` form. These inorganic materials, commonly known as fillers, are generally less expensive than organic polymers and they may serve to increase the bulk of the resultant polymer and so permit a polymer to be used more economically~ ~, and they may also serve to enhance at least some of the physical properties of the polymer, for example the hardness, ~:
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tensile modulus, tensile strength, or resistance to wear of the polymer~
Not only is it desirable to makè such fillers as compatible as possible with organic pol~mers but it is also desirable to be able to make compositions containing high proportions of filler so as to confer the physical and cost advantages of the filler on the resulting composition to the maximum practicable extent. It is especially desirable, when considering possible shortages of hydrocarbon raw materials, to be able to use cheap and readily available fillers as much as possible.
We have now found that it is possible to modify a wide variety of basic fillers in such a way that the modified ~illers are more readily incorporated into an organic polymer and in such a way that the resultant polymer composition containing the modified filler has properties superior to those of a polymer composition containing an unmodified filler.
According to the present invention we provide a process for the production of a coated particulate filler which process comprises binding to the surface of a basic particulate filler an acidic group-containing organic polymer, which polymer contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
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Within the scope of the term "polymer" in the expression "acidic group-containing organic polymer" we include oligomers, indeed the molecular weight of the polymer may be as low as 200 and the number of the repeat units may be suf~iciently low that the polymer (or oligomer) is a liquid.
Within the scope of the term "acidic group" in the expression "acidic group-containing organic polymerl' we include not only organic polymers containing acidic groups in the form of the free acid but also salts of acidic groups and groups convertible to free acid groups under the process conditions, for example anhydride groups.
The invention also provides a basic particulate filler to the surface of which there is bound an organic polymer which contains at least one unsatura~ed group and which has a molecular weight of not greater than 100,000~ -These products of our invention contain the unsaturated organic polymer bound to the surface of the particulate filler.
It is believed that the organic polymer reacts with the basic particulate filler and is chemically-bound to the surface of the particulate filler. ~ndeed the organic polymer is not removed from the filler when the filler is washed in a solvent for the polymer, even in a boiling solvent.
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The fillers of the present invention have some of the properties of the filler particles from which they are derived, and in addition have high compatibility with organic polymers and impart a valuable strengthening of the ultimate association of the fillers with an organic polymer composition in which they are incorporated. The products also have the valuable property of being very much more readily mixed with an organic polymer than does the unmodified filler.
According to a further embodiment of the invention we provide a polymer composition comprising a matrix of an organic polymer having incorporated therein a basic particulate filler to the surface of which there is bound an organic polymer which contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
Any particulate filler may be used in the process of our invention provided that the filler is basic and is thus capable of binding to the acidic group-containing organic polymer. The filler may be for examplean oxide, a hydroxide, a carbonate or a basic carbonate.
The filler should of course be insoluble in water.
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Suitable fillers include oxides, hydroxides, carbonates and basic carbonates of alkaline earth metals and of aluminium and 7inc t and especially carbonates. Preferred carbonates are the carbonates of calcium and magnesium, especially calcium carbonate. A suitable hydroxide is magnesium hydroxide. The filler particles may be of natural or synthetic origin. For example, calcium carbonate may be in the form of ground chalk or in the form of a precipitated calcium carbonate, for example calcium carbonate prepared by carbonation of milk of limeO
Mixtures of basic particulate fillers may be used.
The filler particles for use in our inven~ion may have any form suitable for a filler, and may have a wide variety of particle shapes and sizes. For example, they may be of substantially spherical shape, though they may if desired be of fibrillar or laminar form.
Most commonly the filler particles will have a size in the range 40 Angstrom to 1 mm, though we prefer, on ;~
account of the superior reinforcing effect, that the particle size is in the range 40 Angstrom to 1000 Angstrom, for example about 200 Angstrom.
Most conveniently the basic particulate filler is in the form of a finely divided, free flowing powder, and this is the form in which such fillers are usually available in commerce.
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The acidic group-containing organic polymer to which the basic particulate filler is bound in the process of our invention should contain at least one acidic group per molecule. Suitable acidic groups inclùde carboxylic acid groups. The acidic group-containing organic polymer may contain on average more than one acidic group per molecule and indeed it is preferred that the polymer does contain more than one such group per molecule as in general the greater is the number of such groups per molecule the more likely is the polymer to be water-soluble or at least readily water-dispersible thus permitting the process of our invention to be effected in an aqueous medium.
Water-solubility or dispersibility of the acidic group~containing polymer may be-increased by forming a salt of the acidic group, for example, an alkali metal salt, an ammonium salt, or a trialkyl ammonium salt of a carboxylic acid group. An example of a ; group convertible to a free acid group under the process conditions is a carboxylic acid anhydride group which may be hydrolysed to a free acid in the process, particularly where the process is effected in an aqueous medium.
The acidic group-containing organic polymer also contains at least one unsaturated group per molecule, , 5-~
e.g. an ethylenically unsaturated group. The group preferably should be capable of participating in a cross-linking reaction. The polymer preferably contains a plurality of unsaturated groups. The unsaturated group capable of participating in cross-linking is preferably part o a polydiene structure, that is a polymer derived from a diene, but may be part of a polymer structure of other derivation if desired.
Examples of polydiene structures are polymers or copolymers derived by polymerisation or copolyerisation of one or more dienes, of which the most conveniently available is butadiene, though others may be used if desired, for example isoprenel chloroprene (chloro-butadiene) or mixtures thereof. Examples of other compounds which may be copolymerised with the diene or dienes include a wide range of vinyl monomers, for example styrene, acrylonitrile, and mixtures thereof.
Suitable acidic group~containing organic polymers include polydiene carboxylic acids and polydiene polycar-boxylic acids, especially dicarboxylic acid polydienes eOg. polybutadiene dicarboxylic acid. 5uch polydiene carboxylic acids may be prepared by reacting a polydiene :
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e.g. polybutadiene, polyisoprene, or natural rubber, with mercaptoacetic acid, by oxidising unsaturated groups in a polydiene, or by copolymerising a diene with an unsaturated monomer containing a carboxylic acid group or a group which is capable of being converted into such a group. For example, a diene, e.g. butadiene or isoprene, may be copolymerised with vinyl acetate and the acetate groups in the resultant copolymer may be hydrolysed to carboxylic acid groupsO An acidic group-containing organic polymer may also be prepared byreacting an unsaturated polymer, for example a poly-diene, e.g. polybutadiene, with maleic anhydride. The thus formed adduct of a polydiene and maleic anhydride may if desired be converted to a salt before use in the process of the invention, or it may be used as such in the process.
The acidic group-containing organic polymer is preferably one which has a molecular weight in the range 200 - 50,000, and especially in the range 1000 to 5000 It is also preferred that the acidic group-containing organic polymer is liquid at the temperature at which the process is effected, e.g. at ambient temperature.
Thus, where the acidic group-containing organic polymer is liquid it may conveni.en~ly be bound to the particulate filler without the acid of a solvent or dispersant for the polymer~ Such liquid pol~mers will of course have a relatively low molecular weight, for example , ', , 10. ' a molecular weight in the range lOCO to 5000. Where the acidic group-containing organic polymer is not a liquid the process of the invention should be effected in the presence of a solvent or dispersant for the polymer.
Once again relatively low molecular weight polymers are preferred as such polymers may be more readily dissolved or dispersed in a solvent or dispersant, and may be dissolved or dispersed at a much higher concentration, than may high molecular weight polymers.
The ability of the acidic group-containing organic polymer to bind to the particulate filler depends to some extent upon such factors as the molecular weight and the number of aci,d groups in the polymer. In general the greater the number of acidic groups per molecule the greater will be the ability of the polymer to bind to the filler.
The process of our invention is carried out by forming a mixture of the basic particulate filler and the acidic group-containing organic polymer. The mixture may be heated although heating may not be necessary especially where a solvent or dispersant for the polymer is used and/or the acidic group is particularly reactive. Thus, the binding may be carried ou~ at a temperature over a wicle range, depending upon the materials used. The rate at which the binding of fhe basic particulate filler and the acidic group-containing :
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organic polymer takes place usually increases as higher temperatures are used, but at high temperatures the risk of the decomposition of the organic polymer tends to increase. Thus the binding is preferably effected at a temperature in the range 0C to 200C, though other temperatures may be used if desired. The optimum conditions may be determined by simple trial. The time required also depends upon the materials and the conditions employed, but commonly is in the range 1 minute to 6 hours. The binding may be carried out most conveniently at ambient pressure, though high or lower pressures may be used if desired.
The binding of the components may be further assisted in several ways. For example, the mixture may be stirred or it may be milled, e.g. in a ball mill. Also a solvent or dispersant for the acidic group-containing organic polymer may be used, and is necessary where the polymer is a solidO The solvent or dispersant may serve several -u~eful functions. Thus, it may reduce the viscosity of the acidic group-containing organic polymer, improve the ease and evenness of the spreading of the pol~mer over the basic filler particles~ promote the intimate contact and interaction between the components, assist in controlling the temperature of the mixture, or assist in preventing degradation of the polymer by excluding oxygen from it.
