Classifications

• • 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
  • C09C1/22—Compounds of iron
  • C09C1/24—Oxides of iron
• • 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
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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
  • C09C1/28—Compounds of silicon
  • C09C1/32—Ultramarine
• • 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
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3684—Treatment with organo-silicon compounds
• • 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
  • C09C3/12—Treatment with organosilicon compounds

Definitions

• the present invention relates to the hydrophobizing of particles, particularly inorganic water-insoluble compounds.
• the present invention also relates to the treated particles, per se .
• the treated particles are useful particularly, but not exclusively in the compounding of polymers, especially rubbers and plastics.
• the present invention also relates to dispersions of the treated particles in a polymer-containing matrix (binder) and to a process for preparing such dispersions.
• Polymers either rubbers or plastics rarely have the inherent physical or chemical properties in their pure state that are necessary to make useful articles.
• the polymers must thus be further compounded by mixing with additional ingredients or "additives”.
• Polymer additives may include one or more of: secondary polymers; extender oils; fillers; antioxidants; coloring pigments, stabilizers, flame retardants, processing aids and other ancillary chemicals.
• curatives such as sulfur or organic peroxides
• cure accelerators such as dibenzothiazyl disulphide (MBTS) and tetramethylthiuram disulfide (TMTD)
• inorganic cure activators such as zinc oxide, lead monoxide (PbO, litharge), red lead (Pb 3 O 4 ), and the like.
• the selected additive materials must be mixed intimately with the polymer at the compounding stage (so as to obtain a homogeneous dispersion) in order for the maximum improvements to be realized.
• this mixing is usually accomplished on an open mill, in a mixing extruder or in an internal mixer (such as the Henschel, Welex or Banbury types) using one or more steps until the desired degree of dispersion is achieved.
• Dust losses also change the ratio of the chemicals to the base polymer from what was originally intended; this may lead to poor processing or poor finished properties in the compound.
• very fine particles may act as a lubricant and actually contribute to poor mixing of the bulk, in this case by reducing the shear which is needed for dispersion.
• agglomeration of the particles may occur during mixing, leading to undesirable inhomogeneity and unsatisfactory physical properties.
• inorganic chemicals to the base polymer in a predispersed form, e.g., as fine particles bound in a low viscosity medium (or binder) such as polymer or oil, or combinations thereof with additional additives.
• a low viscosity medium such as polymer or oil
• This bound form of inorganic chemicals overcomes the dust problem in the rubber compounding plant and also greatly shortens the dispersing time of the inorganic materials in the polymer compound, particularly if the binder is chemically similar to the base polymer and the viscosity of the pre-dispersion closely matches that of the rest of the compound. From a compounding standpoint, it is desirable to have the minimum amount of binder that will both facilitate dispersion and eliminate dusting during processing.
• Non-limiting examples of such commercial polymer-bound materials used in the rubber industry are: RHENOGRAN® ZnO-85 (85 weight percent zinc oxide dispersed in an EPDM/EVA binder); POLY-DISPERSION® PLD-90 (90 weight percent lead monoxide dispersed in polyisobutylene); RHENOGRAN® Pb 3 O 4 -90 (90 weight percent red lead oxide dispersed in EPDM/EVA), all available from Rhein-Chemie Corporation and Rhein Chemie Rheinau GmbH.
• Cheaper oil-based binders may also be used; while these address the dust problem, they do not offer as good or as rapid a dispersion as the presence of oil lowers the friction necessary to cause comminution of the inorganic materials during mixing. The presence of oil may also cause other changes in the physical properties (i.e. softening) or appearance (colour) which are undesirable.
• An example of the latter type of dispersion is PolydexTM PPD (ZnO) 75, a 75 weight percent blend of ZnO in a light process oil, available from Polychem.
• these additives in their pure form, may be added directly to the bulk plastic during the processing (compounding) phase; although, it is more customary to use the materials as concentrates in liquid or pellet form in order to obtain better dispersion and better control of the process.
• these concentrates consist of a dispersion of fine particles of the additive in a suitable carrier or 'binder' which may be similar or identical to the base polymer, or it may be another compatible polymer or a combination of polymers and oil.
• ingredients may be included in the base of the binder.
• This concentrate form is used almost exclusively for introducing inorganic colorants into plastics where the high hardness and high melting point of the additives causes dispersion problems.
• a facile known method to prepare fine particle size materials from coarser commercially available ones is by wet grinding, using either a ball, colloid or steam jet mill or other equipment as described under "Wet Grinding” in Ullmann's Encyclopedia of Industrial Chemistry Vol. B2 sec. 5-36, the contents of which are hereby incorporated by reference.
• the concentration of the fine particles in the wetting medium is of necessity low in order to maintain the fluidity required for satisfactory grinding and thus the particles must be insoluble in the grinding medium.
• media other than water is employed during the size reduction process, additional hazards such as flammability must be taken into consideration.
• the resulting dispersions typically require concentration (i.e., solvent removal) before they can be further dispersed in a binder. Moreover, it is difficult to dry such fine particles without generating dust elsewhere in the process or without causing agglomeration (particle growth) during the drying step. Where possible, it would be preferable to produce masterbatches, dispersions and concentrates of these particles in suitable binders while the particles are still in a finely divided wet state. It is also preferable for economy and safety perspectives that the grinding medium be water. An additional benefit of using water is that it is generally a non-solvent for most of the organic and inorganic additives which are sold as dispersions.
