US20050197443A1 - Microgels in non-crosslinkable organic media - Google Patents

Microgels in non-crosslinkable organic media Download PDF

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US20050197443A1
US20050197443A1 US10/947,876 US94787604A US2005197443A1 US 20050197443 A1 US20050197443 A1 US 20050197443A1 US 94787604 A US94787604 A US 94787604A US 2005197443 A1 US2005197443 A1 US 2005197443A1
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microgel
composition according
microgels
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Torsten Ziser
Thomas Fruh
Patrick Galda
Werner Obrecht
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Rhein Chemie Rheinau GmbH
Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a composition containing a non-crosslinkable medium and at least one microgel, to a process for its preparation, to uses of the compositions, and to microgel-containing polymers, rubbers, lubricants, coatings, etc. produced therefrom.
  • rubber gels also modified rubber gels, in blends with a very wide variety of rubbers in order, for example, to improve the rolling resistance in the production of motor vehicle tires (see e.g. DE 42 20 563, GB-PS 10 78 400, EP 405 216 and EP 854 171).
  • the rubber gels are always incorporated into solid matrices.
  • Various dispersing apparatuses such as bead mills, three-roller mills or homogenizers can be used for the dispersion.
  • the use of homogenizers and the operation thereof is described in the Marketing Bulletin of APV Homogenizer Group—“High-pressure homogenizers processes, product and applications” by William D. Pandolfe and Peder Baekgaard, principally for the homogenization of emulsions.
  • US 2003/0,088,036 A1 discloses reinforced heat-curing resin compositions, the preparation of which likewise comprises mixing radiation-crosslinked microgel particles with heat-curing pre-polymers (see also EP 1 262 510 A1).
  • microgels in liquid organic media having a specific viscosity using a homogenizer, for example.
  • the division of the microgels in the organic medium to the primary particle range is, for example, a requirement for utilizing the nano properties of the microgels in applications of any kind, for example in incorporation into plastics.
  • the liquid compositions according to the present invention containing the specific microgels are able to open up a large number of novel applications for microgels which were not accessible with the microgels themselves.
  • compositions according to the present invention owing to the fine distributions that are achievable, can be incorporated into plastics, for example, completely new properties being obtained as a result.
  • the microgel-containing compositions according to the present invention can be used in a large number of fields, such as, for example, in elastomeric PU systems (cold-casting systems and hot-casting systems), in coating compositions or as lubricant additives.
  • materials that are incompatible per se form a homogeneous distribution which remains stable even on prolonged storage (6 months).
  • Microgel-containing compositions have been found for which very different rheological behavior has been demonstrated.
  • a very strong intrinsic viscosity or thixotropy has surprisingly been found, as well as flow behavior similar to that of Newtonian fluids. This can be used to control the flow behavior, as well as other properties, of any desired liquid compositions in a targeted manner by means of microgels.
  • plastics produced from the microgel-containing compositions according to the present invention have been found to have improved tear strength.
  • the present invention accordingly provides a composition containing at least one non-crosslinkable organic medium (A) which has a viscosity of less than 100 mPas at a temperature of 120° C., and at least one microgel (B).
  • A non-crosslinkable organic medium
  • B microgel
  • FIG. 1 illustrates the operation of a homogenizing valve.
  • the viscosity of the organic medium is preferably less than 200 mPas, more preferably less than 100 mPas, at 120° C.
  • the viscosity of the crosslinkable organic medium (A) is determined at 120° C. at a speed of 5 s ⁇ 1 by means of a cone/plate measuring system according to DIN 53018.
  • the microgel (B) used in the composition according to the present invention is a crosslinked microgel.
  • it is not a microgel crosslinked by means of high-energy radiation.
  • High-energy radiation here means electromagnetic radiation having a wavelength of less than 0.1 ⁇ m.
  • the use of microgels crosslinked by means of high-energy radiation, as described, for example, in Chinese Journal of Polymer Science, Volume 20, No. 2, (2002), 93-98, is disadvantageous because it is virtually impossible to produce microgels crosslinked by high-energy radiation on an industrial scale.
  • the use of high-energy radiation from radioactive radiation sources such as radioactive cobalt is associated with serious safety problems.
  • the radiation-crosslinked microgels are generally fully radiation-crosslinked microgels
  • the change in modulus, during incorporation of the composition according to the present invention into plastics, for example, from the matrix phase to the dispersed phase is immediate.
  • sudden stress can cause tearing effects between the matrix and the dispersed phase, with the result that the mechanical properties, the swelling behavior and the stress corrosion cracking, etc. of the microgel-containing plastics produced using the compositions according to the present invention are impaired.
  • the primary particles of the microgel (B) exhibit approximately spherical geometry.
