WO2005026225A1 - Procede pour fabriquer des particules polymeres micro metriques monodispersees spheriques a granulometrie controlee - Google Patents

Procede pour fabriquer des particules polymeres micro metriques monodispersees spheriques a granulometrie controlee Download PDF

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WO2005026225A1
WO2005026225A1 PCT/IB2004/002997 IB2004002997W WO2005026225A1 WO 2005026225 A1 WO2005026225 A1 WO 2005026225A1 IB 2004002997 W IB2004002997 W IB 2004002997W WO 2005026225 A1 WO2005026225 A1 WO 2005026225A1
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particles
monomer
alkyl
dye
process according
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PCT/IB2004/002997
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Hans-Joachim Metz
Jean-Christophe Graciet
Jingshe Song
Mitchell A. Winnik
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Hans-Joachim Metz
Jean-Christophe Graciet
Jingshe Song
Winnik Mitchell A
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Publication of WO2005026225A1 publication Critical patent/WO2005026225A1/fr

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    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Definitions

  • This invention relates to a two-stage process for making spherical, controlled-size micrometer polymer particles from dispersion polymerization compositions, wherein the obtained particles have a very narrow or monodisperse size distribution.
  • a very narrow or monodisperse size distribution pertains to particles in which the coefficient of variation (CV) of particle diameters is preferably less than 5 % and more preferably less than 3 %.
  • the invention relates to a two-stage process for making crosslinked, spherical, controlled-size micrometer polymer particles from dispersion polymerization compositions, wherein the obtained particles have a very narrow or monodisperse size distribution.
  • the obtained spherical, controlled-size micrometer polymer particles further comprise a fluorescent or non-fluorescent dye attached the polymer chain.
  • the invention relates to a two-stage process for making crosslinked and dyed, spherical, controlled-size micrometer polymer particles from dispersion polymerization compositions, wherein the obtained particles have a very narrow or monodisperse size distribution and have pigment-like properties.
  • Polymer beads with diameters between 40 to 600 nm can be prepared by traditional emulsion polymerization methods developed by the paint industry. Larger diameter beads can be made by precipitation polymerization, seeded polymerization or by activated swelling and polymerization methods.
  • US 5,496,897 discloses a two-step seeded polymerization process for preparing uniformly sized, fine polymer particles in aqueous dispersions, wherein in a first step a non-ionic organic compound is admixed with an oil-soluble, ethylenically unsaturated monomer and the mixture is added to an aqueous dispersion of seed polymer particles, so as to make the mixture adsorb into the particles. In a second step the polymerization is initiated with an oil-soluble initiator.
  • EP 0 003 905 and US 4,530,956 disclose a two-step process for aqueous dispersion polymerization, wherein in a first step a dispersion of polymer particles containing one or more materials having a very low solubility in water is formed, and, in a second step, a partly water-soluble material is added, which diffuses into the polymer particles obtained in the first step.
  • said partly water-soluble material is a polymerizable monomer its polymerization can be effected after diffusion into the polymer particles.
  • EP 0 326 383 discloses a similar process (often referred to as the "dynamic swelling” method) to prepare monodisperse polymer particles having increased particle size in a diameter range around 8.5 ⁇ m.
  • the invention of the single-step dispersion polymerization process has greatly facilitated the preparation of monodisperse beads with micrometer diameters, making it a very attractive procedure for a large-scale preparation.
  • Dispersion polymerization is defined as a polymerization reaction in which the monomer is soluble, but the polymer is not. The polymer begins to precipitate as it is formed. Dispersion polymerization differs from precipitation polymerization in that it is carried out in the presence of a second soluble polymer (the dispersant or steric stabilizer). The dispersant becomes attached to the surface of the precipitating polymer formed in the reaction, and forces the precipitate to form micron-sized beads.
  • the reaction mixture for dispersion polymerization is a single-phase (a homogeneous liquid), consisting of a solution of monomers, initiator, and steric stabilizer in a solvent that does not dissolve the resultant polymer.
  • the initial stage is believed to occur as a typical solution polymerization.