• a number of prior art references teach how to make "masterbatches" of fillers and dispersions of other chemicals in polymers by using fine particles dispersed in an aqueous state.
• Burke United States patent 3,689,451, United States patent 3,689,452, United States patent 3,700,690, United States patent 3,716,513 and United States patent 3,840,382, the contents of each of which is hereby incorporated by reference
• Burke teaches how to use an aqueous dispersion of never-dried alkali silica pigment or a mixture of an aqueous dispersion of never-dried alkali silica pigment silica and carbon black to make a dispersion of these fillers in a matrix of rubbers at levels of ⁇ 100 phr of filler.
• These masterbatches are usually prepared by grinding the carbon black in a wet aqueous state and then intensively mixing the black slurry with a solution-polymer "cement” or emulsion polymer latex, with or without added oil, followed by coagulation and drying.
• the levels of black filler are ⁇ 100 phr.
• the polymer is available as an aqueous emulsion (i.e., latex)
• various methods are available for the incorporation of ancillary chemicals to form dispersions; the coprecipitation methods of Leo and Johansson (United States patent 4,110,240) may be used to prepare concentrates containing 80-99.5 wt% of the ancillary chemicals (excluding fillers), either organic or inorganic in the polymeric binder.
• Kanou et al. (United States patent 4,713,411) detail a different coprecipitation process to produce a pigment composition by using a special water-soluble polymeric binder which is then rendered insoluble by pH changes.
• many polymers, especially plastics are prepared by a solution polymerization process and are not readily available in a latex form.
• the present invention provides a process for treating particles to render them hydrophobic, the process comprising the step of: contacting the particles with a compound of Formula I:
• R 1 , R 2 and R 3 preferably two of R 1 , R 2 and R 3 and most preferably R 1 , R 2 and R 3 are hydroxyl or hydrolysable groups;
• R 4 is a divalent group that is resistant to hydrolysis at the Si-R 4 bond
• R 5 is selected from: hydrogen; a C, .40 alkyl; a C 2.40 mono-, di- or tri- unsaturated alkenyl group; a C 5 -C 40 aryl group; a group of the formula:
• R 8 and R 9 which may be the same or different, are each selected from: hydrogen; C M 8 alkyl; C 2 . 18 mono-, di- or tri-unsaturated alkenyl; phenyl; a group of formula:
• R 10 and R ⁇ may be the same or different and are each selected from, hydrogen, C, 10 alkyl group or C 2 10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom; and a group of formula:
• r is an integer from 1 to 6 and d is an integer from 1 to 4,
• R 6 may be any of the groups defined for R 5 with the provisos that: (1) R 5 and R 6 do not have a tertiary carbon atom adjacent to the mtrogen atom, and (ii) at least one of R 5 and R 6 has a carbon chain at least 8 carbon atoms in length uninterrupted by any heteroatoms; or R 5 and R 6 may together form a divalent group of formula:
• the present invention provides a treated particulate material comprising particles having bound thereto an aminohydrocarbonsiloxane (e.g., an (aminoalkyl)siloxane) moiety - i.e., a hydrocarbon moiety comprising both silicon and nitrogen.
• an aminohydrocarbonsiloxane e.g., an (aminoalkyl)siloxane
• the aminohydrocarbonsilane moiety has the formula
• R ⁇ R b and R c are the same or different and each is selected from -O- and -C p H 2p -, optionally substituted by one or more oxygen atoms and wherein p is an integer of from 1 to 10;
• R 12 is a group of formula:
• R 4 is a divalent group that is resistant to hydrolysis at the Si-R 4 bond;
• R 5 is selected from: hydrogen; a C, .40 alkyl; a C 2 _ w mono-, di- or tri- unsaturated alkenyl group; a C 6 -C 40 aryl group; a group of the formula:
• R 8 and R 9 which may be the same or different, are each selected from: hydrogen; C, lg alkyl; C 2 , g mono-, di- or t ⁇ - unsaturated alkenyl; phenyl; a group of formula:
• R i0 and R 11 may be the same or different and are each selected from: hydrogen, C, 10 alkyl group or C 2 10 alkenyl group, provided that there is no double bond m the position alpha to the nitrogen atom; and a group of formula:
• r is an integer from 1 to 6 and d is an integer from 1 to 4;
• R 6 may be any of the groups defined for R 5 with the provisos that: (l) R 5 and R 6 do not have a tertiary carbon atom adjacent to the nitrogen atom, and (ii) at least one of R 5 and R 6 has a carbon chain at least 8 carbon atoms in length uninterrupted by any heteroatoms; or R 5 and R 6 may together form a divalent group of formula:
• A is selected from: a -CHR group or a -NR group in which R is hydrogen or a C ⁇ o alkyl or . ⁇ alkenyl group, a C 6 -C 40 aryl group, an oxygen atom and a sulfur atom, and t and v are each independently 1, 2, 3 or 4; provided that the sum of t and v does not exceed 6, and is preferably 4.
• the present invention provides a paniculate matenal compnsmg panicles having: (i) bound thereto an aminohydrocarbonsiloxane (e.g., an (am ⁇ noalkyl)siloxane) moiety (i.e., a hydrocarbon moiety compnsmg both silicon and nitrogen), and (ii) a contact angle of at least about 100°.