  • primary particles are the microgel particles dispersed in the coherent phase which can be individually recognized by means of suitable physical processes (electron microscope) (see e.g. Römpp Lexikon, Lacke und Druckmaschine, Georg Thieme Verlag, 1998).
  • An “approximately spherical” geometry means that the dispersed primary particles of the microgels recognizably have substantially a circular surface when the composition is viewed, for example, using an electron microscope.
  • microgel-containing compositions such as, for example, plastics, coating compositions, lubricants or the like, obtained using the composition according to the present invention.
  • the variation in the diameters of an individual primary particle is preferably less than 250%, more preferably less than 100%, most preferably less than 50%.
  • At least 80%, more preferably at least 90%, most preferably at least 95%, of the primary particles of the microgel exhibit a variation in the diameters, defined as [( d 1 ⁇ d 2)/ d 1] ⁇ 100, wherein d1 and d2 are any two diameters of the primary particle and d1>d2, of less than 250%, preferably less than 100%, more preferably less than 50%.
  • the above-mentioned variation in the diameters of the individual particles is determined by the following process.
  • a thin section of the composition according to the present invention is first prepared as described in the Examples.
  • An image is then recorded by transmission electron microscopy at a magnification of, for example, 10,000 times or 200,000 times.
  • the largest and smallest diameters d1 and d2 are determined on 10 microgel primary particles. If the variation is less than 250%, more preferably less than 100%, most preferably less than 50%, in all 10 microgel primary particles, then the microgel primary particles exhibit the above-defined feature of variation.
  • the concentration of the microgels in the composition is so high that pronounced overlapping of the visible microgel primary particles occurs, the evaluatability can be improved by previously diluting the measuring sample in a suitable manner.
  • the primary particles of the microgel (B) preferably have an average particle diameter of from 5 to 500 nm, more preferably from 20 to 400 nm, most preferably from 30 to 300 nm (diameter data according to DIN 53206). Because the morphology of the microgels remains substantially unchanged during the further processing of the composition according to the present invention, the average particle diameter of the dispersed primary particles corresponds substantially to the average particle diameter of the dispersed primary particles in the products of further processing obtained using the composition according to the present invention, such as microgel-containing plastics, lubricants, coatings, etc.. This constitutes a particular advantage of the composition according to the present invention.
  • microgel formulations which are customized to a certain degree and exhibit a defined morphology of the microgels and which the customer can readily process further in the desired applications. Previous expensive dispersion, homogenization or even preparation of the microgels is no longer necessary, and it is therefore to be expected that such microgels will also be used in fields in which their use hitherto appeared too costly.
  • the microgels (B) advantageously contain at least about 70 wt. %, more preferably at least about 80 wt. %, most preferably at least about 90 wt. %, portions that are insoluble in toluene at 23° C. (gel content).
  • the portion that is insoluble in toluene is determined in toluene at 23° C.
  • 250 mg of the microgel are swelled in 20 ml of toluene at 23° C. for 24 hours, with shaking. After centrifugation at 20,000 rpm, the insoluble portion is separated off and dried. The gel content is obtained from the difference between the weighed portion and the dried residue and is given in percent.
  • the microgels (B) advantageously exhibit a swelling index in toluene at 23° C. of less than about 80, more preferably of less than 60, most preferably of less than 40.
  • the swelling indices of the microgels (Qi) can preferably be between 1-15 and 1-10.
  • 250 mg of the microgel are allowed to swell in 25 ml of toluene for 24 hours, with shaking.
  • the gel is removed by centrifugation and weighed and then dried at 70° C. until a constant weight is reached and then weighed again.
  • the microgels (B) preferably have glass transition temperatures Tg of from ⁇ 100° C. to +100° C., more preferably from ⁇ 80° C. to +80° C.
  • the microgels (B) used in the composition according to the present invention preferably have a breadth of glass transition of greater than 5° C., preferably greater than 10° C., more preferably greater than 20° C. Microgels that have such a breadth of glass transition are generally not completely homogeneously crosslinked—in contrast to completely homogeneously radiation-crosslinked microgels. This has the result that the change in modulus from the matrix phase to the dispersed phase in the microgel-containing plastics compositions, for example, produced from the compositions according to the invention is not immediate. As a result, sudden stress on these compositions does not lead to tearing effects between the matrix and the dispersed phase, with the result that the mechanical properties, the swelling behavior and the stress corrosion cracking, etc. are advantageously affected.
  • the glass transition temperatures (Tg) and the breadth of the glass transition ( ⁇ Tg) of the microgels are determined by differential scanning calorimetry (DSC) under the following conditions: For determining Tg and ⁇ Tg, two cooling/heating cycles are carried out. Tg and ⁇ ATg are determined in the second heating cycle. For the determinations, 10 to 12 mg of the chosen microgel are placed in a DSC sample container (standard aluminum ladle) from Perkin-Elmer. The first DSC cycle is carried out by first cooling the sample to ⁇ 100° C. with liquid nitrogen and then heating it to +150° C. at a rate of 20 K/min. The second DSC cycle is begun by immediately cooling the sample as soon as a sample temperature of +150° C. has been reached.
