WO2000064953A1 - A process for production of micro-porous microspheres of polymers and polymeric pigments therefrom - Google Patents

A process for production of micro-porous microspheres of polymers and polymeric pigments therefrom Download PDF

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WO2000064953A1
WO2000064953A1 PCT/IN2000/000025 IN0000025W WO0064953A1 WO 2000064953 A1 WO2000064953 A1 WO 2000064953A1 IN 0000025 W IN0000025 W IN 0000025W WO 0064953 A1 WO0064953 A1 WO 0064953A1
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micro
polymers
porous
particles
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PCT/IN2000/000025
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English (en)
French (fr)
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Vinod Chintamani Malshe
Anil Meghshyam Bendale
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Vinod Chintamani Malshe
Anil Meghshyam Bendale
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Priority to AU46094/00A priority Critical patent/AU4609400A/en
Publication of WO2000064953A1 publication Critical patent/WO2000064953A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

  • a process for production of micro-porous microsphers of polymers and polymeric pigments there from is
  • This invention relates to a process for production of micro-porous microsphers of polymers.
  • This invention particularly relates to a process of suspension or emulsion polymerization and cross-linking for production of micro-porous microsphers of polymers of sub-micron size.
  • This invention more particularly relates to preparation of micro-porous microsphers of polymers, which are by themselves transparent colourless pigments and which can then be converted to superior coloured pigments by simple dyeing process.
  • Organic pigments invariably are crystalline particles with a wide variety of shapes such as needles, platelets, different crystal forms and fractured crystal shapes because of which they tend to agglomerate. These particles have excess energy at all the sharp edges and the flat surfaces tend to stick to each other and a large number of particles tend to stay with each other making them difficult to disperse.
  • the process of dispersion is energy intensive and special additives such as wetting agents, dispersing agents, are required to bring about the dispersion.
  • the crystals are unstable and tend to inter-convert from low to high stability state. This brings in loss of colour value, gloss, and change in hue over a period of time.
  • polymeric particles can be coloured and used as coloured particles.
  • US Patent 4636452 (1987) discloses preparation of coloured particles.
  • US Patent 4617249 (1986) describes process for preparing dry toner composition by dispersion polymerization. A gist of most relevant patents in this field, in respect of present invention, is given below. Preparation of porous polymers such as well-known polyurethane foams has been described. In preparation of polyurethane foams, blowing agents such as chlorinated fluorocarbons are employed.
  • US patent 5242954 (1993) describes a process for making cellular and microcellular polyurethane foams.
  • the reactants provide a built-in capability to generate carbon dioxide as an in situ blowing agent.
  • a poly isocynate is reacted with a carboxy-modified polyol to form polyurethane and carbon dioxide.
  • such polymerization process is carried out in a mould to get the product of desired shape.
  • US Patent 4,552,812 (1985) describes a process for production of polyacrolein microsphers and grafted microsphers, which comprises subjecting an aqueous mixture of a polymerizable acrolein-type monomer to polymerization in the presence of an effective amount of a suitable • ionic surfactant which promotes microsphers formation upon polymerization of the monomer so as to form microsphers, the polymerization being effected at a pH between 8.0 and 13.7, and recovering the resulting microsphers and purifying the microsphers so recovered.
  • anionic or catio ⁇ ic surfactants may be used for emulsification. It has been shown that changing the acrolein concentration, surfactant concentration or pH of the polymerization can control size of the microsphers. As the surfactant concentration goes up from 0 -3 % w/v the diameter of the microsphers falls down from 3 ⁇ to 0.5 ⁇ ; as pH rises towards 12 the diameter of the microsphers drops down to ⁇ 0.5 ⁇ . They are hydrophobic in nature.
  • This patent also describes preparation of hybrid microsphers wherein anionic polyacrolein microsphers have been coated with the radical microsphers.
  • US Patent 4,880,432 (1989) discloses a process for preparing particles coloured with a dye which comprises (a) forming, by a free radical dispersion polymerization process in a non- aqueous solution, polymeric particles having attached thereto stabilizing copolymers with at least one functional group capable of undergoing a chemical reaction with a dye, the particles having an average diameter of from about 0.1 to about 20 microns; (b) adding a dye to the polymeric particles having attached thereto stabilizing copolymers; and (c) effecting a chemical reaction between the dye and the stabilizing copolymers that results in the dye becoming covalently bound to the polymeric particles.
  • a liquid electrographic developer composition comprising a liquid medium, a charge control agent, coloured polymeric toner particles prepared as stated above and having an average diameter of from about 0.5 to about 5 microns.
  • colourless stabilized polymeric particles are first formed and subsequently coloured by forming co-valent bonds between the polymers and dye molecules.
  • the polymeric particles comprise a macroscopic thermoplastic resin core to which is chemically or physically attached an amphiphatic block or graft copolymer steric stabilizer.