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In general, it is preferred to use a solvent in which the polymer is substantially completely dissolved rather than dispersed, and the process will be described hereafter with reference to use of such a solvent.
The solvent should be chemically inert towards the polymer and the basic filler and it i5 especially desirable that it should be inert towards the basic filler so that it is not preferentially adsorbed thereon to an extent which appreciably diminishes the affinity of the organic polymer for the surface of the basic filler particles.
Examples of organic solvents include hydrocarbons, for example aliphatic, aromatic, araliphatic or cyclo-aliphatic hydrocarbons, e.g. toluene, xylene and petroleum fractions; halogenated and especially chlorinated hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroet-hane, trichloroethylene and tetrachloroethylene ethers, for example diethyl ether; and mixtures thereof. The choice of solvent will be guided by such factors as low flammability, low toxicity, and boiling poink, which may ~ -be significant both in use and in the removal of the solvent from the treated particulate filler.
A preferred solvent for the acidic group-containing orsanic polymer is water on account of its ease of handling, its low cost, and the absence of toxicity - problems. Furthermore, the basic particulate filler~
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S~ -especially where it is a small particle size synthetically prepared filler, e.g. calcium carbonate prepared by carbonation of milk of lime, may be available as an aqueous dispersion, and use of water as a solvent for the acidic group-containing organic polymer obviates the need to separate the filler from the aqueous dispersion.
The nature of the solvent which is used will have a bearing on the number of acidic groups in the acidic group-containing organic polymer and on the molecular weight of the polymer. Thus, as organic polymers are generally readily soluble in organic solvents the desired concentration of the acidic group-containing organic polymer in an organic solvent may be achieved even where the molecular weight of the polymer varies over a wide range up to the limit of 100,000. Also, as the acidic groups in the polymer may in general have little effect on the solubility in organic solvents the number of such groups per molecule is generally not critical. On the other hand, where water is used as a solvent the molecular weight and the number of acidic groups per molecule is much more critical.
As organic polymers are generally at most only sparingly soluble in water, and as the solubility generally decreases as the molecular weight of the polymer increases, ' ' ' -.
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A molecular weight in the range 200 - 50,000 is preerred.
Especially preferred is a molecular weight of 1000-5000.
A5 the water-solubility of the polymer will tend to increase with an increase in the number of acidic groups per molecule a plurality of acidic groups is preferred where water is used as a solvent~ For a polymer of given molecular weight the number of acidic groups needed to achieve the desired water solubility may be determined experimentally. The precise number will depend on the particular polymer and the molecular welght chosen, and on the concentration of acidic group-containlng organic polymer which is desired on the aqueous solution. Acidic groups in the form of salts may also serve to improve the water solubility of the polyrner.
The proportion of solvent should be sufficient to dissolve the acidic group~containing orgaic pol~ner, as incomplete solution may result in undesirable local - 20 concentration of unbound polymer, and be sufficient to produce a solution which can readily flow and mix with the basic filler particles. Suitable proportions can be determined by simple trial and are not necessarily critical.
It is also important that the amount of solution containing the acidic group-containing organic polymer . .
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lilVS?4 which is used should be sufficient to cover the surface of the basic filler particles as thoroughly as possible if the best products, that is the most useful fillers are to result. Conveniently an excess of solution sufficient to produce a thoroughly wetted mixture may be used. The coated particulate filler may be separated from the solution and dried~
The binding may be carried out in the presence of protecting agents, e.g. antioxidants, and/or in an inert atmosphere, e.g. nitrogen, argon or solvent vapour, if it is desired to guard against deterioration of the polymer during any heating that may be necessaryO
The proportion of the acidic group-containing organic polymer and the basic filler particles may be varied within wide limits according to the particular materials employed and the properties desired in the product and in the polymer composition in which the coated filler particles may ultimately be incorporated.
Commonly, our coated filler particles contain in the range 0.2% to 40~ by weight of the organic polymer and correspondingly 99.8 to 60% by weight of the particulate filler, though products having proportions outside this range may be made if desired. Preferred proportions are in the range 1% to 20% by weight of the organic polymer bound to the basic particulate filler, more preferably 1% to 10% by weightO
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~ .' ' When the acidic group-containing organic polymer has been applied to and bound to the surface of the basic filler particles, the resulting product may be in a form in which it can be used directly as a filler S or it may need to be treated mechanically, e.g. by yrinding, to break up agglomerates and reduce the filler to a suitably small particle size. This is not essential in all cases, however, as any necessary break-down of the agglomerates may take place satisfactorily while the filler is being incorporated into a polymer composition, for example by milling.
As the organic polymer which is bound to the surface o the particulate filler contains at least one unsaturated group the filler, when incorporated in a matrix organic polymer, may be caused to react with the latter polymer through the unsaturated group, especially where the latter organic polymer itself contains such a group, e.g. where the matrix organic polymer is a curable, that is a vulcanisable, rubber. As a result o this reaction the filler may be caused to be bound to the matrix organic polymer in which it is incorporated with the result that the resultant polymer composition will have properties superior to those of a polymer composition containing a filler which has been bound to an acidic group-containing organic polymer which does not contain unsaturation.
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Where the matrix organic polymer with which the filler is mixed and into which it is incorporated does not itself contain unsaturation reaction of this organic polymer with the unsaturated organic polymer bound to the surface of the filler particles may be caused to take place by generating free radials during the mixing operation, for example by shearing the mixture or by including a free radial generator in the mixture.
The matrix organic polymer into which the products of our invention may be incorporated may be in any convenient form and incorporation may be carried out by conventional mixing means. This polymer may be a thermo-setting resin, e.g. a polyester resin, but is preferably thermoplastic and may be any homopolymer or copolymer having physical properties permitting incorporation of our new products as fillers. It i5 more preferably one containing unsaturation and which is thus curable (vulcanisable).
The polymer may be a massive or particulate plastic or rubbery material, into which our filler may be incorporated by mechanical action, for example milling.
Chemically, the polymer may be of widely varying constitution and may be for ex~mple any natural or synthetic rubber or resin known in the art to be usable in conjunction with a filler. The products of our invention are especially useful as fillers in natural or synthetic rubbers, for e~ample butadiene-based rubbers, e.g. butadiene-styrene and butadiene-acrylonitrile rubbers, polybutadiene, polyisoprene; and natural rubber.
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The polymer composition may also be produced by mixing a matrix organic polymer with a basic particulate filler and with an acidic group-containing organic polymer which also contains at least one unsaturated m Sgroup and which has a molecular weight of not greater than 100,000.
It is believed that during the mixing process the basic iller particles bind to the acidic group-containing organic polymer. It is not necessary for all of the 10acidic group-containing polymer to bind to the basic particulate filler during the mixing operation. Indeed binding may not take place as readily as in the case where basic particulate filler is bound to the acidic group-containing organic polymer in the absence of a 15matrix polymer, for example when mixed in the presence of a solvent for the acidic group-containing organic polymer, and it may be desirable to use in this process an amount of acidic group-containing organic polymer by weight of basic particula~e filler which is greater 20than would normally be used.
The optimum proportion of filler to the surface of which an organic polymer is bound to matrix organic polymer in which it is incorporated will be determined by the use to which the filled polymer is to be put.
25In general 5% to 300~ of filler by weight o~ ma rix organic polymer into which it is incorporated will ~, suffice, pre~erably 10~ to 200% by weight.
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The polymer composition may also contain conventional additives, for example antioxidants, plasticisers, vulcanisation acceleratorsr pigments, antiozonants, and fillers other than those of the present invention.
The invention is illuskrated by the following Examples.
Carbon dioxide (300 litres/hour) and air (450 litres/
hour) were passed through 7 litres or milk of lime ~containing 38g Ca(OH)2 per litre) until the pH of the suspension had reached 7Ø The supension was then aged by stopping the carbon dioxide flow and maintaining the air flow and heating the supension until a temperature of 85C was reached after lS minutes. The temperature of the supsension was then maintained at 85C and carbon dioxide (30 litres/hour) and air (45 litres/hour) were passed through the suspension until the pH of the resultant calcium carbonate suspension had reached 8Ø
A polybutadiene - maleic anhydride adduct was prepared by reacting 100 parts by weight of polybutadiene (Mn 1300) with 25 parts by weiyht of maleic anhydride under an atmosphere of nitrogen and in the presence of a small amount o xylene and antioxidant at a temperature of 190C
until little or no free maleic anhydride remained. The triethyl ammonium salt of the methyl half ester of the resultant polybutadiene-maleic anhydride adduct was ~hen prepared by reacting the adduct with methanol and triethyl-amine at a temperature of 80C for 1 hour.