  • DSC differential scanning calorimetry
  • Cooling is carried out at a rate of about 320 K/min.
  • the sample is again heated to +150° C., as in the first cycle.
  • the rate of heating in the second cycle is again 20 K/min.
  • Tg and ⁇ Tg are determined graphically on the DSC curve of the second heating operation. To that end, three straight lines are plotted on the DSC curve. The first straight line is plotted on the part of the DSC curve below Tg, the second straight line is plotted on the branch of the curve passing through Tg with the point of inflection, and the third straight line is plotted on the branch of the DSC curve above Tg. Three straight lines with two points of intersection are thus obtained. The two points of intersection are each characterized by a characteristic temperature.
  • the glass transition temperature Tg is obtained as the mean of these two temperatures, and the breadth of the glass transition ⁇ Tg is obtained from the difference between the two temperatures.
  • microgels present in the composition according to the present invention which microgels have preferably not been crosslinked by high-energy radiation, can be prepared in a manner known per se (see, for example, EP-A-405 216, EP-A-854 171, DE-A 4220563, GB-PS 1078400, DE 197 01 489.5, DE 197 01 488.7, DE 198 34 804.5, DE 198 34 803.7, DE 198 34 802.9, DE 199 29 347.3, DE 199 39 865.8, DE 199 42 620.1, DE 199 42 614.7, DE 100 21 070.8, DE 100 38488.9, DE 100 39 749.2, DE 100 52 287.4, DE 100 56 311.2 and DE 100 61 174.5).
  • EP-A 405 216, DE-A 4220563 and in GB-PS 1078400 the use of CR, BR and NBR microgels in mixtures with double-bond-containing rubbers is claimed.
  • DE 197 01 489.5 describes the use of subsequently modified microgels in mixtures with double-bond-containing rubbers such as NR, SBR and BR.
  • Microgels are understood as being rubber particles which are obtained especially by crosslinking the following rubbers:
  • the preparation of the uncrosslinked microgel starting products is preferably carried out by the following methods:
  • microgels (B) used in the composition according to the preferably invention are preferably those which are obtainable by emulsion polymerization and crosslinking.
  • the following free-radically polymerizable monomers are preferably used in the preparation of the microgels used according to the invention by emulsion polymerization: butadiene, styrene, acrylonitrile, isoprene, esters of acrylic and methacrylic acid, tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichloro-butadiene, and also double-bond-containing carboxylic acids, such as, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc., double-bond-containing hydroxy compounds, such as, for example, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl methacrylate, amine-functionalized (meth)acrylates, acrolein, N-vinyl-2-pyrrolidone, N-allyl-urea and N-allyl
  • Crosslinking of the rubber gel can be achieved directly during the emulsion polymerization, such as by copolymerization with multifunctional compounds having crosslinking action, or by subsequent crosslinking as described herein below.
  • Preferred multifunctional comonomers are compounds having at least two, preferably from 2 to 4, copolymerizable C ⁇ C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ethers, divinylsulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N,N′-m-phenylenemaleimide, 2,4-toluylenebis(maleimide) and/or triallyl trimellitate.
  • acrylates and methacrylates of polyhydric, preferably di- to tetra-hydric, C2 to C10 alcohols such as ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having from 2 to 20, preferably from 2 to 8, oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sorbitol, with unsaturated polyesters of aliphatic diols and polyols, as well as maleic acid, fumaric acid and/or itaconic acid.
  • polyhydric preferably di- to tetra-hydric, C2 to C10 alcohols
  • C2 to C10 alcohols such as ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having from 2 to 20, preferably from
  • Crosslinking to form rubber microgels during the emulsion polymerization can also be effected by continuing the polymerization to high conversions or by the monomer feed process by polymerization with high internal conversions. Another possibility consists in carrying out the emulsion polymerization in the absence of regulators.
  • latices which are obtained in the emulsion polymerization.
  • this method can also be used with non-aqueous polymer dispersions which are obtainable by other means, e.g. by recrystallization. Natural rubber latices can also be crosslinked in this manner.
  • Suitable chemicals having crosslinking action are, for example, organic peroxides, such as dicumyl peroxide, tert.-butylcumyl peroxide, bis-(tert.-butyl-peroxy-isopropyl)benzene, di-tert.-butyl peroxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 2,5-dimethylhexane 3,2,5-dihydroperoxide, dibenzoyl peroxide, bis-(2,4-dichlorobenzoyl) peroxide, tert.-butyl perbenzoate, and also organic azo compounds, such as azo-bis-isobutyronitrile and azo-bis-cyclohexanenitrile, and also di- and poly-mercapto compounds, such as dimercaptoethane, 1,6-dimercapto-hexane, 1,3,5-trimercaptotriazine and mercapto
  • the optimum temperature for carrying out the post-crosslinking is naturally dependent on the reactivity of the crosslinker and can be carried out at temperatures from room temperature to about 180° C., optionally under elevated pressure (see in this connection Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Volume 14/2, page 848).