  • the polymeric chains grow in size until they become insoluble in the reaction medium.
  • the polymer then precipitates from the solution. This step is called the nucleation step.
  • the steric stabilizer forms a graft copolymer and both the graft polymer as well as the ungrafted stabilizer, adsorb on the surface of the particles and prevent their coalescence. Particle growth can then occur by polymerization within the monomer-swollen stabilized particle and by precipitation of polymer formed in the medium onto the growing particle.
  • a wide variety of monomers have been used in dispersion polymerizations. These include methyl methacrylate, styrene, vinyl acetate, vinyl chloride, acrylamide, acrylic acid, vinylpyrrolidone, acrylonitrile, and 4-chloromethylstyrene. Dispersion polymerization has also been used for the preparation of copolymers of styrene with a variety of different monomers.
  • US 6,346,592 discloses compact and spherical polymer particles with a narrow size distribution and a process for their production.
  • the special precipitation polymerization process is carried out in a polar organic medium (or such medium mixed with water), wherein the medium is a good solvent for the monomer and a poor solvent for the polymer.
  • the disclosed process is a one-stage process, i.e. all ingredients are present when the polymerization is initiated.
  • a process for making spherical, controlled-size micrometer polymer particles from dispersion polymerization compositions, wherein the obtained particles have a very narrow or monodisperse size distribution is of interest in the art.
  • a particular interest in the art is the synthesis of colored, spherical, controlled-size micrometer polymer particles from dispersion polymerization compositions, wherein the obtained particles have a very narrow or monodisperse size distribution.
  • Such particles, in particular fluorescent particles can be used in medical diagnostic applications.
  • WO 02/066483 discloses copolymer compositions having pigment like properties comprising a fluorescent or non-fluorescent dye attached to a polymer chain by a spacer.
  • WO 02/066483 further discloses a copolymerisation process to obtain latex particles in a diameter range from 50 to 100 nm, by radical initiated suspension (or miniemulsion) polymerisation in water.
  • the disclosed process is a one-stage process.
  • the physical properties of polymer particles highly depend on the structure of the polymerisable moiety and on the process of polymerization.
  • a typical problem of copolymerisation in general is, that each monomer has its own copolymerization parameters, in the extreme not being copolymerizable at all.
  • WO 02/066483 therefore proposes a concept to allow variation of the dye moieties without significantly changing the copolymerization parameters of the dye monomers, by separating the polymerizable moiety and the dye moiety from each other with a spacer.
  • the spacer is further optimized in chain length and nature to enhance the dye properties in the matrix.
  • WO 02/066483 discloses compounds of the general formulae (a) and (b)
  • R ⁇ is inter alia defined to be substituted or unsubstituted C 3-6 alkylene, C 3-6 alkoxylene or C 6-10 arylene, preferably (CH 2 ) 2 , (CH 2 ) 6 and (CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 2 .
  • Dreyfus et al. describe the use of the following compound (c) as part of a study on the effects of copolymerisation conditions on the viscosity and molecular weight distribution of styrene dye compounds.
  • the objective of the present invention is to provide a process of making spherical controlled-size polymer particles from a copolymer composition in dispersion polymerisation.
  • the obtained particles shall be uniform and of regular shape with a diameter of 1 to 10 ⁇ m, preferably with a diameter of 2 to 6 ⁇ m, and more preferably with a diameter of 2 to 3 ⁇ , with a very narrow or monodisperse size distribution.
  • a very narrow size distribution pertains to particles in which the coefficient of variation (CV) of particle diameters is less than 10%, preferably less than 5 % and more preferably less than 3 %.
  • a monodisperse size distribution pertains to particles in which the coefficient of variation (CV) of particle diameters is less than 5 %, preferably less than 3 % and more preferably less than 1%.
  • D m is the average diameter of all particles
  • D is the diameter of the h particle
  • n is the total number of particles counted in the analysis.
  • a further objective of the present invention is to provide a process of making monodisperse, crosslinked and/or dyed, spherical, controlled-size micrometer polymer particles from a copolymer composition in dispersion polymerisation.