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Finally, a suspension of calcium carbonate (particle size approximately 70 millimicrons) prepared as described above and containing lO0 parts by weight of calcium carbonate was mixed with 3 parts by weight of the above described triethyl ammonium salt tin the form of an aqueous solution containing 609 of the salt per litre) at a temperature of 85C for lS minutes and the thus treated ca~cium carbonate suspension was filtered and the separated product was dried by heating in an oven at 110C. The product was then lightly milled. The product is referred to hereafter as Filler ~.
By way of comparison a calcium carbonate suspension prepared as described above, containing 105 parts by weight of calcium carbonate, was reacted with 2.5 parts : 15 by weight oE ammonium stearate (in the form of an aqueous solution containing 75g of ammonium stearate per litre) at a temperature of 85C for 15 minutes and the thus treated calcium carbonate was separated, dried and : lightly milled following the a~ove-described procedure~
The treated calcium carbonate i5 referred to hereafter as Filler B.
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.3~ 4 In order to compare the reinforcing effects of Filler A and Filler B the fillers were separately compounded on a twin-roll mill with an uncured rubber formulation containing either styrene-butadiene rubber (SBR 1502) .
(Example 1 and comparison example respectively) or natural rubber (SMR5) (Example 2 and comparison example respectively), the compounded compositions were cured by heating at a temperature of 153C, and the properties of the cured rubber compositions were determined.
- 10 Details of the components of the rubber compositions in parts by weiyht, the cure times, and the properties of the cured rubber compositions are given in Table 1.
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5~4 A suspension of calcium carbonate prepared by carbonation of milk of lime following the procedure of Example 1 was filtered, the resultant filte~ cake was S suspended in a mixture of acetone and water and filtered again, the filter cake which was produced was allowed to dry by standing in air at room temperature and thereafter by heating at 100C, and the calcium carbonate was inally lightly milled tparticle size 70 millimicrons).
10250 parts by weight of the particulate calcium carbonate was then mixed with 12.5 parts by weight of a polybutadiene dicarboxylic acid (Mn 4000) and 730 parts by weight of trichloroethylene and the mixture was ball-milled at room temperature for 2 hours. The mixture lS was then filtered and the separated filler cake was dried in air at room temperature followed by heating at 40C
and was finally lightly milled to produce a particulate calcium carbonate having bound thereto 2,5% by weight of polybutadiene. The calcium carbonate is referred here- -after as Filler C.
By way of comparison the above described procedure was repeated in two separate experiments except that the polybutadiene dicarboxylic acid was replaced in one experiment by stearic acid and in the o~her experiment it was omitted.
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S~4 The calcium carbonate fillers produced are hereafter referred to as Fillers D and E respectively.
The reinforcing effects of the Fillers C, D and E
in styrene-butadiene rubber were determined following the procedure described in Examples 1 and 2. Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 2.
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Particulate calcium carbonate having a particle size of 70 millimicrons was prepared following the procedure described in Example 3 (subsequent reaction with poly-S butadiene dicarboxylic acid was not carried out) andthe calcium carbonate thus produced was milled on a twin roll mill with styrene-butadiene rubber, zinc oxide, stearic acid, Vulcafor F, and polybutadiene dicarboxylic acid (Mn 4000) as used in Example 3. The compounded composition was then cured at 153C and the propPrties of the cured rubber composition were determined~
By way of comparison the above compounding procedure was repeated except that the polybutadiene dicarboxylic acid was replaced by polybutadiene (Mn 4000).
lS Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 3.
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Particulate calcium ca.rbonate having a particle size of 70 mllimicrons was prepared following the procedure described in Example 3 (subsequent reaction with poly-butadierle dicarboxylic acid was not carried out) and thecalcium carbonate thus produced was milled on a twin roll mill with styrene-butadiene rubber, zinc oxide, stearic acid, Vulcafor F and the polybutadiene maleic anhydride . adduct prepared as described in Example 1.
The compounded composition was then cured at 153C
and the properties of the cured rubber composition were determined.
By way of comparison, the above procedure was repeated except that the polybutadiene - maleic anhydride adduct was omitted.
Details of the components of the rubber compositions in parts by weight, cure times, and the properties of the cured rubber compositions are given in Table 4.
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_ To the aqueous solution of the triethylammonium salt prepared by reacting the polybutadiene-maleic anhydride with methanol and triethylamine as described in Example 1 there was added dilute hydrochloric acid. The resultant precipitated free carboxylic acid was extracted with diethyl ether 9 the diethyl ether solution was dried over magnesium sulphate, and the solution was distilled and the free carboxylic acid collected. The acid was then milled into Styrene-butadiene rubber together with zinc oxide, stearic acid, Vulcafor F and calcium carbonate as used in Example 5.
~ he compounded composition was then cured at 153C
and the properties of the cured rubber composition were determined.
By way of comparison, the above procedure was repeated except that the carboxylated-polybutadiene was omitted.
Details of the components of the rub~er compositions in parts by weight, cure times, and properties of the cured rubber compositions are given in Table 5.
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A polybutadiene - maleic anhydride adduct prepared following the procedure described in Example 1, was reacted with isobutanol at a temperature of 80C for 1 hour, and then 4~ by weight aqueous ammonium hydroxide solution was added to produce an ammonium salt of an isobutyl half ester of the polybutadiene - maleic anhydride adduct (Mn of polybutadiene 3400)0 In five separate experiment samples of calcium carbonate coated with respectively 2, 3, 4, 6 and 8%
by weight of the above ammonium salt were produced following the procedure described in Example 1 except that the above ammonium salt was used in place of the triethyl ammonium salt of the methyl half ester of the polybutadiene - maleic anhydride adduct used in Example 1.
The samples of coated calcium carbonate will be referred to as Fillers F, G, H, I and J respectivelyO
; The ~amples of coated calcium carbonate were then separately compounded with styrene-butadiene rubber (SBR 1502) and the compounded compositions were cured at a temperature of 153C following the procedure described in Example 1.
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Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 6.
For comparison the properties of a rubber containing a stearate (~ 2.7~) coated precipitated calcium carbonate (Filler K) are also given (prepared following the procedure of Example 1).
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o ~rl ~ ~ ~ r~ rl r~ r~ r~ r~ r~ r~ r~ r~ O O la ta h ~i 80g of fine particle size magnesium hydroxide was mixed with 450 ml of water and the mixture was stirred and heated to 80C. Stirring was continued and 90 ml of a solution in 750 ml o water of 40g of a triethylammonium salt of a methyl half ester of a polybutadiene - maleic anhydride adduct was added (as prepared in Example 1 except that the polybutadiene had an Mn of 3400).
Stirring was continued for 15 minutes at 80~C, the mixture was filtered~ and the filtrate was dried by heating at 110 to 120C for 10 hours. The resultant magnesium hydroxide contained approximately 5% by weight of coating.
Following the procedure of Example 1 75 parts by weigbt of the coated magnesium hydroxide was compounded wlth 100 parts by weight of SBR 1532, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide, ~ :
parts by weight of Vulcafor F, and 2.5 parts by weight of sulphur, and the compounded composition wa~ cured following the procedure of Example 1. The properties of the cured composition are given in Table 7 together with those of a composition in which the coated magnesium hydroxide was replaced by uncoated magnesium hydroxide (for the purposes of comparison).
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-Coated Magnesium _~nesium ~
hydroxide (comparison) Tensile Strength (Rg/sq cm) 95 75 Elongation at break ~ 626 655 100% tensile modulus (Xg/sq cm)24 19 200% ten.sile modulus (Kg/sq cm) 34 23 300% tensile modulus (Rg/sq cm)43 27 Tear Strength (angle) (RgF/mm) 3.3 2.25 Hardness B.S. 73 67 -100 parts by weight of a natural ~alcium carbonate whiting have a particle siæe predominantly less than 10 microns was mixed for 10 minutes in a Henschel mixer with 3 parts by weight of a polybutadiene - maleic anhydride adduct as prepared in Example 1 (except that the poly-butadiene had an Mn of 3400) and 100 parts by weight.of the resultant coated calcium carbonate were compounded with 100 parts by weight of SBR 1502, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide,
This invention relates to novel fillers and to a process for producing the fillers, and in particular to fillers which are useful in organic polymer compositions.
It is well known to modify the properties of a wide variety of organic polymers by incorporating into such polymers one or more inorganic materials in finely divided ` form. These inorganic materials, commonly known as fillers, are generally less expensive than organic polymers and they may serve to increase the bulk of the resultant polymer and so permit a polymer to be used more economically~ ~, and they may also serve to enhance at least some of the physical properties of the polymer, for example the hardness, ~:
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tensile modulus, tensile strength, or resistance to wear of the polymer~
Not only is it desirable to makè such fillers as compatible as possible with organic pol~mers but it is also desirable to be able to make compositions containing high proportions of filler so as to confer the physical and cost advantages of the filler on the resulting composition to the maximum practicable extent. It is especially desirable, when considering possible shortages of hydrocarbon raw materials, to be able to use cheap and readily available fillers as much as possible.