  • Particularly preferred crosslinkers are peroxides.
  • crosslinking of rubbers containing C ⁇ C double bonds to form microgels can also be carried out in dispersion or emulsion with the simultaneous partial, or complete, hydrogenation of the C ⁇ C double bond by means of hydrazine, as described in U.S. Pat. No. 5,302,696 or U.S. Pat. No. 5,442,009, or optionally other hydrogenating agents, for example organometal hydride complexes.
  • Enlargement of the particles by agglomeration can optionally be carried out before, during or after the post-crosslinking.
  • Rubbers produced by solution polymerization can also be used as starting materials for the preparation of the microgels.
  • solutions of the rubbers in suitable organic solvents are used as starting material.
  • the desired sizes of the microgels are produced by mixing the rubber solution by means of suitable apparatuses in a liquid medium, preferably in water, optionally with the addition of suitable surface-active auxiliary substances, such as, for example, surfactants, so that a dispersion of the rubber in the appropriate particle size range is obtained.
  • suitable surface-active auxiliary substances such as, for example, surfactants
  • microgels for the preparation of the composition according to the present invention there may be used both non-modified microgels, which contain substantially no reactive groups especially at the surface, and microgels modified by functional groups, especially microgels modified at the surface.
  • the latter can be prepared by chemical reaction of the already crosslinked microgels with chemicals that are reactive towards C ⁇ C double bonds.
  • reactive chemicals are especially those compounds by means of which polar groups, such as, for example, aldehyde, hydroxyl, carboxyl, nitrile, etc., and also sulfur-containing groups, such as, for example, mercapto, dithiocarbamate, polysulfide, xanthogenate, thiobenzthiazole and/or dithiophosphoric acid groups and/or unsaturated dicarboxylic acid groups, can be chemically bonded to the microgels.
  • polar groups such as, for example, aldehyde, hydroxyl, carboxyl, nitrile, etc.
  • sulfur-containing groups such as, for example, mercapto, dithiocarbamate, polysulfide, xanthogenate, thiobenzthiazole and/or dithiophosphoric acid groups and/or unsaturated dicarboxylic acid groups
  • the purpose of modifying the microgels is to improve the microgel compatibility when the composition according to the invention is used to prepare the subsequent matrix, into which the microgel is incorporated, or the composition according to the present invention is used for incorporation into a matrix, in order to achieve a good distribution capacity during preparation as well as good coupling.
  • Preferred methods of modification are the grafting of the microgels with functional monomers and reaction with low molecular weight agents.
  • aqueous microgel dispersion which is reacted under the conditions of a free-radical emulsion polymerization with polar monomers such as acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, acrylamide, methacrylamide, acrylonitrile, acrolein, N-vinyl-2-pyrrolidone, N-allyl-urea and N-allyl-thiourea, and also secondary amino-(meth)acrylic acid esters such as 2-tert.-butylaminoethyl methacrylate and 2-tert.-butylaminoethylmethacrylamide.
  • microgels having a core/shell morphology, wherein the shell should be highly compatible with the matrix. It is desirable for the monomer used in the modification step to be grafted onto the unmodified microgel as quantitatively as possible.
  • the functional monomers are preferably metered in before crosslinking of the microgels is complete.
  • Suitable reagents for the surface modification of the microgels with low molecular weight agents include the following: elemental sulfur, hydrogen sulfide and/or alkylpolymercaptans, such as 1,2-dimercaptoethane or 1,6-dimercaptohexane, also dialkyl and dialkylaryl dithiocarbamate, such as the alkali salts of dimethyl dithiocarbamate and/or dibenzyl dithiocarbamate, also alkyl and aryl xanthogenates, such as potassium ethylxanthogenate and sodium isopropylxanthogenate, as well as reaction with the alkali or alkaline earth salts of dibutyldithiophosphoric acid and dioctyidithiophosphoric acid as well as dodecyidithiophosphoric acid.
  • alkylpolymercaptans such as 1,2-dimercaptoethane or 1,6-dimercaptohe
  • the mentioned reactions can also be carried out in the presence of sulfur, the sulfur being incorporated with the formation of polysulfide bonds.
  • free-radical initiators such as organic and inorganic peroxides and/or azo initiators can be added.
  • modified microgels such as, for example, by ozonolysis as well as by halogenation with chlorine, bromine and iodine.