• an aminohydrocarbonsiloxane e.g., an (am ⁇ noalkyl)siloxane
• a contact angle of at least about 100° i.g., a contact angle of at least about 100°.
• the aminohydrocarbonsilane moiety has the formula set out hereinabove.
• the particles have a contact angle of at least about 110°, more preferably in the range of from about 115° to about 160°, even more preferably in the range of from about 120° to about 150°, most preferably in the range of from about 120° to about 140°.
• the contact angle of particles which are not treated in accordance with the present process is typically 75°.
• the contact angle of the panicles with water may be readily determined according to the following procedure:
• double-sided tape is attached to a probe (e.g., a stirrup) and coated with the paniculate matenal by immersing the tape in a sample of the particulate material;
• excess powder is removed by gentle tapping and large powder clusters are removed by careful wiping;
• the probe coated with paniculate material is immersed into distilled water using a conventional contact angle analyzer
• the present invention provides a particulate material produced by contacting the particles with a compound of Formula I:
• R 1 , R 2 and R 3 preferably two of R 1 , R 2 and R 3 and most preferably R 1 , R 2 and R 3 are hydroxyl or hydro lysable groups
• R 4 is a divalent group that is resistant to hydrolysis at the Si-R 4 bond
• R 5 is selected from: hydrogen; a C 0 alkyl; a C 2-40 mono-, di- or tri- unsaturated alkenyl group; a C 6 -C 40 aryl group; a group of the formula:
• R 8 and R 9 which may be the same or different, are each selected from: hydrogen; C 8 alkyl; C 2 . lg mono-, di- or tri-unsaturated alkenyl; phenyl; a group of formula:
• R 10 and R" may be the same or different and are each selected from: hydrogen, C M0 alkyl group or C 2.10 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom; and a group of formula:
• r is an integer from 1 to 6 and d is an integer from 1 to 4;
• R 6 may be any of the groups defined for R 5 with the provisos that: (i) R 5 and R 6 do not have a tertiary carbon atom adjacent to the nitrogen atom, and (ii) at least one of R 5 and R 6 has a carbon chain at least 8 carbon atoms in length uninterrupted by any heteroatoms: or R 5 and R 6 may together form a divalent group of formula:
• the present invention provides a dispersion comprising a polymer and treated particulate material; wherein the treated particulate material comprises panicles having bound thereto an aminohydrocarbonsiloxane moiety comprising both silicon and nitrogen.
• the present process of treating a particulate material is carried out in an aqueous solution, suspension or slurry, so that the product of the process is an aqueous suspension or slurry of hydrophobicized mineral particles.
• the suspension or slurry resulting from the present process, and containing the treated particles is then mixed with a hydrocarbon solution of a polymer, and then dried to form a polymer-particle dispersion. Owing to the hydrophobicized nature of the treated particles, they are well dispersed in the polymer.
• This preferred embodiment results in the in situ production of a dispersion comprising the polymer and the treated particles.
• in situ production is meant that treated particles are incorporated into a suspension without being isolated (i.e., separated from the suspension or slurry, and subsequently dried).
• This prefened embodiment is believed to be the first in_ai u production of a dispersion comprising a polymer and a treated particulate material (such as metal oxides and the like will be discussed in more detail hereinbelow), the dispersion having been prepared from a polymer solution.
• a treated particulate material such as metal oxides and the like will be discussed in more detail hereinbelow
• the treated paniculate material may be separated from the suspension or slurry, and subsequently dried for later use (i.e., before addition of the polymer solution).
• the terms “concentrate”, “dispersion” and “pre- dispersion”, when used in the context of the present invention, are intended to mean a composition comprising a particulate material (i.e., the additive(s) to be used for compounding purposes) and a binder therefor, wherein the particulate material is the major component of the composition - i.e., the composition comprises at least about 50 percent by weight particulate material.
• the composition comprises from about 50 to about 95, more preferably from about 60 to about 95, even more preferably from about 70 to about 95, percent by weight particulate material.
• Figure 1 illustrates a schematic of a system useful to conduct the present process.
• the present invention is particularly useful to the treatment of inorganic water insoluble compounds.
• the inorganic water insoluble compounds useful for treatment are those such compounds which contain oxygen, more preferably such compounds which also contain a metal.
• the metal is selected from Groups II-VIII of the Penodic Table of Elements (Group II hydroxide and carbonate compounds). Examples of suitable groups of useful metal compounds may be selected from the group compnsmg oxides, hydroxides, borates, sulfates, carbonates, silicates, phosphates, chromates and the like.
• Non-limiting examples of suitable metal compounds may be selected from the group compnsmg titanium oxide, feme oxide, hydrated feme oxide, fenous oxide, antimony oxide, banum carbonate, zinc oxide, zinc borate, lead oxide (including red lead oxide), dibasic lead phosphite, lead silicate, tnbasic lead sulfate and mixtures thereof.
• suitable metal compounds especially those which are water insoluble or only slightly soluble m water, will be readily apparent to those of skill in the art base on the foregoing discussion.
• a particularly preferred application of the present invention is to hydrophobicize colorant or pigment particles which are typically used in the plastics industry
• suitable such panicles may be selected from the group consisting of ⁇ -FeOOH (goethite), ⁇ -FeOOH (lepidocrocite), ⁇ -Fe 2 O 3 (hematite), ⁇ -Fe 2 O 3 (maghemite) and Fe 3 O 4 .