We have now found that it is possible to modify a wide variety of basic fillers in such a way that the modified ~illers are more readily incorporated into an organic polymer and in such a way that the resultant polymer composition containing the modified filler has properties superior to those of a polymer composition containing an unmodified filler.
According to the present invention we provide a process for the production of a coated particulate filler which process comprises binding to the surface of a basic particulate filler an acidic group-containing organic polymer, which polymer contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
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Within the scope of the term "polymer" in the expression "acidic group-containing organic polymer" we include oligomers, indeed the molecular weight of the polymer may be as low as 200 and the number of the repeat units may be suf~iciently low that the polymer (or oligomer) is a liquid.
Within the scope of the term "acidic group" in the expression "acidic group-containing organic polymerl' we include not only organic polymers containing acidic groups in the form of the free acid but also salts of acidic groups and groups convertible to free acid groups under the process conditions, for example anhydride groups.
The invention also provides a basic particulate filler to the surface of which there is bound an organic polymer which contains at least one unsatura~ed group and which has a molecular weight of not greater than 100,000~ -These products of our invention contain the unsaturated organic polymer bound to the surface of the particulate filler.
It is believed that the organic polymer reacts with the basic particulate filler and is chemically-bound to the surface of the particulate filler. ~ndeed the organic polymer is not removed from the filler when the filler is washed in a solvent for the polymer, even in a boiling solvent.
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The fillers of the present invention have some of the properties of the filler particles from which they are derived, and in addition have high compatibility with organic polymers and impart a valuable strengthening of the ultimate association of the fillers with an organic polymer composition in which they are incorporated. The products also have the valuable property of being very much more readily mixed with an organic polymer than does the unmodified filler.
According to a further embodiment of the invention we provide a polymer composition comprising a matrix of an organic polymer having incorporated therein a basic particulate filler to the surface of which there is bound an organic polymer which contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
Any particulate filler may be used in the process of our invention provided that the filler is basic and is thus capable of binding to the acidic group-containing organic polymer. The filler may be for examplean oxide, a hydroxide, a carbonate or a basic carbonate.
The filler should of course be insoluble in water.
.
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Suitable fillers include oxides, hydroxides, carbonates and basic carbonates of alkaline earth metals and of aluminium and 7inc t and especially carbonates. Preferred carbonates are the carbonates of calcium and magnesium, especially calcium carbonate. A suitable hydroxide is magnesium hydroxide. The filler particles may be of natural or synthetic origin. For example, calcium carbonate may be in the form of ground chalk or in the form of a precipitated calcium carbonate, for example calcium carbonate prepared by carbonation of milk of limeO
Mixtures of basic particulate fillers may be used.
The filler particles for use in our inven~ion may have any form suitable for a filler, and may have a wide variety of particle shapes and sizes. For example, they may be of substantially spherical shape, though they may if desired be of fibrillar or laminar form.
Most commonly the filler particles will have a size in the range 40 Angstrom to 1 mm, though we prefer, on ;~
account of the superior reinforcing effect, that the particle size is in the range 40 Angstrom to 1000 Angstrom, for example about 200 Angstrom.
Most conveniently the basic particulate filler is in the form of a finely divided, free flowing powder, and this is the form in which such fillers are usually available in commerce.
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The acidic group-containing organic polymer to which the basic particulate filler is bound in the process of our invention should contain at least one acidic group per molecule. Suitable acidic groups inclùde carboxylic acid groups. The acidic group-containing organic polymer may contain on average more than one acidic group per molecule and indeed it is preferred that the polymer does contain more than one such group per molecule as in general the greater is the number of such groups per molecule the more likely is the polymer to be water-soluble or at least readily water-dispersible thus permitting the process of our invention to be effected in an aqueous medium.
Water-solubility or dispersibility of the acidic group~containing polymer may be-increased by forming a salt of the acidic group, for example, an alkali metal salt, an ammonium salt, or a trialkyl ammonium salt of a carboxylic acid group. An example of a ; group convertible to a free acid group under the process conditions is a carboxylic acid anhydride group which may be hydrolysed to a free acid in the process, particularly where the process is effected in an aqueous medium.
The acidic group-containing organic polymer also contains at least one unsaturated group per molecule, , 5-~
e.g. an ethylenically unsaturated group. The group preferably should be capable of participating in a cross-linking reaction. The polymer preferably contains a plurality of unsaturated groups. The unsaturated group capable of participating in cross-linking is preferably part o a polydiene structure, that is a polymer derived from a diene, but may be part of a polymer structure of other derivation if desired.
Examples of polydiene structures are polymers or copolymers derived by polymerisation or copolyerisation of one or more dienes, of which the most conveniently available is butadiene, though others may be used if desired, for example isoprenel chloroprene (chloro-butadiene) or mixtures thereof. Examples of other compounds which may be copolymerised with the diene or dienes include a wide range of vinyl monomers, for example styrene, acrylonitrile, and mixtures thereof.
Suitable acidic group~containing organic polymers include polydiene carboxylic acids and polydiene polycar-boxylic acids, especially dicarboxylic acid polydienes eOg. polybutadiene dicarboxylic acid. 5uch polydiene carboxylic acids may be prepared by reacting a polydiene :
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e.g. polybutadiene, polyisoprene, or natural rubber, with mercaptoacetic acid, by oxidising unsaturated groups in a polydiene, or by copolymerising a diene with an unsaturated monomer containing a carboxylic acid group or a group which is capable of being converted into such a group. For example, a diene, e.g. butadiene or isoprene, may be copolymerised with vinyl acetate and the acetate groups in the resultant copolymer may be hydrolysed to carboxylic acid groupsO An acidic group-containing organic polymer may also be prepared byreacting an unsaturated polymer, for example a poly-diene, e.g. polybutadiene, with maleic anhydride. The thus formed adduct of a polydiene and maleic anhydride may if desired be converted to a salt before use in the process of the invention, or it may be used as such in the process.
The acidic group-containing organic polymer is preferably one which has a molecular weight in the range 200 - 50,000, and especially in the range 1000 to 5000 It is also preferred that the acidic group-containing organic polymer is liquid at the temperature at which the process is effected, e.g. at ambient temperature.
Thus, where the acidic group-containing organic polymer is liquid it may conveni.en~ly be bound to the particulate filler without the acid of a solvent or dispersant for the polymer~ Such liquid pol~mers will of course have a relatively low molecular weight, for example , ', , 10. ' a molecular weight in the range lOCO to 5000. Where the acidic group-containing organic polymer is not a liquid the process of the invention should be effected in the presence of a solvent or dispersant for the polymer.
Once again relatively low molecular weight polymers are preferred as such polymers may be more readily dissolved or dispersed in a solvent or dispersant, and may be dissolved or dispersed at a much higher concentration, than may high molecular weight polymers.
The ability of the acidic group-containing organic polymer to bind to the particulate filler depends to some extent upon such factors as the molecular weight and the number of aci,d groups in the polymer. In general the greater the number of acidic groups per molecule the greater will be the ability of the polymer to bind to the filler.
The process of our invention is carried out by forming a mixture of the basic particulate filler and the acidic group-containing organic polymer. The mixture may be heated although heating may not be necessary especially where a solvent or dispersant for the polymer is used and/or the acidic group is particularly reactive. Thus, the binding may be carried ou~ at a temperature over a wicle range, depending upon the materials used. The rate at which the binding of fhe basic particulate filler and the acidic group-containing :
.
. . . .
- . . . . .
.. . . . .
.
organic polymer takes place usually increases as higher temperatures are used, but at high temperatures the risk of the decomposition of the organic polymer tends to increase. Thus the binding is preferably effected at a temperature in the range 0C to 200C, though other temperatures may be used if desired. The optimum conditions may be determined by simple trial. The time required also depends upon the materials and the conditions employed, but commonly is in the range 1 minute to 6 hours. The binding may be carried out most conveniently at ambient pressure, though high or lower pressures may be used if desired.
The binding of the components may be further assisted in several ways. For example, the mixture may be stirred or it may be milled, e.g. in a ball mill. Also a solvent or dispersant for the acidic group-containing organic polymer may be used, and is necessary where the polymer is a solidO The solvent or dispersant may serve several -u~eful functions. Thus, it may reduce the viscosity of the acidic group-containing organic polymer, improve the ease and evenness of the spreading of the pol~mer over the basic filler particles~ promote the intimate contact and interaction between the components, assist in controlling the temperature of the mixture, or assist in preventing degradation of the polymer by excluding oxygen from it.
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In general, it is preferred to use a solvent in which the polymer is substantially completely dissolved rather than dispersed, and the process will be described hereafter with reference to use of such a solvent.