  • Preferred core materials are polyvinyl acetate, poly vinyl pyrrolidone, polyvinyl acetate, methyl methacrylate, styrene, and ethyl acrylate and copolymers of any of these monomers.
  • US Patent 3957741(1976) describes preparation of a composition essentially of uniformly shaped hydrophilic, swellable, porous, round beads, of uniform diam.
  • ⁇ 2 ⁇ prepared by the aqueous suspension polymerization of an acrylic monomer containing an hydroxy or amino group such as hydroxyethylmethacrylate (HEMA), 1-35 % of compatible commoner such as lower alkyl methacrylate, acrylic or methacrylic acid, styrene and vinyl toluene may be present in the polymerizable mixture; a cross linking agent such as liquid [polyvinyl] diene or triene compound.
  • HEMA hydroxyethylmethacrylate
  • Cross-linking is brought about under nitrogen inert atmosphere, by heat about 50 -100°C for about 24 hrs without catalyst or by ⁇ -ray irradiation at ambient temperature for about 15 mts.
  • An aqueous soluble polymer -polyethylene oxide [mol. wt. ⁇ 4, 000,000] is added to the polymerizable mixture, and removed by washing the reaction product with boiling water. The dry material is ground into individual beads.
  • beads are intended for use as adsorbents in chromatography and as markers for studies of cell surface receptors, in gel filtration and permeation, separation and analysis -
  • polyethylene oxide polymer has been extended to polyethers mol.wt 300,000 - 10,000,000; this extension includes polyethers of alkylene oxides such as ethyiene oxide, propylene oxide or their mixtures.
  • the agglomerates of the beads are dispersed in non-solvent liquid and crushed or ground to get the uniformly shaped, hydrophilic, swellable, porous round beads, at least 80% of which are having diameter less than 2 microns. They also claim at least 90% of beads having diameter between 0.001 and 2 microns.
  • Use of cross-li king agent N,N'-methylene-bis- acrylamide has a separate claim. It will be seen that these porous round beads, of the above two US patents 3957741(1976) and 4,046,720(1977) are mainly prepared from acrylic type of monomers.
  • microsphers preparations as described in US Patents 4,552,812 (1985 ) and 4,880,432
  • 3819557(1974) describes method for preparation of improved polymeric pigments for use in paper coatings by an emulsion polymerization process comprising the steps of (1) emulsion polymerizing at least 50 weight percent of total monomer in absence of emulsifier, (2) adding an emulsifier and (3) continuing emulsion polymerization of the remaining monomer charge.
  • US Pat 4476210 discloses process for dispersing or dissolving the dye in the polymeric particles comprising a thermoplastic resin core with an amphipathic block or graft copolymer steric stabilizer irreversibly chemically or physically anchored lo the resin core, iv. US Pat 4636452, colours polymeric particles prepared from selected polymers and monomers by a specific method, by dispersing or dissolving dye molecules therein, v. US Pat 4617249, process entails preparing a solvent medium containing disperse steric stabilizers, monomers and initiator compounds, adding a cross linking compound, heating the mixture to polymerize the monomers, and separating the formed particles from the mixture.
  • Diffusing a dye, present in a solvent solution, into the polymer mixture may effect coloration of the particles.
  • British Pat 1181287 method is coupling diazotized colouring material with monomer during free radical polymerization. The coloured material is then processed by wet grinding ball milling etc.
  • the colorant (pigment or dye) may be attached to polymeric particles colloidally, suspended in a liquid chemically, or by secondary forces or by surface adhesive forces. In another embodiment, bonding brings about chemical bonding with the precursor or grafted side chain of the polymer prior to formation.
  • US Patent 4093793 claims a structurally dyed water-insoluble macromolecular material containing, in copolymerized form, acrylamide, at least one colourless monomer selected from the group consisting of vinyl chloride, vinyl acetate, styrene, acrylic acid, acrylates, and acrylonitrile and at least one anthraquinone dye having a group containing a polymerizable double bond, obtained by reacting for one or two minutes, in an aqueous medium and in the presence of a tetravalent cerium complex, the dye with the acrylamide and then introducing in the medium said colourless monomer and continuing the polymerization, the amount of dye being from 0.1 to 25% by weight of the colourless monomer and the amount of acrylamide being from 0.5 to 50 % by weight of the colourless monomer.
  • acrylamide at least one colourless monomer selected from the group consisting of vinyl chloride, vinyl acetate, styrene, acrylic acid, acrylates, and acrylon
  • the coloured polymer particles described in above patents are in general for use in (liquid) toners, photographic developers and the like jobs; and none of these use microporous microsphers of crosslinked polymeric particles for making colour pigments.
  • the main object of the present invention therefore relates to .a process for preparation of micro-porous microsphers of sub-micron size of polymers by polymerization of any type of monomer including crosslinkers, with or without functional groups to hold the regular dye molecules inside the pores.