• the treatment is earned out in an aqueous dispersion or slurry of the particles.
• the precise make up of the slurry is not particularly restncted provided that it is a mobile suspension.
• the slurry contain up to about 60% by weight, more preferably up to about 50%) by weight, of particles to be treated. While the physical nature of the particles to be treated is not particularly restncted, it is preferred that they have an average particle size in the range of from about 0 1 ⁇ m to about 100 ⁇ m, preferably from about 10 ⁇ m to about 50 ⁇ m, most preferably from about 10 ⁇ m to about 25 ⁇ m. It is desirable that, prior to the addition to the particles of the compound of Formula I, the dispersion or slurry shall have a pH in the range from 6 to about 8, more preferably from about 6.8 to about 7.2. The pH can be adjusted by addition of acid or alkali, for example mineral acid, alkali metal hydroxide, alkaline earth hydroxide, ammonium hydroxide and the like. These can be added as such or in aqueous solution.
• acid or alkali for example mineral acid, alkali metal hydroxide, alkaline earth hydroxide, ammonium hydroxide and the
• the compound of Formula I comprises the following formula:
• R 1 , R 2 and R ⁇ preferably two of R 1 , R 2 and R 3 and most preferably R 1 , R 2 and R 3 are hydroxyl or hydro lysable groups;
• R 4 is a divalent group that is resistant to hydrolysis at the Si-R 4 bond;
• R 5 is selected from: hydrogen; a C,. ⁇ alkyl; a C 2.40 mono-, di- or tri- unsaturated alkenyl group; a C 6 -C 40 aryl group; a group of the formula:
• R 8 and R 9 which may be the same or different, are each selected from: hydrogen; C 8 alkyl; C 2. , 8 mono-, di- or tri-unsaturated alkenyl; phenyl; a group of formula:
• R 10 and R" may be the same or different and are each selected from: hydrogen, C,. 10 alkyl group or C 2. , 0 alkenyl group, provided that there is no double bond in the position alpha to the nitrogen atom; and a group of formula:
• r is an integer from 1 to 6 and d is an integer from 1 to 4;
• R 6 may be any of the groups defined for R 5 with the provisos that: (i) R 5 and R 6 do not have a tertiary carbon atom adjacent to the nitrogen atom, and (ii) at least one of R 5 and R 6 has a carbon chain at least 8 carbon atoms in length uninterrupted by any heteroatoms; or R 5 and R 6 may together form a divalent group of formula:
• A is selected from: a -CHR group or a -NR group in which R is hydrogen or a C 6.40 alkyl or C 6.40 alkenyl group, a C 6 -C 40 aryl group, an oxygen atom and a sulfur atom, and t and v are each independently 1, 2, 3 or 4; provided that the sum of t and v does not exceed 6, and is preferably 4.
• Suitable groups R 1 include hydroxyl groups, acetate groups and hydrolysable groups of formula OC p H 2p+1 , where p has a value from 1 to 10.
• the alkyl chain can be interrupted by oxygen atoms, to give groups, for example, of formula CH ? OCH 2 O-, CH 3 OCH 2 OCH 2 O-, CH 3 (OCH 2 ) 4 O-, CH 3 OCH 2 CH 2 O-, C 2 H 5 OCH 2 O-, C 2 H 5 OCH 2 OCH 2 O-, or C 2 H 5 OCH 2 CH 2 O-.
• R 2 and R 3 can take the same values as R 1 , provided that only one of R 1 ,
• R 2 and R 3 is chloro, bromo or iodo.
• R 1 , R 2 and R 3 is hydroxyl or ONa, OLi or OK.
• Non-limiting examples of groups R 2 and R 3 that are not hydrolysable include C, .10 alkyl, C 2.10 mono- or diunsaturated alkenyl, and phenyl.
• R 2 and R 3 can also each be a group -R 4 -NR 5 R 6 , discussed further below.
• R 2 and R 3 are all the same and are CH 3 O-, C 2 H 5 O- or C 3 H 8 O-. Most preferably they are all CH 3 O-.
• the divalent group R 4 is preferably such that N-R 4 -Si is of the formula:
• N-(CH 2 ) p (O) 0 (C 6 H 4 ) n (CH 2 ) m (CH CH) k -Si in which k, m, n. o and p are all whole numbers
• k, m, n. o and p are all whole numbers
• the order of the moieties between N and Si is not particularly restncted other than neither N or O should be directly bound to Si.
• the value of k is 0 or 1
• the value of m is from 0 to 20 inclusive
• the value of n is 0, 1 or 2
• the value of o is 0 or 1
• the value of p is from 0 to 20 inclusive
• the provisos that the sum of the values of k, m, n, o and p is at least 1 and not more than 20 and that if o is 1, p is 1 or greater and the sum of k, m and n is 1 or greater, i.e. that the Si atom is linked directly to a carbon atom. There should be no hydrolysable bond between the silicon and nitrogen atoms.
• m is 3 and 1, n, o and p are all 0, l e., R 4 is -CH 2 CH 2 CH 2 -
• Prefened compounds of Formula I include those m which R 5 is hydrogen and R 6 is an alkenyl group selected from the group compnsmg soya alkyl, tall oil alkyl.