  • a further reaction of modified microgels such as, for example, the preparation of hydroxyl-group-modified microgels from epoxidized microgels, is also understood as being the chemical modification of microgels.
  • the microgels can be modified by hydroxyl groups, especially also at the surface thereof.
  • the hydroxyl group content of the microgels is determined as the hydroxyl number with the dimension mg of KOH/g of polymer by reaction with acetic anhydride and titration of the acetic acid liberated thereby with KOH according to DIN 53240.
  • the hydroxyl number of the microgels is preferably from 0.1 to 100, more preferably from 0.5 to 50, mg of KOH/g of polymer.
  • the amount of modifying agent used is governed by its effectiveness and the demands made in each individual case and is in the range from 0.05 to 30 wt. %, based on the total amount of rubber microgel used, particular preference being given to from 0.5 to 10 wt. %, based on the total amount of rubber gel.
  • the modification reactions can be carried out at temperatures of from 0 to 180° C., preferably from 20 to 95° C., optionally under a pressure of from 1 to 30 bar.
  • the modifications can be carried out on rubber microgels without a solvent or in the form of their dispersion, it being possible in the latter case to use inert organic solvents or alternatively water as the reaction medium.
  • the modification is preferably carried out in an aqueous dispersion of the crosslinked rubber.
  • compositions according to the present invention that are used for incorporation into non-polar rubbers or non-polar thermoplastic materials, such as, for example, polypropylene, polyethylene and block copolymers based on styrene, butadiene, isoprene (SBR, SIR) and hydrogenated isoprene-styrene block copolymers (SEBS), and conventional TPE-Os and TPE-Vs, etc.
  • non-polar rubbers or non-polar thermoplastic materials such as, for example, polypropylene, polyethylene and block copolymers based on styrene, butadiene, isoprene (SBR, SIR) and hydrogenated isoprene-styrene block copolymers (SEBS), and conventional TPE-Os and TPE-Vs, etc.
  • modified microgels is preferred in the case of compositions according to the invention that are used for incorporation into polar rubbers or polar thermoplastic materials (A), such as, for example, PA, TPE-A, PU, TPE-U, PC, PET, PBT, POM, PMMA, PVC, ABS, PTFE, PVDF, etc.
  • polar rubbers or polar thermoplastic materials such as, for example, PA, TPE-A, PU, TPE-U, PC, PET, PBT, POM, PMMA, PVC, ABS, PTFE, PVDF, etc.
  • the mean diameter of the prepared microgels can be adjusted with high accuracy, for example, to 0.1 micrometer (100 nm) ⁇ 0.01 micrometer (10 nm), so that, for example, a particle size distribution is achieved in which at least 75% of all the microgel particles are from 0.095 micrometer to 0.105 micrometer in size.
  • Other mean diameters of the microgels especially in the range from 5 to 500 nm, can be produced with the same accuracy (at least 75 wt. % of all the particles are located around the maximum of the integrated particle size distribution curve (determined by light scattering) in a range of ⁇ 10% above and below the maximum) and used.
  • the morphology of the microgels dispersed in the composition according to the present invention can be adjusted virtually “point accurately” and hence the properties of the composition according to the present invention and of the plastics, for example, produced therefrom can be adjusted.
  • microgels so prepared can be worked up, for example, by concentration by evaporation, coagulation, by co-coagulation with a further latex polymer, by freeze coagulation (see U.S. Pat. No. 2,187,146) or by spray-drying.
  • flow auxiliaries such as, for example, CaCO 3 or silica, can also be added.
  • the microgel (B) is based on rubber.
  • the microgel (B) has been modified by functional groups reactive towards C ⁇ C double bonds.
  • the microgel (B) has a swelling index in toluene at 23° C. of from 1 to 15.
  • composition according to the present invention preferably has a viscosity at 20° C. of from 2 mPas to 5,000,000 mpas, more preferably from 50 mPas to 3,000,000 mpas, at a speed of 5 s ⁇ 1 in a cone/plate viscometer according to DIN 53018.
  • composition according to the present invention contains at least one organic medium (A) which has a viscosity at a temperature of 120° C. of less than 1000 mPas, preferably 200 mPas, more preferably 100 mPas.
  • Such a medium is liquid to solid at room temperature (20° C.).
  • Organic medium within the scope of the present invention means that the medium contains at least one carbon atom.
  • non-crosslinkable media are understood as being especially media that do not contain groups crosslinkable via hetero-atom-containing functional groups or C ⁇ C groups, such as, especially, conventional monomers or pre-polymers which are crosslinked or polymerized in the conventional manner by means of free radicals, by means of UV radiation, thermally and/or with the addition of crosslinkers (e.g. polyisocyanates) etc. with the formation of oligomers or polymers.
  • Non-crosslinkable media are preferably also solvents, more preferably those according to DIN 55 945.
