EP1155077A1 - Procede de traitement de particules et utilisation de ces particules dans des dispersions - Google Patents

Procede de traitement de particules et utilisation de ces particules dans des dispersions

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Publication number
EP1155077A1
EP1155077A1 EP99972657A EP99972657A EP1155077A1 EP 1155077 A1 EP1155077 A1 EP 1155077A1 EP 99972657 A EP99972657 A EP 99972657A EP 99972657 A EP99972657 A EP 99972657A EP 1155077 A1 EP1155077 A1 EP 1155077A1
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EP
European Patent Office
Prior art keywords
group
process defined
formula
rubber
particles
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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.)
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EP99972657A
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German (de)
English (en)
Inventor
Ahti August Koski
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Bayer Inc
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Bayer Inc
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Publication of EP1155077A1 publication Critical patent/EP1155077A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • 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
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to treating particles, particularly inorganic water-insoluble compounds.
  • the treated particles are useful particularly, but not exclusively in the compounding of polymers, especially rubbers and plastics.
  • Examples of known coupling agents include those described in United States patent 4,704,414, published European patent application 0,670,347 A 1 and published German patent application 4435311 A 1.
  • One suitable coupling agent is a mixture of bis[3-(triethoxy- silyl)propyl]monosulfane, bis[3-(triethoxysilyl)propyl]disulfane, bis[3- (triethoxysilyl)propyl]trisulfane and bis[3-(triethoxysilyl)propyl]tetrasulfane .and higher sulfane homologues - for example, coupling agents available under the trade names Si-69 (average sulfane 3.5) and Silquest A-1589 or Si-75
  • Illustrative examples of other coupling agents include the following: bis[2-(trimethoxysilyl)ethyl]tetrasulfane, bis[2-(triethoxysilyl)ethyl]trisulfane, bis[3-(trimethoxysilyl)propyl]disulfane, 3-mercaptopropyltrimethoxysilane, 3- mercaptopropylmethyldiethoxysilane, 3 -mercaptoethylpropyl- ethoxymethoxysilane, l,3-bis(3-acryloxypropyl)tetramethoxydisiloxane, acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy- silane, allyltrimethoxysilane, diallyldiethoxysilane, 5-(bicyclo- heptenyl)triethoxysilane, 5-(bicycloheptenyl)methyl
  • R 1 is a saturated or unsaturated, branched or unbranched, substituted or unsubstituted hydrocarbon group that is at least trivalent and has from 2 to 20 carbon atoms, provided that there are at least two carbon-sulphur bonds
  • R 2 and R 3 independently of each other, are saturated or unsaturated, branched or unbranched, substituted or unsubstituted hydrocarbon groups with 1 to 20 carbon atoms, halogen, hydroxy or hydrogen, n is 1 to 3, m is 1 to 1000, p is 1 to 5, q is 1 to 3 and x is 1 to 8.
  • R 2 , m and x have the meanings given above.
  • R 1 , R 2 and R 3 are the same or different and are C, profession 8 alkyl, C j.8 alkoxy, phenyl or phenoxy, provided that at least one of R 1 , R 2 and R 3 is an alkoxy or phenoxy group.
  • X 1 and X 2 are the same or different and are divalent linear or branched, optionally unsaturated C,., 2 alkyl groups
  • Y is a di-, tri- or tetravalent linear, branched or cyclic C, .lg alkyl group that is optionally unsaturated and is optionally substituted by C 6 _ 12 aryl, C [.g alkoxy or hydroxy groups and which can be interrupted by oxygen, sulphur or nitrogen atoms or aromatic C 6 . 12 aryl groups, or Y is a C 6 _ ]2 aryl or heteroaryl group, m is an integer from 1 to 20, n is an integer from 1 to 6 and x is an integer from 1 to 6.
  • pre-treated silica material which has been produced by reacting untreated silica with a coupling agent.
  • Such materials are available commercially under the tradenames Ciptane (PPG) and Coupsil (Degussa AG).
  • United States patent 5,834,536 a method to produce coated particles by means of a so-called “in-situ process" wherein the final product of the reaction of a coupling agent and particulate matter is generated without the need for the addition of the coupling agent to the particles, per se.
  • the process is conducted in an aqueous slurry.
  • so-produced particles must be removed from the slurry and dried prior to admixing further with a polymer (and ancillary ingredients such as oils, vulcanizing agents and accelerators) to make a vulcanizable compound.