  • porosity could be generated in the polymer by presence of non- polymerizable low boiling liquid during polymerization process, and venting them out of the system once the cross-linking imparts a rigid structure to the polymer.
  • Such a porous polymer will have same venting channels to fill the pores by dye, or any other required molecule.
  • Our approach is to add non-polymerizable micro porosity generating agents to the polymerizing mixture, and carry out polymerization of the monomers in suspension or emulsion form and remove the porosity-generating agent after the polymerization, without allowing them to be entrapped in the polymer.
  • Pigments such as titanium dioxide, lithopone , zinc oxide or litharge, red lead, iron oxide, chrome yellow, Prussian blue are inorganic; while phthalocyanine blue, carbon black could be considered as organic. They are used mainly for their opaque and protective characteristics. The colour strength of organic, inorganic pigments is limited mainly because of the tendency of complex organic pigment molecules to flocculate.
  • Macromolecular dyes are intrinsically and structurally coloured polymers in which colour groups are incorporated during formation of certain polymers. However, during their preparation structural configuration of the Chromophoric group changes, discoloration occurs due to free radical reactions of polymerization and they are not satisfactory as pigments.
  • Such macromolecular materials have been employed by what is known as combinatorial approach for synthesis of drugs, proteins, catalysts, peptides and in some cases of drug delivery system wherein the relevant molecules are supported on the appropriate tailor made macromolecule.
  • Tinting colours are also at times added to the pigments to get the desired shade / tint effect on the final product to which the pigment is applied. But such products are not stable and discoloration occurs in a short time. There is a need to produce newer pigments with different colours that will be stable in use over a longer period. It would be most preferable to have non-flocculating pigment particles that could be coloured to the desired shade. In our application, we describe processes to obtain such microporous polymers, which could fulfil the need of colorable pigment particles and also process by which to obtain these coloured particles.
  • the present invention relates to a process for manufacture of micro-porous microsphers of sub-micron size of polymers comprising, i. mixing micro-porosity generating agent(s) with the monomers) and/ or additives for some functional groups: ii. emulsifying the mix obtained at the end of step I. in water with the help of emulsifying agent(s) to give homogenous emulsion, or making micro suspension of the said mix in water or non-aqueous phase with the help of suspending agent(s): iii.
  • step iii subjecting the said emulsion or the said suspension obtained at the end of step ii, to polymerizing and/or cross-linking reaction with addition of initiator to form the micro- porous microsphers of the polymer; iv. removing the non-polymerizable micro-porosity generating agent from the reaction mass at the end of step (iii) when the reaction is complete; v. Coagulating the micro-porous microspheric polymer particles in the reaction mass remaining after step (iv) by addition of polymer-coagulating agent(s) to the said reaction mass; separating the coagulated micro-porous microspheric polymer particles from the reaction mass, washing and drying for recovering the polymers formed in the form of micro-porous.
  • step (iii) Separating the soaked particles obtained at the end of step (iii), washing, drying; to obtain the coloured polymeric pigment particles, when contact with coupling component of the colouring compound is not required to develop the colour; ix. Preparing coupling solution comprising said coupling component, when coupling component of the colouring compound is required to develop the colour, x. Soaking the dry particles obtained at the end of step (iii), only when second component of the colouring compound is required to develop the colour, in said -coupling solution of the second component prepared in step (v) for 30 - 60 minutes at 0 - 150 °C under pressure when required; xi. Separating ' the soaked particles obtained at the end of step (vi), drying, washing, and drying; to obtain the coloured polymeric pigment particles.
  • colouring compounds are selected from group consisting of water / alcohol soluble dyes such as direct dyes, acidic dyes, basic dyes, fluorescent dyes; from group consisting of reactive dyes such as vinyl solfones, isocyanurates, sulfonyl and carbonyl azides dyes, particularly when MPMS polymer particles have functional group that supports reaction or from group consisting of water / alcohol soluble Leuco compounds of vat dyes, of alizarin, quinizarin or anilines that develop colour on oxidation on contact with air; from group consisting of water / alcohol soluble components of dyes such as Naphthol or diazo dyes, mordents of mordant dyes, inorganic pigment components such as lead salts such as forming lead chromate, iron salts such as ferric salts forming iron oxide, phthalogens forming phlhalocyanine, that develop colour on subsequent contact with the corresponding coupling / colour forming component.
  • water / alcohol soluble dyes such as direct dyes,
  • the colour development could also be affected by using some part of the polymer support to partake in the reaction. These could be cyano groups or other aromatic phenolic groups which could be a part of the polymer or could be built over the functional groups of the polymers.
  • the colour content of the particles depended on the functional groups present on the polymer support and the strength of the reactive dye. For example, in a polymeric particle which had 9.1% by wt. of the monomers hydroxy functional monomers, the reactive dye content was 27.5 % by wL the dyed polymer. It could be increased to 30 % by wt. using high molecular wt. reactive dyes.