  • the non-crosslinkable medium (A) is preferably a non-crosslinkable medium that is liquid at room temperature (20° C.), more preferably a hydrocarbon (straight-chain, branched, cyclic, saturated, unsaturated and/or aromatic hydrocarbons having from 1 to 200 carbon atoms, which may optionally be substituted by one or more substituents selected from halogens, such as chlorine, fluorine, hydroxy, oxo, amino, carboxy, carbonyl, aceto, amido), synthetic hydrocarbon, polyether oil, ester oil, phosphoric acid ester, silicon-containing oil or halogenated hydrocarbon or carbon halide (see e.g.
  • non-crosslinkable media (A) are distinguished especially by viscosities of from 2 to 1500 mm 2 /s (cSt) at 40° C.
  • the non-crosslinkable medium (A) is preferably a non-crosslinkable medium that is liquid at room temperature (20° C.), preferably a solvent according to DIN 55 495, such as xylene, solvent naphtha, methyl ethyl ketone, methoxypropyl acetate, N-methylpyrrolidone, dimethyl sulfoxide.
  • a solvent according to DIN 55 495 such as xylene, solvent naphtha, methyl ethyl ketone, methoxypropyl acetate, N-methylpyrrolidone, dimethyl sulfoxide.
  • Synthetic hydrocarbons are obtained by polymerization of olefins, condensation of olefins or chloroparaffins with aromatic compounds, or dechlorinating condensation of chloroparaffins.
  • polymer oils are ethylene polymers, propylene polymers, polybutenes, polymers of higher olefins, alkyl aromatic compounds.
  • the ethylene polymers have molecular weights of from 400 to 2000 g/mol.
  • the polybutenes have molecular weights of from 300 to 1500 g/mol.
  • polyether oils In the case of the polyether oils, a distinction is made between aliphatic polyether oils, polyalkylene glycols, especially polyethylene and polypropylene glycols, their mixed polymers, their mono- and di-ethers and also ester ethers and diesters, tetrahydrofuran polymer oils, perfluoropolyalkyl ethers and polyphenyl ethers.
  • Perfluoropolyalkyl ethers have molar masses of from 1000 to 10,000 g/mol.
  • the aliphatic polyether oils have viscosities of from 8 to 19,500 mm 2 /s at 38° C.
  • Polyphenyl ethers are prepared by condensation of alkali phenolates with halobenzenes.
  • the diphenyl ether and its alkyl derivatives are also used.
  • ester oils are the alkyl esters of adipic acid, bis-(2-ethylhexyl) sebacate and bis-(3,5,5-trimethylhexyl) sebacate or adipate.
  • a further class is formed by the fluorine-containing ester oils.
  • phosphoric acid esters a distinction is made between triaryl, trialkyl and alkylaryl phosphates. Examples are tri-(2-ethylhexyl) phosphate and bis-(2-ethylhexyl)-phenyl phosphate.
  • Silicon-containing oils are the silicone oils (polymers of the alkyl- and aryl-siloxane group) and the silicic acid esters.
  • the halogenated hydrocarbons or carbon halides include chlorinated paraffins, such as chlorotrifluoroethylene polymer oils and hexafluorobenzene.
  • Non-reactive solvents according to DIN 55 945 are hexane, special boiling point gasoline, white spirit, xylene, solvent naphtha, balsam turpentine, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, isophorone, butyl acetate, 1-methoxypropyl acetate, butyl glycol acetate, ethyl diglycol acetate and N-methylpyrrolidone (Brock, Thomas, Groteklaes, Michael, Mischke, Peter, Lehrbuch der Lacktechnologie, Curt R. Vincentz Verlag Hannover, (1998) 93 ff).
  • Preferred non-crosslinkable media (A) are the large class of the hydrocarbons, the polyether oils, and the solvents according to DIN 55 945.
  • the composition according to the present invention preferably contains from 0.5 to 90 wt. %, more preferably from 1 to 40 wt. %, most preferably from 2 to 30 wt. %, of the microgel (B), based on the total amount of the composition.
  • composition according to the present invention further contains preferably from 10 to 99.5 wt. %, more preferably from 40 to 97 wt. %, most preferably from 50 to 95 wt. %, even more preferably from 60 to 95 wt. %, of the organic medium (A).
  • composition according to the present invention preferably contains the non-crosslinkable organic medium (A) and the microgel (B) and optionally the further components mentioned herein below.
  • the presence of water is not preferred, more preferably the presence of water is excluded.
  • composition according to the present invention can additionally contain fillers, pigments and additives, such as dispersing aids, de-aerators, flow agents, auxiliary substances for the wetting of substrates, adhesion promoters, anti-settling agents, auxiliary substances for controlling substrate wetting, for controlling conductivity, auxiliary substances for controlling color stability, gloss and floating, oxidation inhibitors, pour-point depressors, high-pressure additives, foam-preventing agents, demulsifying agents.