  • the admixing of the treated particles with rubber as taught in United States patent 5,834,536 is by mechanical mixing. This mixing may be 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 of the treated particles is achieved.
  • the present invention provides a process for treating particles, the process comprising the step of: contacting a particulate material having Formula II:
  • P is a particle
  • R is a hydrocarbylsiloxyl moiety
  • X is an anion, with a sulfur-containing compound to produce a particulate material having one or more of the formulae:
  • n is an integer from 1 to 10.
  • the present invention provides a process for treating particles, the process comprising the steps of: (i) contacting a particulate material with a compound of Formula I:
  • 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
  • X is an anion
  • the present inventor has developed a novel approach for introducing the functionality of a coupling agent into a particulate material. Specifically, the present approach does not necessitate the production of a coupling agent, per se. Rather, the approach taught herein relates to in situ production of the functional moiety of the coupling agent on the particulate material (i.e., as opposed to reaction of the pre-manufactured coupling agent and the particulate material).
  • One of the advantages of this approach is that relatively low cost chemicals can be used to produce the functional moiety of the coupling agent compared to the cost of the independently produced coupling agent, per se.
  • 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 treated 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.
  • a dispersion comprising the polymer and the treated particles.
  • the treated particles may be incorporated into a suspension without being isolated (i.e., separated from the suspension or slurry, and subsequently dried).
  • a dispersion comprising a polymer and a treated particulate material (such as metal oxides and the like as will be discussed in more detail hereinbelow), the dispersion having been prepared from a polymer solution without the need to utilize conventional coupling agents, per se.
  • the treated particulate material may be separated from the suspension or slurry, and subsequently dried for later use (i.e., before addition of the polymer solution).
  • concentration i.e., the additive(s) to be used for compounding purposes
  • 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.
  • masterbatch when used in the context of the present invention, is 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 minor component of the composition - i.e., the composition comprises less than about 50 percent by weight particulate material.
  • the composition comprises from about 5 to about 50, more preferably from about 20 to about 45, even more preferably from about 30 to about 40, percent by weight particulate material.
  • Figure 1 illustrates an example of the use of a conventional coupling agent
  • Figure 2 illustrates an example of an embodiment of the present process.
  • the coupling agent illustrated is a mixture of bis[3-(triethoxy- silyl)propyl]monosulfane, bis[3-(triethoxysilyl)propyl]disulfane, bis[3-
  • the alkoxy groups on the other end of the coupling agent react with the pendant hydroxyl groups on a particle to form a series of siloxyl linkages to the second particle.
  • the first and second particles are thus coupled to one another.
  • opposed ends of the coupling agent it is possible for opposed ends of the coupling agent to form siloxyl linkages with the same silica particle, and indeed this is usually the case with particles that are aggregates; i.e. those particles that are much larger than molecular dimensions.
  • the present process comprises the step of: contacting a particulate material having Formula II:
  • P is a particle
  • R is a hydrocarbylsiloxyl moiety
  • X is an anion (see Figure 2 for further detail on P, R and X), with a sulfur-containing compound to produce a particulate material having one or more of the formulae:
  • n is an integer from 1 to 10, preferably from 2 to 5.
  • silica as the particle having surface hydroxyl groups since this is the preferred particulate material, but it should be appreciated that the invention applies to the use of other such minerals, and the description understood accordingly.
  • carbon black may also be used.
  • carbon-silica dual phase fillers may also be used (e.g., Ecoblack® CRX-2000).
  • 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 in which the chemical formula contains an oxygen atom, more preferably such compounds which the formula also contains a metal atom. More than one metal atom may be present in the chemical formula.
  • suitable groups of useful oxygen atom compounds may be selected from the group comprising oxides, hydroxides, borates, sulfates, carbonates, silicates, phosphates, chromates and the like.
  • Non-limiting examples of suitable oxygen atom and metal atom containing compounds may be selected from the group comprising silicon dioxide (silica), titanium oxide (titania, both rutile and anatase forms), ferric oxide, hydrated ferric oxide, ferrous oxide, antimony oxide, barium carbonate, zinc oxide, zinc borate, lead oxide (including red lead oxide), dibasic lead phosphite, lead silicate, tribasic lead sulfate and mixtures thereof.
  • Other suitable metal atom- and oxygen atom- containing compounds especially those which are water insoluble or only slightly soluble in water, will be readily apparent to those of skill in the art based on the foregoing discussion.