  • a two-stage process is suitable for making monodisperse spherical controlled-size micrometer particles.
  • This two-stage process allows one to control the desired diameter of the polymer particles within the range of 1 to 10 ⁇ m. It also allows the synthesis of particles in which polymerizable dye derivatives can be covalently attached to the polymer chains and it allows one to synthesize crosslinked polymer particles with a diameter from 1 to 10 ⁇ m.
  • the crosslinked and dyed final particles have pigment-like properties and contain covalently bound dye monomers with an absorption at 330-380nm.
  • the invention therefore relates to a process of making monodisperse spherical controlled-size polymer particles comprising the steps of
  • a) providing a dispersion polymerization composition comprising a monomer or a co- monomer mixture, an alcohol or an alcohol mixture, a polymer dispersant and an initiator, b) reacting the monomer or the co-monomer mixture under normal dispersion polymerization conditions until a stable particle dispersion with a defined number of particles is obtained,
  • step (b) growing the particles of step (b) to a size in the micrometer range by adding more monomer solution or more of the co-monorner mixture solution to the reaction and
  • step (b) simultaneously cross-linking and/or dyeing the particles of step (b) by adding a cross-linking agent and/or dye monomer that is soluble in the reaction medium.
  • the important feature of the preferred embodiment of the invention is that the addition of the cross-linking agent and/or the dye monomer is delayed to the second stage. Thereby the number of particles in the system is established in the (sensitive) first stage, without any cross-linking agent or dye monomer being present. Only in the (less sensitive) second stage the polymer particles are grown, cross-linked and/or dyed, simultaneously maintaining a narrow size distribution.
  • the first stage is considered complete at less than 1% conversion of the monomer present in the initial reaction.
  • reaction conditions are chosen by adjusting the monomer and polymeric stabilizer concentrations to give particles with a diameter approximately 10% smaller than the desired diameter.
  • an aliquot is removed from the reaction mixture and is tested for particle size and extent of conversion. Based upon this information, a final particle size is calculated for the case of complete conversion.
  • additional monomer is added to the reaction in the second stage. With the additional monomer additional solvent is added optionally to maintain the solvency of the medium. The amount of additional monomer is the amount necessary for the desired/calculated increase in particle diameter.
  • the particles are cross-linked or dyed in the second stage.
  • the particles are cross-linked and dyed in the second stage.
  • crosslinker up to 0.1 % or 0.2 % by weight based on the total amount monomer
  • the crosslinker will change the particle size, but has only small deleterious effects on the size distribution.
  • a preferred class of dye monomers are imides obtained from 1 ,8-naphthalic anhydride or 1 ,4,5,8-tetracarboxylic naphthalene di-anhydride, preferably with an absorption at 330-380 nm, wherein most preferably the dye moiety is separated from the polymerizable moiety by a spacer.
  • Another possible class of dye monomers are cyanine dyes such as acrylamide derivatives of 5- or 6-aminofluorescein or rhodamine B methacrylate (availble from Polysciences Corp), with an absorption ranging from 450 to 700 nm.
  • cyanine dyes such as acrylamide derivatives of 5- or 6-aminofluorescein or rhodamine B methacrylate (availble from Polysciences Corp), with an absorption ranging from 450 to 700 nm.
  • the dye monomers preferably with an absorption at 330-380 nm, are selected form the group consisting of the compounds with the general formulae (I), (II) and (III)
  • G is hydrogen or methyl
  • X is oxygen or NR' with R' being hydrogen, C 1-6 alkyl, C 6- ⁇ o aryl, (C 6- ⁇ 0 ) aryl- (C 1-6 ) alkyl or (C 1-6 ) alkyl-(C 6 - ⁇ 0 ) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl (-OH), C 1-6 alkoxyl, halogen (-F, -CI, -Br, -I), cyano (-CN), nitro (-N0 2 );
  • Ri is C 1-6 alkyl, C 6-10 aryl, (C 6-10 ) aryl-(C 1-6 ) alkyl or (C 1-6 ) alkyl-(C 6-10 ) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl (-OH), C 1-6 alkoxyl, halogen (-F, -CI, -Br, -I), cyano (-CN), nitro (-NO 2 );
  • R 2 to R 7 are independently of one another, represent hydrogen, hydroxy (-OH), halogen (-F, -CI, -Br, -I), cyano (-CN), nitro (-NO 2 ), C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkylthio, -SO 3 H, -SO 2 Rn, -SOaNRnR ⁇ , -CO 2 Rn, -CONRnR ⁇ , - NHCORn, in which R11 and R
  • R 8 is hydrogen, C 1-6 alkyl, C 6- ⁇ o aryl, (C 6-10 ) aryl-(C 1-6 ) alkyl or (C 1-6 ) alkyl-(C 6- ⁇ o) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl (-OH), C 1-6 alkoxyl, halogen (-F, -CI, -Br, -I), cyano (-CN), nitro (-NO 2 ).