  • Drying of the coloured pigment particles is preferably by vacuum drying at ambient temperature.
  • the MPMS polymer particles are selected from acidic functional polymers.
  • the polymer chosen for making MPMS polymer particles is hydroxyl functional type.
  • Monomers are selected from group consisting of styrene, methyl methacrylate (MMA), acrylonrtrile (ACN).
  • Emulsifiers are selected from group consisting of a) Non-ionic emulsifiers such as nonyl phenol ethylene oxide (Nyp.EO) condensates, ethylene oxide (EO), propylene oxide (PO) co- or block co- polymers, castor oil derivatives, such as castor oil: ethylene oxide condensates, vegetable oil derivatives, silicones, fluorocarbons condensed with EO or EO.PO and / or Gemini surfactants; OR b) Anionic such as sodium lauryl sulphate (SLS)."dodecyl benzene sulphonate (DDBS), soap of different fatty acids or combinations thereof, naphthalinic sulphonate 0.1 - 10 % by wt on monomer and combinations thereof.
  • SLS sodium lauryl sulphate
  • DDBS diodecyl benzene sulphonate
  • Additives for functional groups Addition of a functional monomer 0.5 ⁇ 20 % by wt of total composition is optional. Any monomer having such functionality as carboxylic, amine, quaternary, amide, allyl chloride, hydroxyl, secondary hydroxyl, primary hydroxyl, sulfonic acid, methane sulfonic acid, are useful.
  • Functional monomers are preferably chosen from monomers such as acrylic acid, methacrylic acid, Hydroxy methyl acrylate or hydroxy ethyl acrylate HEMA, Gtycedyl Methacrylate, Acrylamide, 2-acrylamido, 2 methyl propane sulfonic acid (AMPS), Styrene sulfonic acid (SSA), Sulfonyl phenyl methallyl ether (SPME), Strong base Amine type monomers such as trimethyt amino ethanol methacrylate, or their precursors such as vinyl benzyl chloride (VBC), 2 hydroxy 3 chloro propyl methacrylate (CHPMA), 0 -20 % by wt of monomer.0.1 - 10 % by wt. of total composition are usually employed for this job.
  • monomers such as acrylic acid, methacrylic acid, Hydroxy methyl acrylate or hydroxy ethyl acrylate HEMA, Gtycedyl Methacrylate, Acrylamide
  • Cross-linking agent is essential and preferable amount is 15 - 20 % of the monomer mix.
  • Cross linking agents such as divinyl benzene (DVB), Ethylene glycol di methacrylate (EDMA), or any other cross linking agent such as poly functional derivatives of poly hydroxy alcohols and unsaturated acids for example glycerol trimethacrylate, penta erythritol tetra methacrylate or the like may be used from 0.1 - 100 % by wt. of total monomer.
  • Micro-porosity generating agents
  • Micro-porosity generating agents there are 4 types of Micro-porosity generating agents: a) Blowing agents such as low boiling liquids such as pentane, or fluorocarbons, azo bis isobutyronitrile, azodicarbonamide, sodium bicarbonate which blow off in to gaseous products on heating to 120 - 180 °C with or without added catalysts called kickers b) Solid paniculate material that dissolves in acid or alkali, such as calcium carbonate c) Non-crosslinkable polymer such as polystyrene .that dissolves in monomer mix and d) Solvents which are miscible with monomers but do not dissolve resulting polymers.
  • Blowing agents such as low boiling liquids such as pentane, or fluorocarbons, azo bis isobutyronitrile, azodicarbonamide, sodium bicarbonate which blow off in to gaseous products on heating to 120 - 180 °C with or without added catalysts called kickers
  • Solid paniculate material
  • the scope of the invention covers use of any of these Micro-porosity generating agents alone or in combination in the process of present invention.
  • the preferred Micro-porosity generating agent from ease of operation is a solvent with a boiling point below that of water and with very low water miscibility in which the polymer is insoluble
  • the preferred micro-porosity generating agents are selected from group of compounds such as aliphatic or aromatic solvents; primary, secondary or tertiary alcohols that stay unpolymerized in polymerization process and leave the microporous microsphers system on vaporization or on extraction with solvent and are preferably partially water soluble and having low boiling point or forming an azeotrope with water.
  • Micro-porosity generating agents are selected from group of solvents such as tetrahydronaphthalenes, iso butanol, iso amyl alcohol 2-ethyl ..exanol, cyclohexanol, C 12 .
  • Solvents such as iso-butyl alcohol are chosen to control porosity of the product.
  • the solvent chosen has to have low water solubility and low boiling point, preferably less than that of water; or forming an azeotrope with water.
  • Suspension medium Apart from the most preferred non solvent, water, Aliphatic, aromatic, alicyclic hydrocarbon solvents such as octane, toluene cyclohexane are used as suspension medium for polymerizing of monomer in Suspension State.