The solvent should be chemically inert towards the polymer and the basic filler and it i5 especially desirable that it should be inert towards the basic filler so that it is not preferentially adsorbed thereon to an extent which appreciably diminishes the affinity of the organic polymer for the surface of the basic filler particles.
Examples of organic solvents include hydrocarbons, for example aliphatic, aromatic, araliphatic or cyclo-aliphatic hydrocarbons, e.g. toluene, xylene and petroleum fractions; halogenated and especially chlorinated hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroet-hane, trichloroethylene and tetrachloroethylene ethers, for example diethyl ether; and mixtures thereof. The choice of solvent will be guided by such factors as low flammability, low toxicity, and boiling poink, which may ~ -be significant both in use and in the removal of the solvent from the treated particulate filler.
A preferred solvent for the acidic group-containing orsanic polymer is water on account of its ease of handling, its low cost, and the absence of toxicity - problems. Furthermore, the basic particulate filler~
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S~ -especially where it is a small particle size synthetically prepared filler, e.g. calcium carbonate prepared by carbonation of milk of lime, may be available as an aqueous dispersion, and use of water as a solvent for the acidic group-containing organic polymer obviates the need to separate the filler from the aqueous dispersion.
The nature of the solvent which is used will have a bearing on the number of acidic groups in the acidic group-containing organic polymer and on the molecular weight of the polymer. Thus, as organic polymers are generally readily soluble in organic solvents the desired concentration of the acidic group-containing organic polymer in an organic solvent may be achieved even where the molecular weight of the polymer varies over a wide range up to the limit of 100,000. Also, as the acidic groups in the polymer may in general have little effect on the solubility in organic solvents the number of such groups per molecule is generally not critical. On the other hand, where water is used as a solvent the molecular weight and the number of acidic groups per molecule is much more critical.
As organic polymers are generally at most only sparingly soluble in water, and as the solubility generally decreases as the molecular weight of the polymer increases, ' ' ' -.
:
.. : , 1~ . ' low molecular weight acidic group-containing organic polymers are preferred where water is used as a solvent~
A molecular weight in the range 200 - 50,000 is preerred.
Especially preferred is a molecular weight of 1000-5000.
A5 the water-solubility of the polymer will tend to increase with an increase in the number of acidic groups per molecule a plurality of acidic groups is preferred where water is used as a solvent~ For a polymer of given molecular weight the number of acidic groups needed to achieve the desired water solubility may be determined experimentally. The precise number will depend on the particular polymer and the molecular welght chosen, and on the concentration of acidic group-containlng organic polymer which is desired on the aqueous solution. Acidic groups in the form of salts may also serve to improve the water solubility of the polyrner.
The proportion of solvent should be sufficient to dissolve the acidic group~containing orgaic pol~ner, as incomplete solution may result in undesirable local - 20 concentration of unbound polymer, and be sufficient to produce a solution which can readily flow and mix with the basic filler particles. Suitable proportions can be determined by simple trial and are not necessarily critical.
It is also important that the amount of solution containing the acidic group-containing organic polymer . .
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lilVS?4 which is used should be sufficient to cover the surface of the basic filler particles as thoroughly as possible if the best products, that is the most useful fillers are to result. Conveniently an excess of solution sufficient to produce a thoroughly wetted mixture may be used. The coated particulate filler may be separated from the solution and dried~
The binding may be carried out in the presence of protecting agents, e.g. antioxidants, and/or in an inert atmosphere, e.g. nitrogen, argon or solvent vapour, if it is desired to guard against deterioration of the polymer during any heating that may be necessaryO
The proportion of the acidic group-containing organic polymer and the basic filler particles may be varied within wide limits according to the particular materials employed and the properties desired in the product and in the polymer composition in which the coated filler particles may ultimately be incorporated.
Commonly, our coated filler particles contain in the range 0.2% to 40~ by weight of the organic polymer and correspondingly 99.8 to 60% by weight of the particulate filler, though products having proportions outside this range may be made if desired. Preferred proportions are in the range 1% to 20% by weight of the organic polymer bound to the basic particulate filler, more preferably 1% to 10% by weightO
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~ .' ' When the acidic group-containing organic polymer has been applied to and bound to the surface of the basic filler particles, the resulting product may be in a form in which it can be used directly as a filler S or it may need to be treated mechanically, e.g. by yrinding, to break up agglomerates and reduce the filler to a suitably small particle size. This is not essential in all cases, however, as any necessary break-down of the agglomerates may take place satisfactorily while the filler is being incorporated into a polymer composition, for example by milling.
As the organic polymer which is bound to the surface o the particulate filler contains at least one unsaturated group the filler, when incorporated in a matrix organic polymer, may be caused to react with the latter polymer through the unsaturated group, especially where the latter organic polymer itself contains such a group, e.g. where the matrix organic polymer is a curable, that is a vulcanisable, rubber. As a result o this reaction the filler may be caused to be bound to the matrix organic polymer in which it is incorporated with the result that the resultant polymer composition will have properties superior to those of a polymer composition containing a filler which has been bound to an acidic group-containing organic polymer which does not contain unsaturation.
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Where the matrix organic polymer with which the filler is mixed and into which it is incorporated does not itself contain unsaturation reaction of this organic polymer with the unsaturated organic polymer bound to the surface of the filler particles may be caused to take place by generating free radials during the mixing operation, for example by shearing the mixture or by including a free radial generator in the mixture.
The matrix organic polymer into which the products of our invention may be incorporated may be in any convenient form and incorporation may be carried out by conventional mixing means. This polymer may be a thermo-setting resin, e.g. a polyester resin, but is preferably thermoplastic and may be any homopolymer or copolymer having physical properties permitting incorporation of our new products as fillers. It i5 more preferably one containing unsaturation and which is thus curable (vulcanisable).
The polymer may be a massive or particulate plastic or rubbery material, into which our filler may be incorporated by mechanical action, for example milling.
Chemically, the polymer may be of widely varying constitution and may be for ex~mple any natural or synthetic rubber or resin known in the art to be usable in conjunction with a filler. The products of our invention are especially useful as fillers in natural or synthetic rubbers, for e~ample butadiene-based rubbers, e.g. butadiene-styrene and butadiene-acrylonitrile rubbers, polybutadiene, polyisoprene; and natural rubber.
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The polymer composition may also be produced by mixing a matrix organic polymer with a basic particulate filler and with an acidic group-containing organic polymer which also contains at least one unsaturated m Sgroup and which has a molecular weight of not greater than 100,000.
It is believed that during the mixing process the basic iller particles bind to the acidic group-containing organic polymer. It is not necessary for all of the 10acidic group-containing polymer to bind to the basic particulate filler during the mixing operation. Indeed binding may not take place as readily as in the case where basic particulate filler is bound to the acidic group-containing organic polymer in the absence of a 15matrix polymer, for example when mixed in the presence of a solvent for the acidic group-containing organic polymer, and it may be desirable to use in this process an amount of acidic group-containing organic polymer by weight of basic particula~e filler which is greater 20than would normally be used.
The optimum proportion of filler to the surface of which an organic polymer is bound to matrix organic polymer in which it is incorporated will be determined by the use to which the filled polymer is to be put.
25In general 5% to 300~ of filler by weight o~ ma rix organic polymer into which it is incorporated will ~, suffice, pre~erably 10~ to 200% by weight.
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The polymer composition may also contain conventional additives, for example antioxidants, plasticisers, vulcanisation acceleratorsr pigments, antiozonants, and fillers other than those of the present invention.
The invention is illuskrated by the following Examples.
Carbon dioxide (300 litres/hour) and air (450 litres/
hour) were passed through 7 litres or milk of lime ~containing 38g Ca(OH)2 per litre) until the pH of the suspension had reached 7Ø The supension was then aged by stopping the carbon dioxide flow and maintaining the air flow and heating the supension until a temperature of 85C was reached after lS minutes. The temperature of the supsension was then maintained at 85C and carbon dioxide (30 litres/hour) and air (45 litres/hour) were passed through the suspension until the pH of the resultant calcium carbonate suspension had reached 8Ø
A polybutadiene - maleic anhydride adduct was prepared by reacting 100 parts by weight of polybutadiene (Mn 1300) with 25 parts by weiyht of maleic anhydride under an atmosphere of nitrogen and in the presence of a small amount o xylene and antioxidant at a temperature of 190C
until little or no free maleic anhydride remained. The triethyl ammonium salt of the methyl half ester of the resultant polybutadiene-maleic anhydride adduct was ~hen prepared by reacting the adduct with methanol and triethyl-amine at a temperature of 80C for 1 hour.
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Finally, a suspension of calcium carbonate (particle size approximately 70 millimicrons) prepared as described above and containing lO0 parts by weight of calcium carbonate was mixed with 3 parts by weight of the above described triethyl ammonium salt tin the form of an aqueous solution containing 609 of the salt per litre) at a temperature of 85C for lS minutes and the thus treated ca~cium carbonate suspension was filtered and the separated product was dried by heating in an oven at 110C. The product was then lightly milled. The product is referred to hereafter as Filler ~.