  • R represents a substituted or unsubstituted annealed aromatic ring system comprising at least one heteroatom in either the first or the second ring or in both, selected from one of the moieties (1 ) to (4).
  • the preferred spacer R is a C 2-6 alkylen or C 6 . 10 arylen, most preferably C 2 alkylen, C 6 alkylen or a C 6 arylen, preferably substituted by nitro, alkoxy or halogen, more preferably substituted by methyloxy or halogen, most preferably substituted by chlorine.
  • Preferred polymerizable groups are methacrylate ester groups, acrylate ester groups, methacrylamide or acrylamide groups, most preferably methacrylate ester or acrylamide groups.
  • Most preferred dye monomers are of the general formula (I).
  • the dye monomers of formulae (I), (II) and (III) are obtained by the condensation of the dicarboxylic anhydride of the respective dye moiety with an amino alcohol or a diamine comprising the respective spacer in a polar aprotic solvent.
  • A is the 1 ,8 naphthalene core or the 1,4,5,8 naphthalene core as defined in formula (I), (II) and (III) above.
  • the hydroxy or amino group on the free end of the spacer can be further functionalized under acid or basic conditions with acrylic or methacrylic acid or derivates thereof, such, as the acid chloride.
  • the final product is obtained in high yield.
  • A is defined by naphthalene carboxylic anhydride or naphthalene tetracarboxylic dianhydride, Ri, X and G are as defined above.
  • the first stage of the copolymerization process according to the invention is usually carried out as a radical initiated dispersion polymerisation process in polar and protic solvent (in particular in alcohols such as ethanol, methanol, isopropanol) with an optional organic co-solvent (such as toluene, dichlorobenzene).
  • polar and protic solvent in particular in alcohols such as ethanol, methanol, isopropanol
  • organic co-solvent such as toluene, dichlorobenzene.
  • the preferred polar protic solvent is ethanol.
  • co-solvent is to help dissolve the dye in the reaction medium.
  • the preferred content of co-solvent (such as toluene, dichlorobenzene) according to the invention is from 0 to 10, more preferably from 0 to 6 and most preferably from 1 to 3 percent by weight based on the total weight of solvent used.
  • Chain growth monomers suitable for the above process can be acrylate esters, methacrylate esters, styrene, styrene derivatives such as ortho-, meta- or para-methyl styrene, chlorostyrene, vinyl acetate, vinyl chloride, and acrylonitrile.
  • Preferred chain growth monomers are selected from the group consisting of acrylate, methacrylate, styrene or para-methylstyrene, most preferably styrene.
  • Optionally functional monomers can be incorporated into the reaction, preferably in the second stage.
  • These monomers include ethylenically unsaturated carboxylic acids or hydroxy-substituted carboxylate esters, including vinylbenzoic acid, methacrylic acid, itaconic acid, acrylic acid, hydroxyethylacrylate, or hydroxyethylmethacrylate, glycidyl methacrylate, tBoc-protected or other protected derivatives of para-aminostyrene, preferably methacrylic acid, tBoc-protected para-aminostyrene or hydroxyethylmethacrylate.