  • Aliphatic, aromatic, alicyclic hydrocarbon solvents such as octane, toluene cyclohexane are used as suspension medium for polymerizing of monomer in Suspension State.
  • Suspension agents are used as suspending agents in suspension polymerization. They are chosen from group of cnllnklal solution forming/ and protecting, substances such as polyvinyl alcohol, carboxymethyl cellulose, hydroxy ethyl cellulose, starch, lignin, and gelatin when watei is used as suspending medium. Chlorinated rubber can be used for organic medium. The preferred concentration of this agent is in the range of 0.1 to
  • Initiators Common radical polymerization initiators such as peroxides, hydroperoxides and persulfates can be employed for this purpose
  • Irradiation Alternately this polymerization can be brought about by irradiation also. This includes ultraviolet, ⁇ - and ⁇ -radiation produced by radioactive substances.
  • Polymerization temperature is 30 - 100 °C; in a closed container, allowing pressure to build up if necessary. Time for completion of reaction is about 7-8 hrs.
  • Coagulating agents are electrolytes, polyelectrolytes such as sodium chloride, sulphate, alum or cationic or anionic polyelectrolytes.
  • Particle size 0.05 - 5 ⁇ or more as per need; mono spheres or poly-disperse.
  • Pore size distribution 5 - 1000 A 0 narrow or wide as per the need.
  • Water insoluble matter not more than 0.1 % by wt of final polymer
  • Toxicity of. the polymer particles Non-toxic in most cases.
  • the monomers of acrylic type are- in use over number of years as parts of dental products and pharmaceutical preparations
  • the product of the present invention has many uses: the transparent microporous microsphers are useful to carry many organic / inorganic molecules. Particular microporous microsphers having functional groups are useful as carriers for fixing specific colourants; Colourants: These micro-porous microsphers form good substrate for dyeing with normal dyes as described here and the coloured particles so prepared are useful for food, pharmaceuticals, capsules, water based inks, cosmetics (creams, lotions), abrasives for tooth pastes, slow release low contact sunscreens. As pigments and colourants for plastics, sustained release odouronts, carriers of deodorants and medicines.
  • a monomer mixture was made as follows:
  • This monomer composition along with cross linking agent and solvent (monomer mixture) 232 parts was charged through reservoir for monomer in the usual stirred cylindrical glass reaction vessel with assembly providing thermometer, condenser, and Teflon blade stirrer in which was taken aqueous phase - water 250 parts containing 5 parts of an emulsifier sorbitol mono-oleate, and 2.5 parts of sodium lauryl sulfate (as emulsifying agents) over a period of 6 hours.
  • the emulsion (oil in water) was formed on stirring at room temperature.
  • Ammoniupri persulphate 0.2% by wt. on total wt. of monomer mixture added as polymerization initiator to the emulsion either in a single lot or over a period of time as a solid or as a solution.
  • the polymerization reaction was allowed to go to completion by heating the contents to and maintaining the mixing / stirring / homogenizing at 70 °C for 6 hours.
  • the solvent was distilled off by raisiny the temperature of the contents above 90 °C.
  • the mixture was then filtered, washed with demineralized water till the washings were free of NaCI and dried under vacuum of 300 mm Hg at 60-70 °C.
  • the particles were screened through 350 mesh to remove any grit material.
  • the product - microporous microsphers of the polymer particles, obtained (named MPMS-A) was 105 parts representing 90.5% yield of theoretical yield. Water insoluble matter was found to be not more than 0.1 % by wt of final polymer.
  • the product the microporous microspherical polymer particles obtained (named MPMS-B) showed 5.1 % grits, and the particles had 34.6 % pore volume and acid value 47.2.
  • microporous microspherical polymeric particles were prepared from monomer mix of particles of Styrene (commercial, purity 99.7 %by wt.) 54.6 % by wt., acrylonitrile (commercial, purity 99 %by wt.) 31.7% by wL, EGDMA (commercial grade containing 68 % by wt of Styrene (commercial, purity 99.7 %by wt.) 54.6 % by wt., acrylonitrile (commercial, purity 99 %by wt.) 31.7% by wL, EGDMA (commercial grade containing 68 % by wt of Styrene (commercial, purity 99.7 %by wt.) 54.6 % by wt., acrylonitrile (commercial, purity 99 %by wt.) 31.7% by wL, EGDMA (commercial grade containing 68 % by wt of Styrene (commercial, purity 99.7 %by w
  • microporous microspherical polymer particles obtained had the following specifications:
  • microporous microspherical polymeric particles were prepared by the process of Example I above except that the CDmposition of monomers used was, styrene 31.5 % by wt., methyl methacrylate 26.0 % by wt., EGDMA 10.0 % by wt., and HEMA 32.5 % by wt.
  • the microporous microspherical polymeric particles, prepared were screened, grit 3.4 % by wt. separated out.