By way of comparison a calcium carbonate suspension prepared as described above, containing 105 parts by weight of calcium carbonate, was reacted with 2.5 parts : 15 by weight oE ammonium stearate (in the form of an aqueous solution containing 75g of ammonium stearate per litre) at a temperature of 85C for 15 minutes and the thus treated calcium carbonate was separated, dried and : lightly milled following the a~ove-described procedure~
The treated calcium carbonate i5 referred to hereafter as Filler B.
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.3~ 4 In order to compare the reinforcing effects of Filler A and Filler B the fillers were separately compounded on a twin-roll mill with an uncured rubber formulation containing either styrene-butadiene rubber (SBR 1502) .
(Example 1 and comparison example respectively) or natural rubber (SMR5) (Example 2 and comparison example respectively), the compounded compositions were cured by heating at a temperature of 153C, and the properties of the cured rubber compositions were determined.
- 10 Details of the components of the rubber compositions in parts by weiyht, the cure times, and the properties of the cured rubber compositions are given in Table 1.
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~ ,, ' 8 ~ ~ u~ , g l I_ ~ ~q ~1 o o ~ er u- o I t-- ~ ~ o c~r~
I O ~1 0 ~O ~ a~ ~D~ I
~U ~ ~ ~ .,.
. ..
C
~o ~1 ~
o o c~ ~r ~ I o o ~ u- ~ ~ ~ O
o I l o ,, ~ o ~ ~ ~ , ~ In o X
V Gil ,, ..
H _I O O ~ ~r U) O 1~ ) N et~
I ~1 0 1 U~ ~1 ~ ~ L~
a N t~
~ ~ x ~ ~3 E~
-- tr E4 Ei ~ J~ ~ X
~,q _ UD
n c~
~; ~ ~ y ~1 ~ u ~
~ o Q
a~ o -~ ~ ~ o ~
n o m ~ ;~ ~I s a) ,~ x t) o a~ ~ u ~ ~ S a~ ~ rl ~ ~1 ~
~ V ~ ~ ta c d~ S~ rl ~ O
: ~ ~ ~ ~ ~ ~, ~, ~, ~ ~ ~ O o ~ U~ ~ o : ` ~
: .
`
5~4 A suspension of calcium carbonate prepared by carbonation of milk of lime following the procedure of Example 1 was filtered, the resultant filte~ cake was S suspended in a mixture of acetone and water and filtered again, the filter cake which was produced was allowed to dry by standing in air at room temperature and thereafter by heating at 100C, and the calcium carbonate was inally lightly milled tparticle size 70 millimicrons).
10250 parts by weight of the particulate calcium carbonate was then mixed with 12.5 parts by weight of a polybutadiene dicarboxylic acid (Mn 4000) and 730 parts by weight of trichloroethylene and the mixture was ball-milled at room temperature for 2 hours. The mixture lS was then filtered and the separated filler cake was dried in air at room temperature followed by heating at 40C
and was finally lightly milled to produce a particulate calcium carbonate having bound thereto 2,5% by weight of polybutadiene. The calcium carbonate is referred here- -after as Filler C.
By way of comparison the above described procedure was repeated in two separate experiments except that the polybutadiene dicarboxylic acid was replaced in one experiment by stearic acid and in the o~her experiment it was omitted.
~. -:
r ~
S~4 The calcium carbonate fillers produced are hereafter referred to as Fillers D and E respectively.
The reinforcing effects of the Fillers C, D and E
in styrene-butadiene rubber were determined following the procedure described in Examples 1 and 2. Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 2.
, U~
.,., a~
~ o u~o o X
C~
~o a~
~ O U~O ~ D O
o X
C~ ~
N ~
~:1 ~ o u~ i l u O ~ ;
/':C X `:
E-l G3 . .
~q _ Ul ::C Y
~0 ~ ~ ~ O
V ~
3 m - ~ ta ~ ~ ~u~ o In rl C
x e~ ~ ~ ~, h o o , ` ~ . - : ' :., ` .. , ~ ,:
::
`. '` ~ :
Particulate calcium carbonate having a particle size of 70 millimicrons was prepared following the procedure described in Example 3 (subsequent reaction with poly-S butadiene dicarboxylic acid was not carried out) andthe calcium carbonate thus produced was milled on a twin roll mill with styrene-butadiene rubber, zinc oxide, stearic acid, Vulcafor F, and polybutadiene dicarboxylic acid (Mn 4000) as used in Example 3. The compounded composition was then cured at 153C and the propPrties of the cured rubber composition were determined~
By way of comparison the above compounding procedure was repeated except that the polybutadiene dicarboxylic acid was replaced by polybutadiene (Mn 4000).
lS Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 3.
~ . ,.~ . : ~ ;
-.:
:.
,... . ~ ...
o - ~1 ~ ~ ~ , o x : `
c~ ~ ~ ~
a~
Ut ~ o ~7 x IY G~
~` ~
E~
x ~Q
d~
h ^ K ~
-- ~ u a~ ~ i C ~ ~
:~ ~q 5) U ~ ~ ~ C rl Q U~ rl C
~v x ~ o C ~ O r~
n ~ ~ ~
Ll Q O ~ C dP
:~ R ~ C O O
10 0 0 ~ I o :
.
5'~
Particulate calcium ca.rbonate having a particle size of 70 mllimicrons was prepared following the procedure described in Example 3 (subsequent reaction with poly-butadierle dicarboxylic acid was not carried out) and thecalcium carbonate thus produced was milled on a twin roll mill with styrene-butadiene rubber, zinc oxide, stearic acid, Vulcafor F and the polybutadiene maleic anhydride . adduct prepared as described in Example 1.
The compounded composition was then cured at 153C
and the properties of the cured rubber composition were determined.
By way of comparison, the above procedure was repeated except that the polybutadiene - maleic anhydride adduct was omitted.
Details of the components of the rubber compositions in parts by weight, cure times, and the properties of the cured rubber compositions are given in Table 4.
5~
~n ~1 ~
~1 ~ O U~ I ~
a~
~ oO ~ O ~ ~ ~ O
,~ :
~r ~3 a~
E~
~ .
U ~ ~Q
.,, .. ~ ~ ~
,JJ ,,9 0 ~:
o ~ ~ ,, ~ ~
~ m a~ u x U O ~ E5 ~-~
Q t.) ~1) U P:. O ~ C ~P i :~n ~ s ~ ~ o o J~ 5 ~ O ~ O
, : : .. ..
:, : ` , :
., , . , " . -,:, ' . . .
`. ' . ' ` ' ' , 5~
_ To the aqueous solution of the triethylammonium salt prepared by reacting the polybutadiene-maleic anhydride with methanol and triethylamine as described in Example 1 there was added dilute hydrochloric acid. The resultant precipitated free carboxylic acid was extracted with diethyl ether 9 the diethyl ether solution was dried over magnesium sulphate, and the solution was distilled and the free carboxylic acid collected. The acid was then milled into Styrene-butadiene rubber together with zinc oxide, stearic acid, Vulcafor F and calcium carbonate as used in Example 5.
~ he compounded composition was then cured at 153C
and the properties of the cured rubber composition were determined.
By way of comparison, the above procedure was repeated except that the carboxylated-polybutadiene was omitted.
Details of the components of the rub~er compositions in parts by weight, cure times, and properties of the cured rubber compositions are given in Table 5.
`' '. ~ `
'' ' : "
.
o ~
~ ~ o ~ o o ~ ~ ~
' E3 ~ ~ ~ O I , ~D
a~
U~ ~1 ~ Ll~ O~ n O O
~ ,,1 ~ _1 o In ,, n E3 ~ ` ~
~ ~ ~ cp h O) ~0 0~ Q O
,~ c ~ c ~ æ
O ~ C: JJ
I O rl a~ u. x ~ o ~ ~ ~ ~1 ~ ~ a C ~ O rl q-l :) 5 o ~1 ~
h O a O Q ~ .aal U~ C ~P
~1 ~ h ~: O O
, ~ . , -', ' , ' ~ ' . ' . .~:
'~ ' ~ ' : . ' :'-: . . . ' ' ' .. ' .''' ' . ~ ' , ' ' .'' ' ' ~ ' :
. . .
A polybutadiene - maleic anhydride adduct prepared following the procedure described in Example 1, was reacted with isobutanol at a temperature of 80C for 1 hour, and then 4~ by weight aqueous ammonium hydroxide solution was added to produce an ammonium salt of an isobutyl half ester of the polybutadiene - maleic anhydride adduct (Mn of polybutadiene 3400)0 In five separate experiment samples of calcium carbonate coated with respectively 2, 3, 4, 6 and 8%
by weight of the above ammonium salt were produced following the procedure described in Example 1 except that the above ammonium salt was used in place of the triethyl ammonium salt of the methyl half ester of the polybutadiene - maleic anhydride adduct used in Example 1.