  • carboxylic acids or hydroxy-substituted carboxylate esters including vinylbenzoic acid, methacrylic acid, itaconic acid, acrylic acid, hydroxyethylacrylate, or hydroxyethylmethacrylate, glycidyl methacrylate, tBoc-protected or other protected derivatives of para-aminostyrene, preferably methacrylic acid,
  • Further functional monomers are ortho, meta-, or para- substitued styrene derivatives, preferably meta- or para-chloromethylstyrene or meta- or para-vinylphenol, or meta- or para-hydroxymethylstyrene, and most preferably, meta- or para-chloromethylstyrene.
  • Further functional monomers are aminoalkyl methacrylates, hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • the purpose of these monomers is to introduce functional groups, preferably at the particle surface, for the attachment of dyes, antibodies, DNA fragments, nucleic acid oligomers, proteins, peptides, oligosaccharides, or other groups.
  • the functional momoner or mixture of functional monomers are added in a final addition step, when the conversion of monomer to polymer in the second stage is between 50% and 95% complete, preferably between 60 and 90% complete and most preferably between 70% and 85% complete.
  • Initiators for the polymerization are oil-soluble initiators.
  • Preferred initiators are lauroyl peroxide, benzoyl peroxide, 2,2'-azobis(iso-butyronitrile) (AIBN) or 2,2'-azobis(2- methylbutyronitrile) (AMBN), most preferably 2,2'-azobis(2-methylbutyronitrile) (AMBN).
  • the preferred content of initiator is from 1 to 10, more preferably from 1 to 5 and most preferably between 1 and 2 percent by weight based on the total weight of the chain growth monomer.
  • a particularly preferred feature of the present invention is that the initiator is added only in the first stage of the polymerization process.
  • Any polymeric dispersant effective for dispersion polymerization in alcohol solvents will work for the process of the present invention.
  • examples include polyvinylpyrrolidone
  • PVP poly(2-ethyl-2-oxazoline), hydroxypropyl cellulose (HPC), poly(ethylene oxide), or poly(acrylic acid) (PAA).
  • a preferred polymeric dispersant is polyvinylpyrrolidone (PVP).
  • a nonionic surfactant such as an ethoxylated alkylphenol, or an ionic surfactant such as Aerosol OT, can be added to the reaction mixture.
  • a preferred surfactant is Triton ® X- 305, which is an octylphenol ethoxylate with a mean degree of ethoxylation of 30, and which is available from Union Carbide Corp.
  • the preferred content of polymeric dispersant is from 10 to 30, more preferably from 15 to 25 and most preferably between 16 and 20 percent by weight based on the weight of the chain growth monomer present in the first stage of the reaction.
  • the dye monomer is only added after the polymer particles have formed and their number is established.
  • the preferred content of the polymerizable dye-monomer in the particles according to the invention is from 0.01 to 10, more preferably from 1 to 5 and most preferably between 2 and 3 percent by weight based on the total weight of the final particles.
  • cross-linking agent if cross-linking agent is added, the cross-linking agent is only added after the polymer particles have formed and their number is established.
  • the copolymer particles are thereby obtained as monodisperse, fine latex particles of very uniform regular spherical shape wherein the particle diameter deviates with a coefficient of variation (CV) of less than 10%, and preferably less than 5%, and most preferably, less than 3%.
  • the average particle diameter is from 1 to 10 ⁇ m, preferably from 2 to 6 ⁇ m and most preferably from 2 to 4 ⁇ m.
  • Figure 1 shows an optical microscope image of dye-labeled polystyrene particles manufactured according to the process of the invention, containing 1 wt% of NSA- DCAR-MMA (according to example 8).
  • Figure 2 shows a scanning electron microscope (SEM) image of dye-labeled polystyrene particles manufactured according to the process of the invention, containing 1 wt% of NSA-DCAR-MMA (according to example 8).
  • Figure 5 shows the correlation of the particle volume (proportional to D 3 ) and the amount of styrene added (according to example 3). A total of five aliquots of the same amount of styrene (St) and ethanol was added and the diameter (D) of the paricles was determined. The particle size (particle volume D 3 ) increases linear with the amount of styrene.