• Vanous of these prefened compounds of Formula I may be produced, for example, by the process descnbed in International patent application S N PCT/CA98/0500 [Koski], the contents of which are hereby incorporated by reference.
• this copending patent application relates to a process for producing the following preferred compounds of Formula I
• R 1 is a C 6 -C 0 alkyl or alkenyl group that is straight-chained or branched, a C 6 -C 40 aryl group, a C-C 40 aralkyl group or a group R 5 A(CH 2 ) p wherein R ⁇ is a C 6 -C 30 alkyl or alkenyl group that is straight-chained or branched, p is an integer from 2 to 6 and A is O or NH,
• R 2 is a C,-C 12 alkyl group (preferably a C,-C 5 alkyl group) or a C 3 -C 12 alkenyl group (preferably a C r C 5 alkenyl group);
• R 3 is a C,-C 12 alkyl group (preferably a C,-C 5 alkyl group), a C,-C l2 alkoxy group (preferably a C,-C 5 alkoxy group), a C 2 -C 12 alkenyl group (preferably a C 2 -C 5 alkenyl group) or a C 3 -C 12 alkenyloxy group (preferably a C 3 -C 5 alkenyloxy group);
• R 4 has the same definition as R 3 and may be the same as R 4 or different;
• R 6 is a divalent alkylene group having up to 10 carbon atoms and is optionally interrupted one, two or three times by a phenylene group;
• X is an anion
• R 2 , R 3 , R 4 , R 6 and X are as defined above, in the absence of a solvent; or (b) reacting a compound of the Formula IV:
• R 2 , R 3 , R 4 and R 6 are as defined above, in the absence of a solvent
• R 4 , R 8 and R 9 has a chain of at least 8 carbon atoms, more preferably at least 10 carbon atoms, uninterrupted by any heteroatom
• the compound of Formula I can be used as the free base, or in the form of its acid addition or quaternary ammonium salt, l e
• R 1 , R 2 , R 3 , R 4 , R 5 and R° are as defined above
• R 7 is selected from hydrogen, a C, 40 alkyl group or C 2 40 mono-, di- or tn-unsaturated alkenyl group
• X is an anion X is suitably acetate, chlonne, bromine, or sulphate, of which chlonne and bromine are prefened.
• R is preferably hydrogen
• Non-limiting examples of suitable salts of compounds of Formula I may be selected from the group compnsmg N-oleyl-N-[(3-tnethoxys ⁇ lyl)propyl] ammonium chlonde, N-3-ammopropylmethyld ⁇ ethoxy-s ⁇ lane hydrobromide, (am ⁇ noethylam ⁇ no-methyl)phenyltnmethoxys ⁇ lane hydrochlonde, N-[(3- tnmethoxys ⁇ lyl)propyl]-N-methyl, N-N-diallylammonium chlonde, N-tetradecyl-N,N- d ⁇ methyl-N-[(3-tnmethoxys ⁇ lyl)propyl] ammonium bromide, 3[2-N- benzylammoethyl-ammopropyl]tnmethoxysilane hydrochlonde, N-octadecyl-N,N-
• the amount of the compound of Formula I may be between 0.1 and 20 percent by weight of the mineral particles in the slurry (dry basis) and preferably between 0.25 and 10 percent by weight and most preferably between 0.5 and 2 percent by weight.
• the amount of the compound of Formula I used varies inversely with the mineral particle size.
• the chemical nature of the particles being treated also may affect the amount of the compound of Formula I which is used.
• the compound of Formula I may be added to the aqueous slurry of particles in its natural state, either as a liquid or a solid. However, to facilitate dispersion, it is preferred where possible to add the compound as a liquid.
• the melting point of the compound is below 95°C, it is preferred to add it to the slurry in a molten state at a temperature at least 5°C above the melting point, provided the temperature of the compound in the liquefied state does not exceed 100°C and provided that the compound does not decompose under these conditions. If the melting point exceeds 95°C, it is most prefened to use a solvent to dissolve the compound of Formula I.
• Prefened solvents are water and C,. 5 alcohols, most preferably C, .3 alcohols - e.g., methanol, ethanol, n-propanol, isopropanol and mixtures thereof.
• the alkoxy group of the solvent alcohol will be the same as the alkoxy group of the alkoxysilane.
• the preferred solvent is methanol.
• the concentration of the compound of Formula I in the solvent is in the range of from about 10 to about 90 percent by weight, more preferably in the range of from about 25 to about 75 percent by weight, most preferably about 50 percent by weight.
• the solution can be prepared and added to the slurry at a temperature in the range of from about 0°C to the lower of at least 10°C below the boiling point of the solvent and 95°C.
• the dispersion of the compound conveniently may be effected by mixing. It is prefened that, for the specific compound of Formula I which is added, the equivalent balance (EB) should be calculated.
• the EB is used to determine whether mineral acid or alkali metal hydroxide, or solution thereof, should be added.
• the equivalent balance (EB) may be determined from the absolute value of the sum of the group values of X (if present), R 1 , R 2 and R 3 and the magnitude of the sum of the group contributions of X (if present), R 1 , R 2 and R 3 together with the weight added and the molecular weight of the compound of Formula I, according to the following scheme:
• each of R 1 , R 2 and R 3 is generally zero for all groups except as follows: if the group is CH 3 COO, CI or Br, in which case it is -1 , or if it is amine (including an imine), ONa, OK or OLi in which case it is +1. If the sum of the group contributions for X, R 1 , R 2 and R 3 is zero, no adjustment with mineral acid or alkali metal hydroxide (or solutions thereof) is necessary. If the sum of the group values is a positive integer, adjustment with mineral acid is desirable, and if it is negative, adjustment with alkali metal hydroxide is desirable.