The samples of coated calcium carbonate will be referred to as Fillers F, G, H, I and J respectivelyO
; The ~amples of coated calcium carbonate were then separately compounded with styrene-butadiene rubber (SBR 1502) and the compounded compositions were cured at a temperature of 153C following the procedure described in Example 1.
s~
Details of the components of the rubber compositions in parts by weight, the cure times, and the properties of the cured rubber compositions are given in Table 6.
For comparison the properties of a rubber containing a stearate (~ 2.7~) coated precipitated calcium carbonate (Filler K) are also given (prepared following the procedure of Example 1).
,'- - :
: :- . . . : ' , ~:
' g5~
I ,.
I
.,, I o o ~ ~ ~n I I I I I o ~D ~ r~ ~g t` r~
o ~ o ~ ~ o ~ ,i ~ t I
~1 ,, ,, , EP~ o o ~ ~ Ll~ I I I I o I ~ o ~1 ~D ~ 0~
o ,1 I
E O ~ ~`1 d' U) I I o ~I t` t` u~
~`I t`~ d' I
o o ~ ~ U~ I I o I I I ~ ~ o U~
E3 o ~1 o N ~I d' ~C
CO
I
O O t`3 d' Ul I o I I I I In ~D O ~D O ~9 ~
~3 o ~1 ~ ~9 d' d' ~ d' r-t~ ~`I t~ ~) d' H I X ~1 ~0 ~
~j I
~ I a m l ~ O O ~ ~ u) O ~ CO O ~
3 o ~ o ,~
~ l ~
E~ E3 U ~
E3 ~ ,,J~ :
0 ~ ~
.a)~ ~ 3 ~:
U 14 ~ i ~ rl ~ aJ H
rl S~ H ~ E3 ~ l ~
~ m x u o 5, ,~
o ~rl ~ ~ ~ r~ rl r~ r~ r~ r~ r~ r~ r~ r~ O O la ta h ~i 80g of fine particle size magnesium hydroxide was mixed with 450 ml of water and the mixture was stirred and heated to 80C. Stirring was continued and 90 ml of a solution in 750 ml o water of 40g of a triethylammonium salt of a methyl half ester of a polybutadiene - maleic anhydride adduct was added (as prepared in Example 1 except that the polybutadiene had an Mn of 3400).
Stirring was continued for 15 minutes at 80~C, the mixture was filtered~ and the filtrate was dried by heating at 110 to 120C for 10 hours. The resultant magnesium hydroxide contained approximately 5% by weight of coating.
Following the procedure of Example 1 75 parts by weigbt of the coated magnesium hydroxide was compounded wlth 100 parts by weight of SBR 1532, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide, ~ :
parts by weight of Vulcafor F, and 2.5 parts by weight of sulphur, and the compounded composition wa~ cured following the procedure of Example 1. The properties of the cured composition are given in Table 7 together with those of a composition in which the coated magnesium hydroxide was replaced by uncoated magnesium hydroxide (for the purposes of comparison).
.
., .
~ ' ~ , .. ..
-Coated Magnesium _~nesium ~
hydroxide (comparison) Tensile Strength (Rg/sq cm) 95 75 Elongation at break ~ 626 655 100% tensile modulus (Xg/sq cm)24 19 200% ten.sile modulus (Kg/sq cm) 34 23 300% tensile modulus (Rg/sq cm)43 27 Tear Strength (angle) (RgF/mm) 3.3 2.25 Hardness B.S. 73 67 -100 parts by weight of a natural ~alcium carbonate whiting have a particle siæe predominantly less than 10 microns was mixed for 10 minutes in a Henschel mixer with 3 parts by weight of a polybutadiene - maleic anhydride adduct as prepared in Example 1 (except that the poly-butadiene had an Mn of 3400) and 100 parts by weight.of the resultant coated calcium carbonate were compounded with 100 parts by weight of SBR 1502, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide,
2 parts by weight of Vulcafor F and 2.5 parts by weight of sulphur. The compounded composition was cured following the procedure of Example 1 (Example 13)~
The above procedure of Example 13 was repeated except that the polybutadiene - maleic anhydride adduct was `: 25 replaced by a methyl half e~ter of the same adduct .
`, (Example 14).
.
, . ~
.. ' ~' :
i :
. ~
The compounding procedure of the above described Example 13 was repeated except that the coated calcium carbonate was replaced by 97 parts by weight o~ the natural calcium carbonate whiting and 3 parts by weight of the polybutadiene - maleic anhydride adduct used in Example 13~ (Example 15).
The properties of the cured compositions are given in Table 8 together with, and for comparison, those of a composition containing the calcium carbonate but no poly-butadiene - maleic anhydride adduct or methyl hal ester.
Example Example Example Comparison Tensile Strength (Kg/sq cm)50 34 45.5 28 Elongation at break % 343 324 369 493 100% tensile modulus (Kg/sq cm~ 23 20 23 14.5 200% tensile modulus (Kg/sq cm)37.6 28 34 16 300% tensile modulus ~Kg/sq cm) 46 33 41 18.5 ~ -Tear Strength ~angle) (KgF/mm)2.93 2.66 2.66 1.84 - DAGW/~R
: RD/3/44/A-12-30 ~ 45 A-2-10 . . .
~ i .. . . . .
:
The above procedure of Example 13 was repeated except that the polybutadiene - maleic anhydride adduct was `: 25 replaced by a methyl half e~ter of the same adduct .
`, (Example 14).
.
, . ~
.. ' ~' :
i :
. ~
The compounding procedure of the above described Example 13 was repeated except that the coated calcium carbonate was replaced by 97 parts by weight o~ the natural calcium carbonate whiting and 3 parts by weight of the polybutadiene - maleic anhydride adduct used in Example 13~ (Example 15).
The properties of the cured compositions are given in Table 8 together with, and for comparison, those of a composition containing the calcium carbonate but no poly-butadiene - maleic anhydride adduct or methyl hal ester.
Example Example Example Comparison Tensile Strength (Kg/sq cm)50 34 45.5 28 Elongation at break % 343 324 369 493 100% tensile modulus (Kg/sq cm~ 23 20 23 14.5 200% tensile modulus (Kg/sq cm)37.6 28 34 16 300% tensile modulus ~Kg/sq cm) 46 33 41 18.5 ~ -Tear Strength ~angle) (KgF/mm)2.93 2.66 2.66 1.84 - DAGW/~R
: RD/3/44/A-12-30 ~ 45 A-2-10 . . .
~ i .. . . . .
:
Claims (38)
1. A process for the production of a coated particu-late filler which comprises binding to the surface of a basic particulate filler an acidic group-containing organic polymer, which polymer contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
2. A process as claimed in Claim 1 in which the filler is a hydroxide or carbonate of an alkaline earth metal.
3. A process as claimed in Claim 2 in which the filler is magnesium hydroxide.
4. A process as claimed in Claim 2 in which the filler is calcium carbonate.
5. A process as claimed in Claim 1 in which the filler has a particle size in the range 40 Angstrom to 1 mm.
6. A process as claimed in Claim 5 in which the filler has a particle size in the range 40 to 1000 Angstrom.
7. A process as claimed in Claim 1 in which the acidic group is a carboxylic acid group.
8. A process as claimed in Claim 1 in which the acidic group is an anhydride group.
9. A process as claimed in Claim 1 in which the acidic group is an alkali metal, ammonium, or trialkyl am-monium salt of a carboxylic acid group.
10. A process as claimed in Claim 1 in which the unsaturated group is an ethylenically unsaturated group.
11. A process as claimed in Claim 10 in which the acidic group containing organic polymer is a polydiene.
12. A process as claimed in Claim 11 in which the polydiene is polybutadiene.
13. A process as claimed in Claim 11 or 12 in which the acidic group-containing organic polymer is prepared by reacting a polydiene with maleic anhydride.
14. A process as claimed in Claim 1 in which the molecular weight of the acidic group-containing organic polymer is in the range 200 to 50,000.
15. A process as claimed in Claim l4 in which the molecular weight of the acidic group-containing organic polymer is in the range 1000 to 5000.
16. A process as claimed in Claim 1 in which the acidic group-containing organic polymer is liquid at the temperature at which the process is effected.
17. A process as claimed in Claim 1 in which the process is effected in the presence of a solvent or dispersant for the acidic group-containing organic polymer.
18. A process as claimed in Claim 17 in which the solvent or dispersant is water.
19. A process as claimed in Claim 1 which is effect-ed at a temperature in the range 0°C to 200°C.
20. A process as claimed in Claim 1 in which the basic particulate filler and acidic group-containing organic polymer are present in proportions which result in the pro-duction of a basic particulate filler having an organic polymer bound to the surface thereof in a proportion of 0.2% to 40%
by weight of organic polymer to 99.8% to 60% by weight of filler.
by weight of organic polymer to 99.8% to 60% by weight of filler.