  • additives such as dispersing aids, de-aerators, flow agents, auxiliary substances for the wetting of substrates, adhesion promoters, anti-settling agents, auxiliary substances for controlling substrate wetting, for controlling conductivity, auxiliary substances for controlling color stability, gloss and floating, oxidation inhibitors, pour-point depressors, high-pressure additives, foam-preventing agents, demulsifying agents.
  • the mentioned additives can preferably be incorporated into the compositions according to the present invention uniformly, which in turn leads to an improvement in the polymer compositions produced therefrom.
  • pigments and fillers for the preparation of the compositions according to the present invention containing the non-crosslinkable medium (A), and of microgel-containing plastics produced therefrom are, for example: inorganic and organic pigments, silicate-like fillers such as kaolin, talcum, carbonates such as calcium carbonate and dolomite, barium sulfate, metal oxides such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, highly dispersed silicas (precipitated silicas and silicas produced by thermal means), metal hydroxides such as aluminum hydroxide and magnesium hydroxide, glass fibers and glass fiber products (laths, threads or glass microspheres), carbon fibers, thermoplastic fibers (polyamide, polyester, aramid), rubber gels based on polychloroprene and/or polybutadiene, and also any other gel particles described above having a high degree of crosslinking and a particle size of from 5 to 1000 nm.
  • inorganic and organic pigments such as kaolin,
  • the mentioned fillers can be used alone or in a mixture.
  • from 0.5 to 30 parts by weight of rubber gel (B), optionally together with from 0.1 to 40 parts by weight of fillers, and from 30 to 99.5 parts by weight of the non-crosslinkable liquid medium (A) are used to prepare the compositions present according to the invention.
  • compositions according to the present invention can contain further auxiliary substances, such as anti-ageing agents, heat stabilizers, light stabilizers, anti-ozonants, processing aids, plasticizers, tackifiers, blowing agents, colorings, waxes, extenders, organic acids and also filler activators, such as, for example, trimethoxysilane, polyethylene glycol, or other auxiliary substances known in the described industries.
  • auxiliary substances such as anti-ageing agents, heat stabilizers, light stabilizers, anti-ozonants, processing aids, plasticizers, tackifiers, blowing agents, colorings, waxes, extenders, organic acids and also filler activators, such as, for example, trimethoxysilane, polyethylene glycol, or other auxiliary substances known in the described industries.
  • the auxiliary substances are used in the conventional amounts, which are governed inter alia by the intended use.
  • Conventional amounts are, for example, amounts of from 0.1 to 50 wt. %, based on the amounts of liquid medium (A) used.
  • the composition according to the present invention is prepared by means of a homogenizer, a bead mill or a three-roller mill.
  • a homogenizer for example, a homogenizer
  • bead mills Disadvantages of bead mills are the comparatively limited viscosity range (tendency towards thin compositions), the high outlay in terms of cleaning, the expensive change-over of the compositions that can be used, and wear of the beads and the grinding apparatus.
  • Homogenization of the compositions according to the present invention is preferably carried out by means of a homogenizer or a three-roller mill.
  • Disadvantages of three-roller mills are the comparatively limited viscosity range (tendency towards very thick compositions), the low throughput and the fact that the procedure is not closed (poor working protection).
  • Homogenization of the compositions according to the present invention is more preferably carried out by means of a homogenizer.
  • the homogenizer allows thin and thick compositions to be processed with
  • the dispersion of the microgels (B) in the liquid medium (A) takes place in the homogenizer in the homogenizing valve (The FIGURE).
  • agglomerates are comminuted into aggregates and/or primary particles. Agglomerates are physically separable units which undergo no change in primary particle size during dispersion.
  • the product to be homogenized enters the homogenizing valve at low speed and is accelerated to high speeds in the homogenizing gap. Dispersion takes place downstream of the gap, principally as a result of turbulence and cavitation (William D. Pandolfe, Peder Baekgaard, Marketing Bulletin of APV Homogenizer Group—“High-pressure homogenizers processes, product and applications”).
  • the temperature of the composition according to the present invention on introduction into the homogenizer is advantageously from ⁇ 40 to 140° C., preferably from 20 to 80° C.
  • composition according to the present invention to be homogenized is preferably homogenized in the apparatus at a pressure of from 200 to 4000 bar, preferably from 500 to 2000 bar, more preferably from 900 to 2000 bar.
  • the number of passes is governed by the desired dispersion quality and can vary from 1 to 20, preferably from 1 to 10, passes.
  • compositions prepared according to the present invention have a fine particle distribution, which is achieved especially with the homogenizer and is extremely advantageous also in respect of the flexibility of the process with regard to varying viscosities of the liquid media and of the resulting compositions and necessary temperatures as well as the dispersion quality.