• EB N j x weight in grams of the chemical added molecular weight of the added chemical
• the prefened technique according to the invention is to dissolve the alkali metal hydroxide or mineral acid m water so as to obtain a concentration in the range of from about 5 to about 25 percent by weight, most preferably in the range of from about 5 and about 10 percent by weight pnor to adding the solution to the slurry.
• the process descnbed thus far provides an aqueous slurry or dispersion of hydrophobicized particles (l e., it has not yet been contacted with a polymer or other substrate to be filled), which can be used as such or can be filtered and dned.
• the hydrophobicized particles may be used as a compounding agent in a multitude of matenals including, but not limited to, the following: polymers, alkyd paints, toners such as those used in photocopiers, modified plastics and rubber vulcanizates.
• matenals typical include a chemical of interest which is predispersed in high concentrations (at least about 50 percent by weight as discussed hereinabove) in a binder, preferably a polymenc matenal, and are supplied in the form of pellets, slabs and the like.
• the polymer acts as a binder for the chemical of interest.
• the chemical of interest may, for example, be a silica filler, a colorant, a pigment, an inorganic activator, a stabilizer and/or a flame retardant tor use to produce a polymer-based product.
• the hydrophobicized particles, in the aqueous dispersion or slurry are incorporated into a binder matenal.
• a binder matenal for example a polymer in the form of a polymer solution or cement.
• the slurry of treated particles is mixed with a hydrocarbon or other non-aqueous solution of the binder.
• the solvent in which the binder is dissolved is immiscible with, or mostly immiscible with, water to form a preblend
• This binder solution (e g , polymer cement) may be made by dissolving the solid polymer in a solvent or, in the case of a solution polymer, it may be the solution resulting from the polymensation of monomers in the solvent
• the binder is a polymer It will, however, be appreciated by those of skill in the art that the binder may be a quasi- or non-polymenc matenal such as a polyethylene wax, a rosin, a fatty acid, a high molecular weight liquid and the like, or a combination of polymer and such quasi- or non-polymenc matenal.
• a quasi- or non-polymenc matenal such as a polyethylene wax, a rosin, a fatty acid, a high molecular weight liquid and the like, or a combination of polymer and such quasi- or non-polymenc matenal.
• the polymer may be an elastomer (e.g., a hydrocarbon rubber), a graft polymer or block polymer of monomers having at least one ethylenically unsaturated bond and polymenzable through this unsaturation, a plastic and the like.
• elastomer e.g., a hydrocarbon rubber
• graft polymer or block polymer of monomers having at least one ethylenically unsaturated bond and polymenzable through this unsaturation e.g., a plastic and the like.
• Elastomers are well known to those of skill in the art.
• suitable elastomers may be selected from the group compnsmg natural rubber (NR), depolymenzed NR. c ⁇ s-l,4-poly ⁇ soprene rubber (LR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), acrylomtnle-butadiene rubber (NBR), hydrogenated acrylomtnle-butadiene rubber (HNBR), butyl rubber (IIR), halogenated butyl rubber (HILR), ethylene-propylene monomer (EPM) rubber, ethylene-propylene- diene monomer (EPDM) rubber, chloroprene 1 rubber (CR), ethylene-vmyl acetate (EVM) rubber, silicone rubber (Q), epichlorohyd ⁇ n (ECO) rubber, urethane rubber (AU EU) and the like.
• NR natural rubber
• BR polybutad
• Plastics are well known to those of skill in the art.
• suitable plastics may be selected from the group compnsmg polystyrene, polyethylene, polypropylene, chlonnated polyethylene, acrylonitnle-butadiene-
• NeopreneTM styrene (N3S) polymers ethylene-vmyl-acetate (EVA) pastic, polyvinyl chlonde (PVC), plasticized polyvinyl chlonde (PVC), polymethylmethacrylate (PMMA), epichlorohyd ⁇ n (ECO) plastic and the like.
• EVA ethylene-vmyl-acetate
• PVC polyvinyl chlonde
• PVC plasticized polyvinyl chlonde
• PMMA polymethylmethacrylate
• ECO epichlorohyd ⁇ n
• a suitable solvent for preparation of the polymer binder solution is within the purview of a person skilled in the art and depends on the specific polymer to be dissolved
• suitable solvents may be selected from the group compnsmg cyclohexane, chlorobenzene, hexane, benzene, toluene, pentane and the like
• processing oil. antioxidants and other chemicals known m the art as processing aids may be added to the hydrocarbon solution pnor to mixing with the slurry, or they may be added after mixing the slurry and the polymer solution
• the viscosity of the final polymer solution is preferably such that it closely matches the viscosity of the slurry of treated particles and is generally between 1,000 and 50,000 centipoise This may depend, at least in part on the specific gravity and/or particle size of the particles dispersed in the slurry
• the temperature of the polymer solution is preferably the same as that of the slurry
• the dispersion compnses at least about 50 percent by weight particulate matenal
• the dispersion compnses from about 50 to about 95, more preferably from about 60 to about 95, even more preferably from about 70 to about 95, percent by weight paniculate matenal.