  • Figure 6 shows an optical microscope image of polystyrene particles manufactured according to example 3 at the points where the aliquots of the same amount of styrene (St) and ethanol were added and where the diameters (D) of the paricles were determined.
  • the particle size distribution remains monodisperse.
  • Figure 7 shows a scanning electron microscope (SEM) image of dye-labeled polystyrene particles manufactured according to the process of the invention, containing 1.35 wt%, 1.55 wt %, 1.85 wt %, 8.1 wt % of NY-E3-NMA (according to example 10)
  • step (c) and (d) the second stage monomer or co-monomer mixture, the cross-linking agent and/or the dye monomer and optionally additional solvent are added at once.
  • the cross-linking agent and/or the dye monomer and optionally additional solvent are added slowly in small amounts.
  • the colored particles according to the invention are suitable as pigments or coloring agents in polymer applications.
  • the fluorescent particles according to the invention are suitable for biomedical and medical diagnostic applications if functional monomers are introduced in the second stage of the reaction to put reactive functional groups such as carboxylic acid, primary alcohol, or amino groups at the particle surface.
  • copolymer pigments in the following:
  • the copolymer pigments according to the invention are suitable for the mass pigmentation of substrates including synthetic polymers, synthetic resins and regenerated fibers optionally in the presence of solvents.
  • substrates more particularly include oil, water and solvent based surface coatings, polyester spinning melts, polyethylene, polystyrene and polyvinyl chloride melts, polymethacrylate and polymethylmethacrylate melts, polyurethane masses, rubber and synthetic leather.
  • the pigments can be used in the manufacture of printing inks, for the mass coloration of paper and for coating and printing textiles.
  • copolymer pigments according to the invention are also suitable as pigments in electrophotographic toners and developers, such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and specialty toners.
  • electrophotographic toners and developers such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and specialty toners.
  • Typical toner binders are addition polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, polysulphones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may comprise further constituents, such as charge control agents, waxes or flow assistants, or may be modified subsequently with these additives.
  • polyaddition and polycondensation resins such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, polysulphones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may comprise further constituents, such as charge control agents, waxes or flow assistants, or may be modified subsequently with these additives.
  • copolymer pigments according to the invention are suitable, furthermore, as colorants in powders and powder coating materials, especially in triboelectrically or electrokinetically sprayable powder coating materials which are used for the surface coating of articles made, for example, from metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
  • Powder coating resins that are typically employed are epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane resins and acrylic resins, together with customary hardeners. Combinations of resins are also used. For example, epoxy resins are frequently employed in combination with carboxyl- and hydroxyl-containing polyester resins.
  • Typical hardener components are, for example, acid anhydrides, imidazoles and also dicyanodiamide and its derivatives, blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
  • the particle size in the examples is examined by optical microscopy and scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the molecular weight and molecular weight distribution are determined by gel permeation chromatography (GPC).
  • the dye content is determined by UV-VIS absorption measurements or, for soluble polymers, by GPC coupled with UV-VIS detection.
  • Example 1 Synthesis of NSA-DCAR-MMA dye monomer Naphthalene carboxylic anhydride (10 parts) is condensed to 2,5-dichloro- paraphenylenediamine (18 parts) at 130°C under nitrgogen atmosphere in presence of catalytic p-toluene sulfonic (0.1 part) acid in dimethylformamide (50 parts). After reaction completion at same temperature, the resulting mixture is cooled to room temperature. After filtration and washing with 50 parts of methanol, the cake is dried under vacuum for 4 hours. The product (18 parts) is then suspended in 100 parts of toluene in presence of 5.6 parts of triethylam ⁇ ne at 80°C.
  • reaction mixture 5.8 parts of methylmethacryloyl chloride are then added over 30 minutes to the suspension and the whole reaction mixture stirred for 4 hours at 90°C. After reaction completion, reaction mixture is cooled to 60°C, filtered and washed with 30 parts of methanol and 30 parts of water. After drying, the final dye monomer is obtained with 95% yield (20 parts) as a colorless product.