  • the present invention relates also to the use of the composition according to the present invention in the production of microgel-containing polymers or plastics, as discussed above.
  • compositions according to the present invention are incorporated into thermoplastic polymers, it is surprisingly found that microgel-containing polymers that behave like thermoplastic elastomers are obtained.
  • the present invention relates also to the molded bodies and coatings produced therefrom by conventional processes.
  • Example 1 described herein below it is shown that compositions according to the present invention having specific rheological characteristics, such as intrinsic viscosity, thixotropy and approximately Newtonian flow behavior, are obtained using microgels based on SBR.
  • composition of the microgel phase is given in the table below: 1. T 110 80% 2. Micromorph 5P 20% Total 100%
  • T 110 is hydrogenated naphthenic oil from Nynas Naphthenics AB.
  • Micromorph 5P is an SBR-based crosslinked rubber gel having an OH number of 4 from RheinChemie Rheinau GmbH. Micromorph 5P consists of 40 wt. % styrene, 57.5 wt. % butadiene and 2.5 wt. % dicumyl peroxide.
  • Micromorph 1P is an SBR-based, crosslinked, surface-modified rubber gel from RheinChemie Rhienau GmbH.
  • Micromorph 1P consists of 80 wt. % styrene, 12 wt. % butadiene, 5 wt. % ethylene glycol dimethacrylate (EGDMA) and 3 wt. % hydroxyethyl methacrylate (HEMA).
  • Microgel based on hydroxyl-modified SBR prepared by direct emulsion polymerization using the crosslinking comonomer ethylene glycol dimethacrylate (Micromorph 1P).
  • the reaction mixture was heated to 30° C., with stirring.
  • An aqueous solution containing 170 g of water, 1.69 g of ethylenediaminetetraacetic acid (Merck-Schuchardt), 1.35 g of iron (II) sulfate * 7H2O, 3.47 g of Rongalit C (Merck-Schuchradt) and 5.24 g of trisodium phosphate * 12H2O was then metered in.
  • the reaction was started by addition of an aqueous solution of 2.89 of p-menthane hydroperoxide (Trigonox NT 50 from Akzo-Degussa) and 10.53 g of Mersolat K 30/95, dissolved in 250 g of water.
  • Trigonox NT 50 from Akzo-Degussa
  • T110 was placed in the vessel and Micromorph 5P was added with stirring by means of a dissolver.
  • the composition was passed through the homogenizer four times at 950 bar.
  • the rheological properties of the composition were determined by means of a rheometer, MCR300, from Physica. A plate/cone system, CP25-1, was used as the measuring body. The measurements were carried out at 20° C.
  • the table shows the viscosities v′, which were measured at shear rates of 5 s ⁇ 1 , 100 s ⁇ 1 , 1000 s ⁇ 1 , 3000 s ⁇ 1 and 0.1 s ⁇ 1 .
  • the quotient v′(0.1 s ⁇ 1 )/v′(3000 s ⁇ 1 ) was defined as an arbitrary measure of the viscosity-increasing action of microgel.
  • composition containing 80% T110 and 20% Micromorph 5P which was passed through the homogenizer four times at 950 bar, exhibits Theological behavior comparable to that of Li-120H AK33 or E301.
  • Micromorph 1P exhibits no appreciable thickening in Nynas T110.
  • the measured values show a thickening which, with suitable selection of the microgel/lubricant combination, is suitable for the production of lubricating greases.
  • compositions according to the present invention are valuable as thickeners, as anti-dripping and anti-settling agents and as a rheological additive.
  • compositions can advantageously be used in lubricants, paints and inks, adhesives, rubber and gel coats.
  • compositions prepared in Example 1 can be used in lubricating greases. They result in advantageous properties therein, such as high intrinsic viscosity.

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  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
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RU2404200C2 (ru) 2010-11-20
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CA2539906A1 (en) 2005-04-07
WO2005030843A1 (de) 2005-04-07
CN1856527A (zh) 2006-11-01
JP5647933B2 (ja) 2015-01-07
ATE414121T1 (de) 2008-11-15
CN100528939C (zh) 2009-08-19
BRPI0414461B1 (pt) 2014-09-09
EP1664157A1 (de) 2006-06-07
UA84161C2 (ru) 2008-09-25
JP2011174078A (ja) 2011-09-08
US20080064768A1 (en) 2008-03-13
JP2007506831A (ja) 2007-03-22
RU2006114342A (ru) 2007-11-20
CA2539906C (en) 2012-04-03
ES2317056T3 (es) 2009-04-16
BRPI0414461A (pt) 2006-11-14
DE10344975A1 (de) 2005-04-21
US7842732B2 (en) 2010-11-30

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