  • Example 1 Example 2
  • Example 3 Example 4 MPMS-A MPMS-B MPMS-C MPMS-D
  • the particle size was determined by sedimentation and the porosity, by weight increase on saturating dry powder with water followed by filtration under vacuum. Microscopic examination of particles by electron microscopy revealed them to be perfectly spherical uniform particles .
  • Particle size 0.5 - 5 ⁇ or more as per need ; mono spheres or poly disperse particles can be controlled from 0.5 - 6 ⁇ by choosing right agitator in the polymerisation reaction
  • Porosity 0 - 70 % by vol. of the particles. Porosity can be controlled 0 - 70 % of the volume of particles by choosing right % concentration of the porogenic agent or the blowing agent.
  • Pore size distribution : 5 - 1000 A 0 narrow or wide as per the need can be obtained by varying the swellability of the polymer in the solvent
  • Example V Preparation 61 Bright Pink Pigment based on MPMS-A :
  • Rhodamin B 5 g was dissolved in 100-ml water to prepare the dyeing solution.
  • Example I 20g microporous microspherical polymeric particles obtained in Example I (MPMS-A) were added to the dyeing solution. The mixture was heated to 80 °C and the particles were allowed to soak for one hour.
  • the particles were separated by filtration, washed with demineralized water and dried in vacuum below 90 °C.
  • the bright pink coloured Pigment based on MPMS-A was obtained.
  • This example shows that there is no need to premix the moulding powder with this pigment, which is commonly required for organic or inorganic pigments.
  • a dyeing solution of a reactive dye Remazol Red D was prepared in water at a concentration of 100 gpl.
  • Example II The dried microporous microspherical polymer particles of Example II (MPMS -B) . were soaked in the above dyeing solution at room temperatures and the temperature was raised to 60 °C for 2 hrs. The dye was fixed by its reaction with the functional group. The product was washed, and dried as in Example V above.
  • the colour content of the particles depended on the functional groups present on the polymer support and the strength of the reactive dye. Since 9.1% by wt. of the monomers were hydroxy functional monomers, the reactive dye content was ⁇ 27.5] % by w the dyed polymer.
  • Example VII Preparation of Red Pigment based on MPMS -A:
  • Example 2 a pigment molecule was synthesized inside the hollow space micro pores of the microspherical polymeric particle.
  • a solution of ⁇ -Naphthol was prepared in an equimolar amount of alkali and it was filled inside the pores of the microporous microspherical polymeric particles obtained as per Example I (MPMS -A) by soaking the solution at room temperature and particles were dried without washing .
  • a solution of a diazotized p-nitroaniline was prepared at 5 °C.
  • the dry ⁇ -Naphthol deposited MPMS-A particles were soaked in the diazo solution of equivalent to the ⁇ -Naphthol . This resulted in coupling of the two components inside the pores of the microporous microsphers to give polymeric pigment particles.
  • the resulting pigment particles had bright red colour and a very fine texture.
  • Rhodamin B dye (Colour Index No. C I 560) 5 g was dissolved in 100 ml water to make the dyeing solution.
  • micro-porous microspherical polymeric particles prepared as per Example III were added to the dyeing solution.
  • the mixture was heated to 80 °C and the panicles soaked in it for one hour.
  • the dyed particles were separated by filtration, washed with water, and dried in vacuum below 90 °C.
  • the dry particles were screened through a 350 mesh sieve, removing a small portion of grit material.
  • Reactive dye Ramazole Red B 10 g was dissolved in 300 ml water containing sodium sulfate (Na 2 S0 4 1/2 H 2 0) 20g, sodium carbonate ( Na C0 3 ) 2.48g.
  • Example IV were added to the dyeing solution.
  • the mixt ⁇ re was heated to 80 °C for one hour, with addition of soda ash as required to maintain pH alkaline.
  • the dyed particles were then filtered and washed with water, and dried in vacuum, at 70 °C.
  • the bright red coloured Pigment based on MPMS-D was obtained.
  • Novinone Jade Green 10g. was dispersed in water 37 ml. To this dispersion was added
  • Example II MPMS-B with 1cc /g of pore volume. The particles were allowed to soak in the solution for an hour. The dyed particles were filtered, dried in the air for 30 minutes at 60 °C and finally in vacuum at 80 °C /300mm Hg.
  • the green coloured particles were found useful for colouring polyethylene as in ⁇ Example I.
  • Example 3 a pigment molecule was synthesized inside the hollow space of the microporous microspherical polymer particles MPMS-C, prepared as described in Example III and having 50% porosity.
  • ⁇ -naphthol solution 20 % by wt. was prepared in an alkali .