  • a particularly preferred application of the present invention is to render hydrophobic colorant or pigment particles which are typically used in the plastics industry.
  • suitable such particles 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 preferred particulate material for use herein is silica.
  • the particles of Formula II are selected from the group comprising:
  • R 4 is a divalent group that is resistant to hydrolysis at the Si-R 4 bond
  • R a and R b are the same or different and each is selected from the group comprising hydroxyl, a hydrolysable group, C 0 alkyl, C 2.40 mono- or C 3.40 diunsaturated alkenyl and C 6.40 aromatic; w is an integer in range of 1 to 10 6 or more. As will be appreciated by those of skill in the art the value of w depends, at least in part, on the size of the particle and the number of pendent reactive moieties.
  • R 4 has the formula:
  • n, o and p are all 0.
  • each of n, o, p and k are 0, and m is 3, i.e., R 4 is -CH 2 CH 2 CH 2 -.
  • X is selected from the group comprising acetate, chloride, bromide, iodide and sulphate, more preferably from the group comprising chloride and bromide.
  • the present process involves the use of a sulfur-containing compound.
  • sulfur-containing compound is intended to encompass any compound capable of reaction with the particles of Formula II to leave the sulfane residue in the particulate material having the Formula III, wherein n is an integer of from 1 to 10.
  • the sulfur- containing compound has the formula M 2+y S n or M(SH) y , where M is ammonium or a metal, y is an integer which specifies the valency of M and n is an integer of from 1 to 10.
  • the sulfur-containing compound is selected from the group comprising polysulfides, hydrosulfides and mixtures thereof. More preferably, the polysulfides comprise ammonium polysulfide compounds and alkali metal polysulfide compounds.
  • suitable alkali metal polysulfides may be selected from the group comprising Na j S., K 2 S n and mixtures thereof, wherein n is as defined above.
  • the most preferred sulfur-containing compound for use in the present process is Na j S. wherein n is as defined above. It will be clearly apparent to those of skill in the art that mixtures of the same type of sulfur-containing compound may be used.
  • a mixture comprising two or more of Na ⁇ , Na ⁇ , Na ⁇ , Na ⁇ , etc. may be used to provide a desired overall average sulfane content - e.g., in the range of 2-5.
  • Suitable sulfur-containing compounds include ammonium hydrosulfide (NH 4 SH) and alkali metal hydrosulfide compounds (M(SH) y ).
  • NH 4 SH ammonium hydrosulfide
  • M(SH) y alkali metal hydrosulfide compounds
  • suitable alkali metal hydrosulfide compounds may be selected from the group comprising NaSH, KSH and mixtures thereof. The use of these hydrogen sulfide compounds will result in production of a treated particulate material having the general formula
  • the sulfur-containing compound in the form of an aqueous solution thereof.
  • the sulfur-containing compound is present in a concentration in range of from about 20% to about 50%, more preferably from about 25% to about 40%, most preferably from about 30% to about 40%, by weight of the aqueous solvent.
  • Organic solvents for the sulfur- containing compounds may be used although these are less preferred.
  • the treatment is carried out in an aqueous dispersion or slurry of the particles.
  • the precise make up of the slurry is not particularly restricted provided that it is a mobile suspension and remains so during the treatment. Practically, it is preferred that the slurry contain up to about 60%o by weight, more preferably up to about 50% by weight, of particles to be treated.
  • the particles to be treated While the physical nature of the particles to be treated is not particularly restricted, 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 0.1 ⁇ m to about 50 ⁇ m, most preferably from about 1 ⁇ m to about 25 ⁇ m.
  • the treatment is carried out in an aqueous dispersion or slurry and the concentration of the aqueous dispersion or slurry of silica particles may be between 1 and 30 percent by weight of silica in water, preferably between 5 and 25 percent by weight of silica in water and most preferably between 8 and 22 percent by weight of silica in water.
  • Dried amorphous silica suitable for use in accordance with the invention may have a mean agglomerate particle size between 0.1 and 100 microns, preferably between 0.1 and 50 microns and most preferably between 1 and 25 microns. It is preferred that less than 10 percent by volume of the agglomerate particles are below 5 microns or over 50 microns in size.
  • a suitable amorphous dried silica moreover has a BET surface area, measured in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 and 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601, of between 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight.
  • BET surface area measured in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 and 450 square meters per gram and a DBP absorption, as measured in accordance with DIN 53601, of between 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight.