• the polymer cement and, optionally, oil and antioxidants is mixed with the slurry of treated particles until the mixture becomes homogeneous. This is confirmed by assessing the uniformity of colour and/or solids dissolution (I e., the present of a substantially single phase although a small insubstantial amount of water may separate at this stage) If not added previously, or if additional amounts are desired, oil and antioxidants may be added next and the mixing continued further until the oil and antioxidant become incorporated in the continuous phase
• Any water which separates from the preblend may be removed, discarded or recycled for slurry make-up by stopping the agitator for a suitable penod and allowing the water phase to separate in the mixing tank from which it may be removed p ⁇ or to proceeding with the next step. Agitation is preferably restarted after the water layer is removed
• antioxidants and processing oil were not previously added, or if additional amounts are desired, they may be added at this stage and sti ⁇ ed to disperse them
• the preblend is then added to water heated to a temperature equal to, or preferably higher than the boiling point of the solvent used for the polymer cement so as to remove the solvent and produce a dispersion coagulum m the form of a crumb suspended in water.
• the temperature of the water pnor to addition of the preblend is in the range of from about 50°C to about 100°C, more preferably in the range of from about 90°C and to about 95°C.
• the agitation is set sufficiently high so as to maintain the crumb in a suspended state within the water, but not so high as to cause the crumb to subdivide into particles smaller than approximately 5 mm.
• the solvent may be recovered from the coagulator by condensing the vapours
• the matenal containing the suspended crumb may then be passed through a filter screen sized so as to recover the wet composition
• the filtrate from this step may be optionally recycled for further slurry make-up.
• the wet crumb is dned such as by using forced air or fluidized bed or microwave or other drying techniques. If microwave or other drying techmques are used, it is prefe ⁇ ed to conduct these at a temperature in the range of from about 75°C to about 135°C, preferably in the range of from about 85°C to about 120°C, most preferably in the range of from about 85°C to about 105°C, until a suitably dry dispersion crumb is obtained.
• the dried crumb may be further processed according to industry and customer requirements.
• Figure 1 there is illustrated a schematic drawing of a system suitable for carrying out the process described hereinabove.
• the legend in Figure 1 is as follows:
• RI A balance-mounted portable paint pot of nominal capacity 120 litres.
• the pot is equipped with a Strahman (piston) bottom valve (Vs), an oversized air-operated motor, one 6-inch radial flow agitator (top) and one 10-inch marine impeller (bottom) on a single shaft, and an external steam coil (J) for heating.
• the lower impeller has approximately 2 inches of clearance from the bottom of RI ; the top impeller is attached at a point 9 inches higher.
• a valved chemical addition port (PI) is available on the removable lid and the pot may be purged with nitrogen through another port (Nl) when transfer of the contents is required.
• a water line may be coupled to an additional port (W).
• a portable exhaust snorkel (E) is available in the vicinity to remove fugitive chemical emissions.
• RI is used for the slurry makeup and as a vessel to carry out the above-mentioned additions of the compond of Formula I and the coupling agent (if used) to produce a slurry of hydrophobicized particles.
• Tl A nominal 500 USG glass-lined chemical reactor used for cement make-up and storage and as a mixing vessel for the slurry of treated particles and polymer cement prior to coagulation. It is equipped with a 200 rpm pneumatic drive, a marine impeller and heating jacket to speed dissolution of polymers. It has various addition ports including: M, a small manhole for introducing polymer, oil or other chemicals; P2, for solvent addition; and a nitrogen line port (N2) for pressure transfer of the contents through a large bottom drain with a valve (V2). The bottom valve is located a short distance from the tank bottom in order to reduce dead space in the piping.
• H Armoured flex hose. 2 inch diameter, for slurry and cement transfers.
• VI A 3-way valve to control the direction of flow.
• T2 A steam coagulator of nominal capacity 400 litres. It is equipped with a steam sparge port near the bottom and a connection to service water. An overflow port (P3) and overflow channel are situated close to the top to allow for product discharge. A large pipe at the top directs solvent vapours to a condenser (C). The tank is sti ⁇ ed by means of an air operated motor and an 8-inch diameter marine impeller.
• V4 A condenser for solvent recovery from coagulation. It is connected to cold process water through a valve (V4).
• T3 A solvent decanter, approx. 250 USG, for recycle solvent storage and water separation.
• a valve (V3) allows for sampling and water discharge.
• T4 A 60 litre plastic tank for fines settling.
• a binder solution ["cement”] was prepared by dissolving Buna VSL 5025-0 solution SBR (Bayer AG., 84.7 grams) and Sundex 8125 High aromatic process oil (Sun Oil Co., 40.3 grams) in 480 grams of mixed hexanes contained in a 2 Ljug.
• Antimony trioxide (Amspec Chemical Corp. Sb 2 O 3 , 500 grams) and 1 L of water were placed in a 4 L glass beaker. The solid was evenly dispersed by use of mechanical agitation. The resultant slurry was heated to 55°Celsius by means of a hot plate while being continuously agitated.
• a stabilized binder solution ["cement”] was prepared by dissolving Krynac 34.35 acrylomtnle-butadiene copolymer (NBR, Bayer AG., 200 grams), t ⁇ s(nonylphenyl)phosph ⁇ te (Polygard 2.1 grams) and Irganox 1076 (Ciba-Geigy 1.0 gram) in 1133.3 grams of toluene in a 2 L jug.