21. A basic particulate filler to the surface of which there is bound an organic polymer which contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
22. A basic particulate filler as claimed in Claim 21 in which the filler is a hydroxide or carbonate of an alkaline earth metal.
23. A basic particulate filler as claimed in Claim 22 in which the filler is magnesium hydroxide.
24. A basic particulate filler as claimed in Claim 23 in which the filler is calcium carbonate.
25. A basic particulate filler as claimed in any one oE Claims 21 to 23 in which the filler has a particle size in the range 40 Angstrom to 1 mm.
26. A basic particulate filler as claimed in any one of Claims 21 to 23 in which the unsaturated group is an ethylenically unsaturated group.
27. A basic particulate filler as claimed in Claim 21 in which the organic polymer is a polydiene.
28. A basic particulate filler as claimed in Claim 27 in whieh the polydiene is polybutadiene.
29. A basic partieulate filler as claimed in any one of Claims 21 to 23 in whieh the molecular weight of the organic polymer is in the range 1000 to 5000.
30. A basie particulate filler as claimed in any one of Claims 21 to 23 comprising 0.2 to 40% by weight of prganic polymer and 99.8% to 60% by weight of particulate filler.
31. A polymer composition comprising a matrix of an organic polymer having incorporated therein a basic partieulate filler to the surface of which there is bound an organic polymer which contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
32. A polymer composition as claimed in Claim 31 which comprises 5% to 300% of filler to the surface of whieh there is bound an organie polymer by weight of the matrix organie polymer.
33. A polymer composition as claimed in Claim 32 which comprises 10% to 200% of filler to the surface of which there is bound an organic polymer.
34. A polymer composition as claimed in any one of Claims 31 to 33 in which the matrix organic polymer is a vulcanisable rubber.
35. A polymer composition as claimed in Claim 31 in which the matrix organic polymer is a vulcanised rubber and in which the polymer bound to the surface of the par-ticulate filler is reacted with the vulcanised rubber.
36. A polymer composition as claimed in Claim 35 in which the rubber is styrene-butadiene rubber or natural rubber.
37. A process for the production of a polymer composition as claimed in any one of Claims 31 to 33 which comprises mixing a matrix organic polymer with a basic par-ticulate filler to the surface of which there is bound an organic polymer which contains at least one unsaturated group and which has a molecular weight of not greater than 100,000.
38. A process for the production of a polymer composition as claimed in any one of Claims 31 to 33 which comprises mixing a matrix organic polymer, a basic particulate filler, and an acidic group-containing organic polymer which contains at least one unsaturated group and which has a mole-cular weight of not greater than 100,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB22277/77 | 1977-05-26 | ||
| GB22277/77A GB1603300A (en) | 1977-05-26 | 1977-05-26 | Fillers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1110504A true CA1110504A (en) | 1981-10-13 |
Family
ID=10176782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA304,247A Expired CA1110504A (en) | 1977-05-26 | 1978-05-25 | Polymer coated inorganic fillers |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS53147743A (en) |
| AT (1) | AT371134B (en) |
| AU (1) | AU522211B2 (en) |
| BE (1) | BE867333A (en) |
| CA (1) | CA1110504A (en) |
| DE (1) | DE2823156A1 (en) |
| ES (2) | ES470237A1 (en) |
| FR (1) | FR2392068A1 (en) |
| GB (1) | GB1603300A (en) |
| IT (1) | IT1158721B (en) |
| NL (1) | NL185726C (en) |
| NZ (1) | NZ187318A (en) |
| ZA (1) | ZA782861B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0038620A3 (en) * | 1980-03-21 | 1982-06-09 | Imperial Chemical Industries Plc | Particulate filler and polymer composition containing the filler |
| CA1211319A (en) * | 1982-11-24 | 1986-09-16 | Gerson M.F. Vas | Coated particulate fillers |
| FR2554119B1 (en) * | 1983-10-26 | 1986-01-24 | Omya Sa | CALCIUM CARBONATE TREATED FOR HIGHLY LOADED COMPOSITIONS OF THERMOSETTING OR THERMOPLASTIC RESINS |
| GB8421288D0 (en) * | 1984-08-22 | 1984-09-26 | Ici Plc | Filler |
| US4717496A (en) * | 1984-12-03 | 1988-01-05 | Giulini Chemie Gmbh | Stiffening material with melt-adhesive properties |
| GB8502928D0 (en) * | 1985-02-05 | 1985-03-06 | Bicc Plc | Cross-linkable compositions |
| EP0292233A3 (en) * | 1987-05-22 | 1989-01-25 | Imperial Chemical Industries Plc | Fillers |
| EP0292232A3 (en) * | 1987-05-22 | 1990-12-12 | Imperial Chemical Industries Plc | Fillers |
| EP0292231A3 (en) * | 1987-05-22 | 1990-12-12 | Imperial Chemical Industries Plc | Fillers |
| US5952429A (en) * | 1995-06-14 | 1999-09-14 | Nippon Shokubai Co., Ltd. | Carbon black graft polymer, method for production thereof, and use thereof |
| FR2742446B1 (en) | 1995-12-14 | 1999-01-15 | Coatex Sa | USE OF COPOLYMERS OF STYRENE AND MALEIC ANHYDRIDE AS DISPERSING AND / OR MINERAL LOAD TREATMENT AGENTS. THERMOPLASTIC COMPOSITIONS CONTAINING THEM |
| DE102012015958A1 (en) | 2012-08-11 | 2014-02-13 | Plasma Technology Gmbh | Apparatus for producing mixture of plastic polymers with inorganic filler, for thermoplastic processing in plastic industry, by a plasma pretreatment of fillers, where formed reactive groups are introduced into plastic polymer during mixing |
| DE102012023428A1 (en) | 2012-11-29 | 2014-06-05 | Plasma Technology Gmbh | Device for drying three-dimensional coated components with UV rays of gas discharge lamps in automobile field, has alternating current generator for generating low-pressure plasma such that post-treatment is processed in plasma |
| JP7237649B2 (en) | 2019-02-27 | 2023-03-13 | 株式会社ジャパンディスプレイ | Display device |
| CN117467287A (en) * | 2023-11-01 | 2024-01-30 | 广西双文材料科技有限公司 | Modified heavy calcium carbonate, production method and application in preparing high-performance sealant |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1345475A (en) * | 1971-02-01 | 1974-01-30 | Mitsubishi Petrochemical Co | Mthod of forming a filler and resin or rubber composition |
| US3969313A (en) * | 1972-06-14 | 1976-07-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic composite compositions |
| JPS5027842A (en) * | 1973-07-12 | 1975-03-22 |
-
1977
- 1977-05-26 GB GB22277/77A patent/GB1603300A/en not_active Expired
-
1978
- 1978-05-18 ZA ZA00782861A patent/ZA782861B/en unknown
- 1978-05-19 NZ NZ187318A patent/NZ187318A/en unknown
- 1978-05-22 AU AU36315/78A patent/AU522211B2/en not_active Expired
- 1978-05-22 BE BE187919A patent/BE867333A/en not_active IP Right Cessation
- 1978-05-25 NL NLAANVRAGE7805676,A patent/NL185726C/en not_active IP Right Cessation
- 1978-05-25 IT IT7823804A patent/IT1158721B/en active
- 1978-05-25 CA CA304,247A patent/CA1110504A/en not_active Expired
- 1978-05-25 FR FR7815647A patent/FR2392068A1/en active Granted
- 1978-05-26 DE DE19782823156 patent/DE2823156A1/en active Granted
- 1978-05-26 JP JP6237378A patent/JPS53147743A/en active Pending
- 1978-05-26 ES ES470237A patent/ES470237A1/en not_active Expired
- 1978-05-26 AT AT0384678A patent/AT371134B/en not_active IP Right Cessation
-
1979
- 1979-03-15 ES ES478665A patent/ES478665A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2392068B1 (en) | 1984-03-23 |
| DE2823156A1 (en) | 1978-12-21 |
| ES478665A1 (en) | 1980-01-16 |
| NL7805676A (en) | 1978-11-28 |
| AU522211B2 (en) | 1982-05-20 |
| NL185726C (en) | 1990-07-02 |
| NZ187318A (en) | 1980-03-05 |
| FR2392068A1 (en) | 1978-12-22 |
| NL185726B (en) | 1990-02-01 |
| JPS53147743A (en) | 1978-12-22 |
| ES470237A1 (en) | 1979-09-16 |
| GB1603300A (en) | 1981-11-25 |
| AU3631578A (en) | 1979-11-29 |
| ATA384678A (en) | 1982-10-15 |
| BE867333A (en) | 1978-11-22 |
| AT371134B (en) | 1983-06-10 |
| IT7823804A0 (en) | 1978-05-25 |
| IT1158721B (en) | 1987-02-25 |
| ZA782861B (en) | 1979-05-30 |
| DE2823156C2 (en) | 1987-06-25 |
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