  • filter cake it may be made by any known means such as described in Ullmann's Encyclopedia of Industrial Chemical Nol A23 pages 642-643, VCH Publishers, ⁇ 1993.
  • the filter cake has a preferred solids content of between 5 and 30 percent by weight, most preferably between 15 and 25 percent by weight, and it may be redispersed in water in accordance with the present process to give a silica concentration of between 5 and 20 percent by weight and most preferably between 8 and 12 percent by weight. It is preferred to use a filter cake. If a never-filtered slurry prepared from the known reaction of a solution of alkali metal silicate with either mineral acid or carbon dioxide is used, it is preferred that the solids content of the never-filtered slurry be between 1 and 30, more preferably between 5 and 10, percent by weight of silica.
  • the slurry temperature may be between 0° and 100°C if the process is conducted at atmospheric pressure or between 0° and 135 °C if the operation is conducted in a pressure vessel. Most preferably, the process is conducted at atmospheric pressure in which case the preferred temperature is between 30° and 95 °C and most preferably between 45 ° and 90°C.
  • the selection of atmospheric pressure or a pressure vessel is within the purview of a person skilled in the art having regard to a number of factors, including temperature and the respective volatilities of the specific reactants chosen for the process.
  • the reaction between the particles of Formula II and the sulfur-containing compound is conducted for a period sufficient to achieve a chemical reaction between the two reactants.
  • the particles of Formula II are prepared by a process comprising the step of: contacting a particulate material with a compound of Formula I:
  • R 1 , R 2 and R 3 are hydroxyl or hydrolysable groups; and X and R 4 are as defined above.
  • 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. If necessary, 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 like.
  • Suitable groups R 1 include hydroxyl 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 3 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-.
  • Suitable hydrolysable groups include phenoxy, acetoxy, chloro, bromo, iodo, ONa, OLi, OK or amino or mono- or dialkylamino, wherein the alkyl group(s) have 1 to 30 carbon atoms.
  • 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. Preferably, only one or two of R 1 , R 2 and R 3 is hydroxyl or ONa, OLi or OK.
  • groups R 2 and R 3 that are not hydrolysable include C M0 alkyl, C 2 . 40 mono- or C 3 . 40 diunsaturated alkenyl and C 6.40 aromatic, preferably C,_ 10 alkyl, C 2 . 10 mono- or diunsaturated alkenyl and phenyl. It is preferred that R 1 , 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 X-R 4 -Si is of the formula:
  • k, m, n, o and p are all whole numbers.
  • the order of the moieties between X and Si is not particularly restricted other than neither X or O should be directly bound to Si, nor should there exist the bond X-O.
  • 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, with 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, m is 1 or greater or the sum of k, m and n is 1 or greater, i.e.
  • the Si atom is linked directly to a carbon atom. There should be no hydrolysable bond between the Si and X atoms.
  • m is 3 and 1
  • n, o and p are all 0, i.e., R 4 is -CH 2 CH 2 CH 2 -.
  • R 4 is -CH 2 CH 2 CH 2 -.
  • the mechanism of the present process can be illustrated with reference to Figure 2.
  • the particulate material being treated is silica
  • R 1 , R 2 and R 3 are each -OCH 3
  • R 4 is -CH 2 CH 2 CH 2 -
  • X is -Cl
  • the sulfur-containing compound is Na j S,,.
  • 3-chloropropyltrimethoxysilane is reacted with the untreated silica particle to produce the illustrated treated particle having a chloropropylsiloxyl moiety (this an example of the particle of Formula II).
  • two such treated particles are reacted with Na ⁇ ,, to produce the illustrated coupled particulate material.
  • the sulfur-containing compound, Na ⁇ S- it is possible for the sulfur-containing compound, Na ⁇ S-, to react with a singe silica particle.
  • R a , 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; and 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 2.40 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, .18 alkyl; C 2.18 mono-, di- or tri- unsaturated alkenyl; phenyl; a group of formula:
  • R 10 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 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 oft and v does not exceed 6, preferably the sum oft and v is 4.
  • the above aminohydrocarbonsilane moiety can be formed on the surface of the particles in situ using the approach described in copending Canadian patent application 2,254,315 (Bayer Ref: POS-1061), filed on November 20, 1998. If the particle has an aminohydrocarbonsilane moiety formed thereon, it is preferred that the amount of sulfur-containing compound used in the present process is less than the stoichiometric amount necessary to react with substantially all of the pendant reactive groups on the surface of the particles.