• Titanium dioxide DuPont "Ti-Pure” rutile type, 800 grams
• 1.6 L of water were placed m a 4 L glass beaker.
• the solid was evenly dispersed by use of mechanical agitation.
• the resultant slurry was warmed to 35°C by means of a hot plate while being continuously agitated
• a binder mixture was prepared by adding EP306 ethylene-propylene copolymer (Bayer AG., 87 grams), liquid paraffin (heavy mineral oil, U.S.P., 43.0 grams), isostea ⁇ c acid (Emersol 875 - Henkel, 28.45 grams), Bayfe ⁇ ox 720N (red iron oxide pigment, Bayer AG., 5.3 grams) and 493.0 grams of cyclohexane to a 2 L glass bottle and agitating until a homogeneous mixture was obtained.
• Bayfe ⁇ ox 720 red iron oxide pigment (Bayer AG., 836 25 grams), and 1673 mL of water were placed in a 6 L stainless steel beaker. The solid was evenly dispersed by use of mechanical agitation. The resultant slurry was warmed to 55°C by means of a hot plate while being continuously agitated.
• the slurry was then removed from the hot plate and allowed to cool to ambient temperature without stirnng.
• the bulk of the binder mixture was then added to the slurry
• the bottle of the binder mixture was then nnsed with 200 mL of cyclohexane and the washings were added to the slurry
• the mass was mixed vigorously with an air dnven impeller for 9 minutes at which point the phases began separating. After a total of 25 minutes of stirnng, the phases were completely separated giving a reddish sticky mass and a small amount of crystal-clear aqueous serum.
• a binder mixture was prepared by adding EP306 ethylene-propylene copolymer (Bayer AG., 87 grams), Sunthene 310 naphthemc process oil, (Sun Oil, 43.0 grams), isosteanc acid (Emersol 875 - Henkel, 29.5 grams), French process Zinc Oxide (4 23 grams) and 493 0 grams of cyclohexane to a 2 L glass bottle and agitating until a homogeneous mixture was obtained
• Example 5 Iltramanne Blue Dispersion in EP Binder Ultramanne Blue pigment (255 grams), and 1020 mL of water were placed in a 4 L glass beaker. The solid was evenly dispersed by use of mechanical agitation. The resultant slurry was heated to 80°C using a hot plate while under continuous agitation.
• Example 7 Titanium Dioxide in EP Binder Titanium Dioxide (DuPont "Ti-Pure” rutile type, 255 grams), and 510 mL of water were placed in a 4 L glass beaker. The solid was evenly dispersed by use of mechanical stirring. The resultant slurry was heated to 60°C using a hot plate while under continuous agitation.
• the contents of the coagulator vessel were allowed to cool to room temperature and were then passed through a 1 mm. screen to collect the wet product crumb.
• the coagulation serum (filtrate) was observed to be clear.
• the moist product crumb was transfe ⁇ ed to a forced-air oven thermostatted at 80°C and dried to give 326 grams of a white sticky solid.
• Banum carbonate 800 grams
• 1600 mL of water were placed in a 6 L stainless steel beaker.
• the solid was evenly dispersed by use of mechamcal agitation.
• Zinc Borate (ZB-45, The Polymer Additives Group, 800 grams), and 1200 grams of tap water were placed in a 6 L stainless steel beaker The contents were sti ⁇ ed and warmed to 50°C by means of a hot plate The mixture was then intensively sheared for 5 minutes with a Gifford-Wood homogemzer to ensure even dispersion The sides of the vessel were washed free of solids using a small quantity (100 mL) of cold water
• the EVNchlonnated paraffin solution in toluene was added in the same fashion.
• the bottle containing the EPDM was nnsed with 100 grams of cyclohexane and the washings were addded to the mi ure
• the mixture in the steel beaker was then intensively sheared with an air-operated axial impeller at 250 ⁇ m to give a thick paste. No water was observed to separate In a fume hood, a low-pressure (15 psi) steam hose was inserted into the vessel and the contents were heated with continuous stirnng in order to remove the solvents. Once the odor of solvent was absent, the steam was removed and the matenal was allwed to cool. The water phase from the coagulation was crystal clear.
• the solid crumb was removed by filtenng through a 1 mm. screen. It was then transfe ⁇ ed to a forced-air oven thermostatted at 90°C and dned for 6 hours to yield 952 grams of the product in the form of 1-2 mm. easily-deformable white spheroids.

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• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Silicon Compounds (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)
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• 1998
  • 1998-11-20 CA CA002254330A patent/CA2254330A1/en not_active Abandoned
• 1999
  • 1999-11-19 WO PCT/CA1999/001094 patent/WO2000031178A1/en not_active Application Discontinuation
  • 1999-11-19 BR BR9915528-1A patent/BR9915528A/pt not_active Application Discontinuation
  • 1999-11-19 JP JP2000584000A patent/JP2002530502A/ja active Pending
  • 1999-11-19 AU AU11452/00A patent/AU1145200A/en not_active Abandoned
  • 1999-11-19 KR KR1020017006300A patent/KR20010089476A/ko not_active Application Discontinuation
  • 1999-11-19 EP EP99972659A patent/EP1131379A1/en not_active Withdrawn

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