  • the quantity taken was equal to pore volume of MPMS-C polymer particles to be soaked in it. After soaking the porous polymeric pigment particles with the above solution , the particles were dried. 10
  • Example XJJ Preparation of Blue Copper phthalocyanine Pigment based on MPMS-A: Materials used in this example were : Phthaloge ⁇ , Copper chloride and Urea. A solution of phthalogen (6 %) by wL in alcohol was prepared. Urea (3.5 %)was added to it with 1% cuprous chloride. Micro-porous microspherical polymeric particles MPMS-A (100g), prepared as per process of Example I, were added to- the dyeing solution till it was saturated. The particles were filtered and dried at 80 °C and repeatedly soaked in the same solution till about 20% phthalocyanine was Jeposited in the pores of the particles and dried at 130 °C _tor 10 min.
  • the process of present invention is simple and provides beautiful microporous microspherical (MPMS) polymeric particles, which are opaque or transparent. Such particles find a variety of applications, the central point of their utility lies around their ability to hold different molecules in their pores. Their major application is in forming a base for making pigments. These particles can be converted into coloured particles by dyeing with basic, acidic, reactive, disperse or any other form of dyes suitable for dyeing textile fibres or precipitating pigmentary materials in these pores by carrying out the reaction in side the pore.
  • MPMS microporous microspherical
  • Polymeric pigment particles of the present invention made by using reactive dves are non- toxic and could be used for colouring food products or pharmaceutical preparations.
  • these pigments could be successfully used for blending with several commercial polymers such as polyethylene, polypropylene, polystyrene without any dispersing aid. These may be specially prepared from monomers, which have identical solubility parameter as that of the polymer in which they are desired to be added thus increasing their compatibility.
  • processes such as rotational moulding which are known to be zero shear processes, the dispersion of the colour was very uniform and the properties of the plastics remained substantially unaffected as seen from Table 2 The tensile strength, the elongation at break and the uniformity of colour were reasonably unaffected even when pigments were simply blended with the powders prior to rotational molding.
  • the tensile strength of the plastic is not significantly altered by the presence of as much as 1% polymeric pigment which is more than adequate for saturating the colour of the plastic. % elongation is , how ever affected on pigment loading beyond 2%.

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PCT/IN2000/000025 1999-03-19 2000-03-21 A process for production of micro-porous microspheres of polymers and polymeric pigments therefrom WO2000064953A1 (en)

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DE10112561A1 (de) * 2001-03-15 2002-10-02 Infineon Technologies Ag Verfahren zur Erzeugung von porösen Schichten
GB2427869A (en) * 2005-07-01 2007-01-10 Petrochina Co Ltd Drag reducing polymers and oil dispersions
WO2008041001A1 (en) * 2006-10-07 2008-04-10 Regentec Limited Porous particles
EP2036927A1 (en) * 2007-09-11 2009-03-18 Fujifilm Corporation Ionic polymer particle dispersion liquid and method for producing the same
CN101798372A (zh) * 2010-04-13 2010-08-11 苏州大学 一种聚合物微球及其制备方法
US7878644B2 (en) 2005-11-16 2011-02-01 Gerber Scientific International, Inc. Light cure of cationic ink on acidic substrates
WO2010077094A3 (en) * 2008-12-31 2011-05-19 Kolon Industries, Inc. Spherical polymer beads and preparation method thereof
CN101701054B (zh) * 2009-12-01 2011-06-29 福州大学 一种多孔聚合物微球的表面修饰方法
CN102432744A (zh) * 2011-09-07 2012-05-02 天津大学 一种制备单分散功能聚合物微球的方法
CN104275161A (zh) * 2014-11-07 2015-01-14 中国科学院兰州化学物理研究所 一种粒状阳离子染料吸附剂及其制备方法
TWI476233B (zh) * 2008-12-31 2015-03-11 Kolon Inc 球形聚合物珠粒及其製備方法
CN107936167A (zh) * 2017-12-21 2018-04-20 苏州希尔盖森新材料有限公司 一种具有亲水性的聚苯乙烯微球