  • the product of the present process is further reacted with a compound of Formula III: R 15
  • R 15 , R 16 and R 17 have the same definitions as R 1 , R 2 and R 3 in Formula I hereinabove;
  • R 12 is selected from the group comprising a C 8.40 alkyl group or a C 8.40 mono-, di- or tri -unsaturated alkenyl group, either of which can be interrupted by one or more aryl groups, preferably phenyl groups; a group of formula:
  • R 18 is a divalent group resistant to hydrolysis at the Si-R 18 bond
  • R 19 is selected from the group comprising hydrogen, a C 0 alkyl group, a C 2 . 40 mono-, C 3 .
  • R 20 mono-, di- or tri-unsaturated alkenyl group; and R 20 may be any of the groups defined for R 19 , with the provisos that R 19 and R 20 do not have a tertiary carbon atom adjacent to the nitrogen atom and that at least one of R 19 and R 20 has a carbon chain at least 8 carbon atoms in length uninterrupted by any hetero atoms.
  • R 18 is a C,-C 40 saturated or unsaturated group (e.g., alkenyl, aryl, cycloalkyl and the like).
  • the particulate filler material is in the form of an aqueous slurry or a dispersion, and the compound of Formula III is added to the slurry or dispersion under intense mixing.
  • the possible and preferred values for R 15 , R 16 and R ⁇ are the same as the possible and preferred values for R 1 , R 2 and R 3 that are discussed above in relation to Formula I.
  • R 12 is an amino group of formula -R 18 -NR 19 R 20
  • preferred values for R 18 are such that N-R 18 -Si includes groups of the formula:
  • k is 0 or 1
  • m is 0 to 20 inclusive
  • n is 0, 1 or 2
  • o is 0 or 1
  • p is 0 to 20 inclusive, provided that the sum of k, m, n, o and p is at least 1 and not greater than 20, and further provided that if o is 1 , p is also 1 or greater, and the sum of k, m and n is 1 or greater.
  • the order of the moieties between N and Si is not particularly restricted other than neither N or O should be directly bound to Si and there should be no N-O bond. There should be no hydrolysable group between the silicon and nitrogen atoms.
  • k, n, o and p are all 0 and m is 3, i.e. R 18 is -CH 2 CH 2 CH 2 -.
  • R 12 may be a moiety containing at least one primary, secondary, or tertiary amine nitrogen.
  • amino group bonded to R 18 - is given by the formula -NR 19 R 20 .
  • R 19 may be a H or a C, .40 alkyl group or a C 2.40 mono-, di- or tri-unsaturated alkenyl group.
  • R 19 may also be a C ⁇ Q alkyl- substituted or C 2.20 alkenyl-substituted aromatic group.
  • the aromatic group may be, for example, the phenylene group -(C 6 H 4 )-, the biphenylene group -(C 6 H 4 )-(C 6 H 4 )-, the -(C 6 H 4 )-O-(C 6 H 4 )- group, or the naphthylene group -(C 10 H 6 )-.
  • R 20 may be one of the same groups as R 19 with the further proviso that at least one of R 19 and R 20 must contain a continuous carbon chain of at least 8 carbons in length, uninterrupted by any heteroatoms.
  • R 19 and R 20 are other than hydrogen, the carbon atom attached to the nitrogen atom is not tertiary.
  • the carbon atom attached to the nitrogen atom is primary, i.e., -CH 2 -.
  • R 19 is a mono-unsaturated alkenyl group of 12-20 carbons in length and most preferable that R 19 is a monounsaturated alkenyl group of 16 to 18 carbons in length. It is most preferable also that R 20 is H.
  • R 12 may be a moiety which contains a mineral acid salt or a quaternary ammonium salt of an amine.
  • R 12 may thus be described by the extended formula -R 18 -NR 19 R 20 -R 21 X wherein -R 18 -, R 19 and R 20 are as previously defined and R 21 may be a H, or a C ⁇ alkyl or C 2.40 mono-, di- or tri-unsaturated alkenyl group and X is an anion, preferably Cl or Br, although sulphate can be used.
  • R 19 and R 20 must contain a continuous carbon chain of at least 8 carbons in length, uninterrupted by any heteroatom. It is preferred to use an amine salt where R 19 is a mono- or di -unsaturated alkenyl group of 12-20 carbons in length and most preferably that R 19 is a mono- or di-unsaturated alkenyl group of 16 to 18 carbons in length. It is most preferable also that R 20 is H and that R 21 is H and X is chlorine.