  • Example 2 Synthesis of NTCA-C2-M MA dye monomer 10 parts of naphthalene tetracarboxylic dianhydride are suspended into 100 parts dimethylformamide in presence of 4.6 parts of 2-ethanolamine and p-toluenesulfonic acid (0.1 part). The mixture is then heated to 90°C and stirred until reaction completion. The resulting colorless solution is cooled to room temperature and filtered. The presscake is then washed with methanol and dried. 12.5 parts of colorless powder are obtained (yield 94%). The product is then suspended into 75 parts of o- dichlorobenzene in presence of 7.5 parts of triethylamine and heated to 90°C.
  • Methylmethacryloyl chloride (7.8 parts) are added over 45 minutes and the reaction mixture is stirred at this temperature for 5 hours. After reaction completion, the mixture is cooled to room temperature, filtered and washed with 50 parts of methanol and then with 50 parts of water. Product is dried and obtained in 95% yield (16.3 parts) as a colorless compound.
  • Comparative Example 4 Synthesis of monodisperse polystyrene particles (one stage process according to the prior art)
  • example 3 In the first part of example 3 (dispersion polymerization separated into two stages, a "nucleation stage” and a “particle growing stage") only half of the styrene and ethanol were added at the beginning of the dispersion polymerization together with the stabilizer (PVP), the co-stabilizer (Triton X-305) and the initiator (AMBN). In example 4 (dispersion polymerization in one stage) the full amount of the styrene and ethanol were added at the beginning of the dispersion polymerization together with the stabilizer (PVP), the co-stabilizer (Triton X-305) and the initiator (AMBN).
  • the particle size obtained in the two stage process as of the invention is larger than in the one-stage process of example 4, where all the reactants are added initially to the reaction mixture.
  • Example 3 was continued to further increase the size of the particles. Before most of the monomer added in the second stage had reacted, another aliquot containing the same amount of styrene and ethanol was added to the reaction. No additional initiator or PVP was added at this stage. As the reaction continued, the particle size continued to increase. The beads remained colloidally stable in the solution. A total of five aliquots of the same amount of styrene and ethanol was added. The particle size continued to increase.
  • Example 8 Synthesis of size-controlled dyed monodisperse particles of PS-co-(1 wt%-NSA-DCAR- A) polymer (two-stage process)
  • Example 9 Synthesis of size-controlled dyed monodisperse particles of PS-co-(3.1 wt%-NSA-DCAR-MMA) polymer (two-stage process)
  • a hot prepared solution (70°C) of styrene (6.25 g) and NSA-DCAR-MMA dye (0.391 g) [as obtained from example 1] in ethanol (19 g) is added to the reaction mixture at 70°C under nitrogen atmosphere over 10 minutes. Copolymerization of dye and styrene was carried out at 70°C for 24 hours. As most part of the dye monomer is not dissolved, a mixture of ethanol / dichlorobenzene (respectively 18.5 g / 4.1 g) is added at 70°C. The reaction mixture is stirred at this temperature for further 17 hours. The copolymer particles formed spontaneously during the polymerization reaction. No purification of obtained polymer particles is required.
  • Comparative Example 10 Synthesis of dyed polydisperse particles of PS-co- (HY-E3-NMA) polymer according to the prior art (one-stage process)
  • 0.018 g (0.46 wt % to styrene) HY-E3-NMA is dissolved in 26.1 g ethanol.
  • 1.27 g PVP, 0.32 g Triton N-20 and 1.1 g styrene are added to the flask and then the flask was placed in an oil bath.
  • the solution was deoxygenated by bubbling nitrogen, heated to the reaction temperature 80 °C, and stirred mechanically at 100 rpm.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé en deux étapes pour fabriquer des particules polymères micrométriques monodispersées sphériques à granulométrie contrôlée, à partir de compositions à polymérisation en dispersion, les particules obtenues présentant un diamètre compris entre 1 et 10 νm. Dans un mode préféré de réalisation, les particules sont réticulées. Dans un autre mode préféré de réalisation, les particules obtenues renferment un colorant, de préférence un colorant absorbant de 330-380 nm lié au polymère. Dans un mode particulièrement préféré de réalisation, les particules sont réticulées et colorées et elles possèdent des propriétés à effet pigmentaire. Ces particules polymères présentent d'excellentes propriétés, notamment une stabilité à haute température et une aptitude à la mise en oeuvre aisée comme pigments absorbants de 330-380 nm dans différents polymères courants.