US10441548B2 (en) 2015-11-12 2019-10-15 Graybug Vision, Inc. Aggregating microparticles for medical therapy
CN111650292A (zh) * 2020-04-20 2020-09-11 广东省测试分析研究所（中国广州分析测试中心） 一种致病性大肠杆菌非靶向挥发性代谢物的富集和检测方法及其应用
US11160870B2 (en) 2017-05-10 2021-11-02 Graybug Vision, Inc. Extended release microparticles and suspensions thereof for medical therapy
CN114100679A (zh) * 2021-12-03 2022-03-01 王义成 一种树脂催化剂及其制备方法和应用
CN114516931A (zh) * 2022-02-25 2022-05-20 苏州仁端生物医药科技有限公司 一种基于静电作用的纳米级彩色微球制备方法
WO2022247375A1 (zh) * 2021-05-24 2022-12-01 上海交通大学 一种二次电池用含硫正极材料、其制备方法及二次电池
US11548861B2 (en) 2017-03-23 2023-01-10 Graybug Vision, Inc. Drugs and compositions for the treatment of ocular disorders
CN115651267A (zh) * 2022-11-10 2023-01-31 河北德福佳昌化工有限公司 一种循环水阻垢剂
CN117903356A (zh) * 2024-03-19 2024-04-19 四川省纺织科学研究院有限公司 双交联型无酚无醛酸性固色剂及其制备方法和应用

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US5492960A (en) * 1994-10-28 1996-02-20 Eastman Kodak Company Method of making polymeric particles
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Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273821B2 (en) 2001-03-15 2007-09-25 Infineon Technologies Ag Method for producing a porous coating
DE10112561C2 (de) * 2001-03-15 2003-12-18 Infineon Technologies Ag Verfahren zur Erzeugung von auf einem Substrat haftenden porösen organischen Schichten
DE10112561A1 (de) * 2001-03-15 2002-10-02 Infineon Technologies Ag Verfahren zur Erzeugung von porösen Schichten
GB2427869B (en) * 2005-07-01 2010-06-30 Petrochina Co Ltd An oil-based dispersing method of drag reduction polymers
RU2412395C2 (ru) * 2005-07-01 2011-02-20 Петрочайна Компани Лимитед Дисперсная композиция на основе масла, содержащая полимеры для снижения гидравлических потерь, и способ ее получения
GB2427869A (en) * 2005-07-01 2007-01-10 Petrochina Co Ltd Drag reducing polymers and oil dispersions
US7878644B2 (en) 2005-11-16 2011-02-01 Gerber Scientific International, Inc. Light cure of cationic ink on acidic substrates
US7896485B2 (en) 2005-11-16 2011-03-01 Gerber Scientific International, Inc. Light cure of cationic ink on acidic substrates
WO2008041001A1 (en) * 2006-10-07 2008-04-10 Regentec Limited Porous particles
EP2036927A1 (en) * 2007-09-11 2009-03-18 Fujifilm Corporation Ionic polymer particle dispersion liquid and method for producing the same
TWI476233B (zh) * 2008-12-31 2015-03-11 Kolon Inc 球形聚合物珠粒及其製備方法
WO2010077094A3 (en) * 2008-12-31 2011-05-19 Kolon Industries, Inc. Spherical polymer beads and preparation method thereof
CN101701054B (zh) * 2009-12-01 2011-06-29 福州大学 一种多孔聚合物微球的表面修饰方法
CN101798372A (zh) * 2010-04-13 2010-08-11 苏州大学 一种聚合物微球及其制备方法
CN101798372B (zh) * 2010-04-13 2011-09-14 苏州大学 一种聚合物微球及其制备方法
CN102432744A (zh) * 2011-09-07 2012-05-02 天津大学 一种制备单分散功能聚合物微球的方法
CN104275161A (zh) * 2014-11-07 2015-01-14 中国科学院兰州化学物理研究所 一种粒状阳离子染料吸附剂及其制备方法
US11331276B2 (en) 2015-11-12 2022-05-17 Graybug Vision, Inc. Aggregating microparticles for medical therapy
US11564890B2 (en) 2015-11-12 2023-01-31 Graybug Vision, Inc. Aggregating microparticles for medical therapy
US10441548B2 (en) 2015-11-12 2019-10-15 Graybug Vision, Inc. Aggregating microparticles for medical therapy
US11548861B2 (en) 2017-03-23 2023-01-10 Graybug Vision, Inc. Drugs and compositions for the treatment of ocular disorders
US11160870B2 (en) 2017-05-10 2021-11-02 Graybug Vision, Inc. Extended release microparticles and suspensions thereof for medical therapy
CN107936167A (zh) * 2017-12-21 2018-04-20 苏州希尔盖森新材料有限公司 一种具有亲水性的聚苯乙烯微球
CN111650292A (zh) * 2020-04-20 2020-09-11 广东省测试分析研究所（中国广州分析测试中心） 一种致病性大肠杆菌非靶向挥发性代谢物的富集和检测方法及其应用
WO2022247375A1 (zh) * 2021-05-24 2022-12-01 上海交通大学 一种二次电池用含硫正极材料、其制备方法及二次电池
CN114100679A (zh) * 2021-12-03 2022-03-01 王义成 一种树脂催化剂及其制备方法和应用
CN114516931A (zh) * 2022-02-25 2022-05-20 苏州仁端生物医药科技有限公司 一种基于静电作用的纳米级彩色微球制备方法
CN115651267A (zh) * 2022-11-10 2023-01-31 河北德福佳昌化工有限公司 一种循环水阻垢剂
CN117903356A (zh) * 2024-03-19 2024-04-19 四川省纺织科学研究院有限公司 双交联型无酚无醛酸性固色剂及其制备方法和应用
CN117903356B (zh) * 2024-03-19 2024-05-31 四川省纺织科学研究院有限公司 双交联型无酚无醛酸性固色剂及其制备方法和应用

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