  • the preferred hydrophobicizing agent of Formula III is N-oleyl-N-(3-trimethoxysilyl)propyl ammonium chloride.
  • the amount of the hydrophobic compound of Formula III to add is generally between 0.5 and 20 percent by weight of the weight of the particles (preferably mineral particles such as silica) in the slurry (dry basis), and is inversely proportional to the particle size of the silica particles.
  • the compound may be added to the slurry 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 liquified 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 preferred to use a solvent. Suitable solvents are alcohols containing 1 to 5 carbon atoms and most preferably those containing 1 to 3 carbon atoms, that is to say methanol, ethanol, n-propanol or isopropanol.
  • 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 in the solvent may be from 10 to 90 percent by weight and most preferably between 25 and 75 percent by weight and most preferably 50 percent by weight.
  • the solution is prepared and added to the slurry at a temperature between a lower limit of 0°C and an upper limit which is the lower of at least 10°C below the boiling point of the solvent and 95 °C.
  • the equivalent balance (EB) should be calculated to determine how much, if any, mineral acid or alkali metal hydroxide (or solutions thereof) to add.
  • the group contribution of each of R 15 , R 16 and R 17 is generally zero for all groups except as follows: if the group is
  • the negative sign in front of the sum indicates adjustment with alkali metal hydroxide is required.
  • the number of equivalents of alkali required is given by the equivalent balance (EB) which includes the absolute value of the sum of the group contributions ( ⁇ ) as a scaling factor.
  • the preferred technique according to the invention is to dissolve the alkali hydroxide or mineral acid in water so as to obtain a concentration between 5 and 25% by weight and most preferably between 5 and 10% by weight prior to adding the solution to the slurry.
  • the temperature of the solution may be from 0° to 100° C under atmospheric pressure, or if a pressure vessel is used for preparation of the solution, it may be from 0° to 130°C. It is preferred that the temperature of the solution be within 10°C of the solution of the slurry.
  • the dispersion of the solution in the slurry is effected by mixing.
  • the product of this preferred embodiment of the present process described thus far relates an aqueous slurry or dispersion of hydrophobicized particles (i.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 dried.
  • the hydrophobicized particles may be used as a compounding agent in a multitude of materials including, but not limited to, the following: polymers, alkyd paints, toners such as those used in photocopiers, modified plastics and rubber vulcanizates.
  • the hydrophobicized particles, in the aqueous dispersion or slurry is incorporated into a polymer, for example an elastomer to form a rubber masterbatch.
  • the slurry is mixed with a hydrocarbon or other solution of the elastomer.
  • the solvent in which the elastomer is dissolved is immiscible with, or mostly immiscible with, water to form a preblend.
  • This elastomer solution may be made by dissolving the solid elastomer in a solvent, or it may be the solution resulting from the polymerisation of monomers in the solvent.
  • the elastomer may be a hydrocarbon rubber, a graft polymer or block polymer of monomers having at least one ethylenically unsaturated bond and polymerizable through this unsaturation.
  • suitable polymers include, but are not limited to butyl rubber (IIR), halogenated butyl rubber (HIIR) , cis-l,4-poyisoprene rubber (IR), ethylene-propylene-diene monomer (EPDM) rubber, ethylene-propylene monomer (EPM) rubber, styrene-butadiene rubber (SBR), polybutadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), HSRE, natural rubber (NR), polystyrene (PS), chloroprene 1 rubber (CR), ethylene-vinyl acetate (EVM) rubber, epichlorohydrin (ECO) rubber, chlorinated
  • Suitable solvents include but are not limited to cyclohexane, hexane, benzene, toluene and pentane.
  • processing oil and antioxidants may be added to the hydrocarbon solution prior to mixing with the slurry, or they may be added after mixing the slurry and the elastomer solution.
  • the viscosity of the final elastomer solution sometimes referred to as an elastomer cement, containing the optional ingredients is preferably such that it closely matches the viscosity of the silica slurry and is generally between 1,000 and 50,000 centipoise.
  • the temperature of the elastomer solution is preferably the same as that of the slurry and the amount of cement that is added is such that the final masterbatch may contain from 5 to 250 parts of silica per hundred parts of elastomer, preferably from 35 to 100 parts of silica per hundred parts of elastomer, most preferably from 60 to 80 parts of silica per hundred parts of elastomer.