PCT/IB2004/002997 2003-09-15 2004-09-10 Procede pour fabriquer des particules polymeres micro metriques monodispersees spheriques a granulometrie controlee WO2005026225A1 (fr)

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EP03020872 2003-09-15
EP03020872.2 2003-09-15

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WO2005026225A1 true WO2005026225A1 (fr) 2005-03-24

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US7897407B2 (en) 2005-07-11 2011-03-01 Rikshospitalet Hf Multicolored particles
US8685900B2 (en) 2009-04-03 2014-04-01 Halliburton Energy Services, Inc. Methods of using fluid loss additives comprising micro gels
CN105924557A (zh) * 2016-05-16 2016-09-07 佳易容相容剂江苏有限公司 长支链共聚树脂及其制备方法
US9688880B2 (en) 2015-04-09 2017-06-27 Ppg Industries Ohio, Inc. In situ assembled crystalline colloidal arrays
CN109232781A (zh) * 2018-09-21 2019-01-18 福州大学 一种含氮多孔有机聚合物的制备方法
CN110818361A (zh) * 2019-12-17 2020-02-21 北京建工新型建材有限责任公司 机喷厚层聚合物修补砂浆
CN111003995A (zh) * 2019-12-17 2020-04-14 北京建工新型建材有限责任公司 增强柔韧型抹面抗裂砂浆
CN111363074A (zh) * 2020-05-13 2020-07-03 上海捷门生物技术有限公司 一种具有核壳结构的聚(苯乙烯-co-油酸)纳米颗粒的制备方法
CN113156782A (zh) * 2021-04-15 2021-07-23 联想万像(深圳)科技有限公司 一种带电荷量均匀的荧光墨粉及其应用
US11999808B2 (en) 2018-02-27 2024-06-04 Waters Technologies Corporation Polymer particles with a gradient composition and methods of production thereof

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7897407B2 (en) 2005-07-11 2011-03-01 Rikshospitalet Hf Multicolored particles
US8685900B2 (en) 2009-04-03 2014-04-01 Halliburton Energy Services, Inc. Methods of using fluid loss additives comprising micro gels
US9688880B2 (en) 2015-04-09 2017-06-27 Ppg Industries Ohio, Inc. In situ assembled crystalline colloidal arrays
CN105924557A (zh) * 2016-05-16 2016-09-07 佳易容相容剂江苏有限公司 长支链共聚树脂及其制备方法
US11999808B2 (en) 2018-02-27 2024-06-04 Waters Technologies Corporation Polymer particles with a gradient composition and methods of production thereof
CN109232781A (zh) * 2018-09-21 2019-01-18 福州大学 一种含氮多孔有机聚合物的制备方法
CN111003995A (zh) * 2019-12-17 2020-04-14 北京建工新型建材有限责任公司 增强柔韧型抹面抗裂砂浆
CN110818361B (zh) * 2019-12-17 2021-12-14 北京建工新型建材有限责任公司 机喷厚层聚合物修补砂浆
CN111003995B (zh) * 2019-12-17 2021-12-14 北京建工新型建材有限责任公司 增强柔韧型抹面抗裂砂浆
CN110818361A (zh) * 2019-12-17 2020-02-21 北京建工新型建材有限责任公司 机喷厚层聚合物修补砂浆
CN111363074A (zh) * 2020-05-13 2020-07-03 上海捷门生物技术有限公司 一种具有核壳结构的聚(苯乙烯-co-油酸)纳米颗粒的制备方法
CN111363074B (zh) * 2020-05-13 2023-01-24 上海捷门生物技术有限公司 一种具有核壳结构的聚(苯乙烯-co-油酸)纳米颗粒的制备方法
CN113156782A (zh) * 2021-04-15 2021-07-23 联想万像(深圳)科技有限公司 一种带电荷量均匀的荧光墨粉及其应用

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