  • the elastomer cement and, optionally, oil and antioxidants is mixed with the silica slurry until the mixture becomes homogeneous and the milky colour of the silica slurry disappears to form a preblend. A small amount of water may separate at this stage.
  • 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 silica slurry make-up by stopping the agitator for a suitable period and allowing the water phase to accumulate in the bottom of the mixing tank from which it may be drained prior 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 stirring continued until the preblend is again homogeneous.
  • 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 elastomer cement so as to remove the solvent and produce a masterbatch coagulum in the form of a crumb suspended in water.
  • the preferable temperature of the water prior to addition of the preblend is between 50° and 100°C, most preferably between 90° and 95 °C, and the preblend is added at a rate so as to maintain a so-fixed or reasonably so-fixed water temperature throughout the coagulation.
  • 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 millimeters.
  • the solvent may be recovered from the coagulator by recondensing the vapours.
  • the material containing the suspended crumb is passed through a filter screen sized so as to recover the wet masterbatch.
  • the material passing through the screen may be optionally recycled for further silica slurry makeup.
  • the wet crumb is dried such as by using forced air or fluidized bed or microwave drying techniques at a temperature between about 75 ° and about 135°C, preferably between about 85° and about 120°C, most preferably between about 85 ° and about 105°C, until a suitably dry masterbatch crumb is obtained.
  • the dried crumb may be further processed according to industry and customer requirements.
  • Another advantageous application of the hydrophobicized particles is in the production of predispersions or concentrates of polymer compounding chemicals. These materials 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 polymeric material, 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 for use to produce a polymer-based product.
  • the hydrophobicized particles, in the aqueous dispersion or slurry are incorporated into a binder material, for example a polymer in the form of a polymer solution or cement.
  • a binder material 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
  • This binder solution 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 polymerisation 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-polymeric material 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-polymeric material.
  • the binder may be a quasi- or non-polymeric material 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-polymeric material.
  • 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 polymerizable 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 polymerizable 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 comprising natural rubber (NR), depolymerized NR, cis-l,4-polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile- butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), butyl rubber (IIR), halogenated butyl rubber (HIIR), ethylene- propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, chloroprene rubber (CR), ethylene-vinyl acetate (ENM) rubber, silicone rubber (Q), epichlorohydrin (ECO) rubber, urethane rubber (AU EU) and the like.
  • NR natural rubber
  • IR cis-l,4-polyisoprene rubber
  • Plastics are well known to those of skill in the art. ⁇ on-limiting examples of suitable plastics may be selected from the group comprising polystyrene, polyethylene, polypropylene, chlorinated polyethylene, acrylonitrile-butadiene-styrene (ABS) polymers, ethylene-vinyl-acetate (ENA) pastic, polyvinyl chloride (PNC), plasticized polyvinyl chloride (PNC), polymethylmethacrylate (PMMA), epichlorohydrin (ECO) plastic and the like.
  • ABS acrylonitrile-butadiene-styrene
  • EVA ethylene-vinyl-acetate
  • PNC polyvinyl chloride
  • PNC plasticized polyvinyl chloride
  • PMMA polymethylmethacrylate
  • ECO epichlorohydrin
  • 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 comprising cyclohexane, chlorobenzene, hexane, benzene, toluene, pentane and the like.
  • processing oil, antioxidants and other chemicals known in the art as processing aids may be added to the hydrocarbon solution prior 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 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.
  • 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).
  • 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 period and allowing the water phase to separate in the mixing tank from which it may be removed prior 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 stirred 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 in the form of a crumb suspended in water.
  • the temperature of the water prior 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 material 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 dried such as by using forced air or fluidized bed or microwave or other drying techniques. If microwave or other drying techniques are used, it is preferred 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.
  • Buna®NSL 5025-1 oil extended solution SBR cement in hexane Vulcanox® 4020
  • 3 -Chloropropyltrimethoxy silane (30.1 gm, 152 millimoles) was added to the vortex dropwise over 5 minutes and stirring was continued for 30 minutes.
  • the above slurry was then heated to 60 °C while agitation was maintained.
  • Sodium tetrasulfide solution (28.5 grams of 34 wt% Na ⁇ in water) was then added over 15 minutes. The colour gradually changed from a dark yellow through greenish-grey to a Kelly green.
  • the slurry was stirred for an additional 5 hours while the temperature was held at between 60-62 °C. When the slurry became too thick for good agitation, additional water was added as required to enable circulation to be maintained.
  • N-oleyl-N-(trimethoxysilyl) propyl ammonium chloride as 46.0 grams of a 50 wt% solution in methanol was added into the vortex in 1 mL aliquots over 5 minutes. A marked thickening was noted.
  • Sodium hydroxide 2.07 grams was dissolved in 25 mL of water and shaken to dissolve. This solution was added to the vortex in 1 mL aliquots over 1 minute. The sides of the beaker were then washed down with a small amount of water and the heater and stirrer were turned off.
  • the cement When cool, the cement was quantitatively transferred to a 2.5 gallon plastic bucket in the fume hood by using a spatula and a small amount ( ⁇ 50 mL) of water from a wash bottle.
  • Oil extended solution styrene-butadiene copolymer cement (3188 grams of 20 wt% Buna® VSL 5025-1 in cyclohexane) and Vulcanox® 4020 antioxidant (5.0 grams) were then added and the mixture was stirred manually with a spatula to homogenize.
  • Example 1 The ingredients and conditions of Example 1 were repeated with the exception that 3188 grams of a 20 wt% solution of Buna® CB24 polybutadiene rubber in hexane and 191 grams of Sundex® 8125 were added to the treated slurry in place of the oil extended solution styrene-butadiene copolymer cement. Product yield was 1306 grams, dry basis.
  • the coagulation serum was then cooled and passed through Whatman #41 filter paper in order to pick up any unincorporated silica.
  • the filter paper was then dried at 85°C. A total of 6.1 grams of silica was recovered.
  • the filler incorporation efficiency was calculated as 98.8%.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne des particules pouvant être rendues hydrophobes par formation in situ d'une fraction contenant des groupes amino et silanes. L'invention est particulièrement utile pour un traitement de particules inorganiques hydrophiles visant à déterminer la fonctionnalité d'un agent de pontage, sans nécessité de procéder à une réaction des particules inorganiques hydrophiles avec un agent de pontage per se. Les particules traités peuvent être utilisées, par exemple, comme agent de composition pour des polymères.
EP99972657A 1998-11-20 1999-11-22 Procede de traitement de particules et utilisation de ces particules dans des dispersions Withdrawn EP1155077A1 (fr)

Applications Claiming Priority (3)

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CA2254315 1998-11-20
CA002254315A CA2254315A1 (fr) 1998-11-20 1998-11-20 Procede pour traiter des particules et utilisation de celles-ci dans des dispersions
PCT/CA1999/001097 WO2000031175A1 (fr) 1998-11-20 1999-11-22 Procede de traitement de particules et utilisation de ces particules dans des dispersions

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EP1155077A1 true EP1155077A1 (fr) 2001-11-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019219819A2 (fr) 2018-05-18 2019-11-21 Gustav Klauke Gmbh Outillage avec un vérin hydraulique ainsi qu'outillage manuel, comme une pince ou une presse

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US6837923B2 (en) 2003-05-07 2005-01-04 David Crotty Polytetrafluoroethylene dispersion for electroless nickel plating applications

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EP0176062A3 (fr) * 1984-09-27 1987-07-15 Dow Corning Corporation Agents d'accrochage à base de silanes applicables à température élevée et procédé d'application
DE19529916A1 (de) * 1995-08-16 1997-02-20 Bayer Ag Verfahren zur Herstellung von immobilisierten polysulfidischen Silanen und deren Verwendung zur Herstellung von Kautschukmischungen und -vulkanisaten
CA2205790A1 (fr) * 1997-05-22 1998-11-22 Ahti August Koski Methode pour preparer des aminosilanes; nouveaux aminosilanes ainsi obtenus
CA2205789A1 (fr) * 1997-05-22 1998-11-22 Bayer Inc. Procede pour rendre des particules hydrophobes; leur emploi comme charges dans des melanges maitres polymeriques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019219819A2 (fr) 2018-05-18 2019-11-21 Gustav Klauke Gmbh Outillage avec un vérin hydraulique ainsi qu'outillage manuel, comme une pince ou une presse

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BR9915530A (pt) 2001-07-31
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JP2002530500A (ja) 2002-09-17
AU1145500A (en) 2000-06-13
TW401316B (en) 2000-08-11

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