WO2015074988A1 - Matière composite nanoporeuse ayant une faible densité comprenant des particules creuses - Google Patents

Matière composite nanoporeuse ayant une faible densité comprenant des particules creuses Download PDF

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Publication number
WO2015074988A1
WO2015074988A1 PCT/EP2014/074731 EP2014074731W WO2015074988A1 WO 2015074988 A1 WO2015074988 A1 WO 2015074988A1 EP 2014074731 W EP2014074731 W EP 2014074731W WO 2015074988 A1 WO2015074988 A1 WO 2015074988A1
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gel
particles
dispersion
water
composite material
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PCT/EP2014/074731
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English (en)
Inventor
Bernd Bruchmann
Daniel KEHRLÖSSER
Massimo Morbidelli
Guiseppe Storti
Daswani POOJA
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Basf Se
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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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • 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
    • C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2325/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • Nanoporous composite material with low density comprising hollow particles
  • This invention concerns a nanoporous composite material comprising hollow particles, a process for producing the nanoporous composite material and also the use of the composite material.
  • Nanoporous composite materials are useful as catalyst supports, solid phases for
  • chromatography or insulating materials can be made in different ways, such as by reaction (WO 2006/128872), by gelation of colloidal dispersions (WO 2005/095502), by adhering aerogels (WO 2012/76489) or by linking together hollow particles by inorganic or organic binders (US 2,797,201 ).
  • WO 2009/043191 relates to a method for producing macro-porous materials comprising the following steps: a) synthesis of narrowly dispersed cross-linked polymeric particles starting from a monomer and a cross-linker by emulsion polymerization; b) swelling of the particles with a liquid mixture comprising at least an additional charge of monomer and cross-linker and subsequent destabilisation; c) initiation of the polymerization reaction of the swollen particles to form a monolithic structure.
  • Such monoliths can be very efficiently functionalised if after the synthesis of the polymeric particles in step a) and before the initiation of the reaction of the swollen particles in step c) the polymeric particles are chemically functionalised or prepared for subsequent functionalization of the monolithic structure. This method is known as "reactive gelation".
  • DE 102 33 702 A1 discloses a process for preparation of nanocellular polymer foams involving: (a) cooling of a dispersion of polymers in a sublimable dispersion agent over a maximum of 10 seconds to a temperature below the melting point of the dispersion agent to give a frozen mixture and (b) removal of the dispersion agent by freeze drying.
  • Dispersions comprising hollow particles and binders, such as water soluble polyacrylates, are preferred. This process is economically not viable in big scale because of the extremely fast cooling rate and subsequent freeze-drying step.
  • WO 2012/065288 discloses the preparation of a nanoporous composite material by dispersing nanoporous particles, such as silica aerogels, in a latex of polymeric hollow particles with rigid inner shell and adhesive outer shell.
  • nanoporous particles such as silica aerogels
  • the hollow latex particles are bound directly to one another to form a continuous matrix and the nanoporous particles are dispersed within the continuous matrix of hollow latex particles.
  • This composite material comprises of 50 to 99 vol% of nanoporous silica, so handling of large volumes of solid, dust generating inorganic nanomaterial is prerequisite, which can cause environmental and safety issues.
  • RAFT interfacial reversible addition-fragmentation chain transfer
  • the problem addressed by this invention was therefore that of providing nanoporous composite materials with low densities, low thermal conductivity and homogeneous and narrow pore size and pore volume distribution.
  • the nanoporous composite materials shall also be producible in a simple manner and in commercial scale without the need of organic solvents and additional inorganic or organic binders.
  • the invention provides a process for producing a nanoporous composite material comprising at least the following steps: a) providing a dispersion of hollow latex particles C, comprising a hard shell,
  • Dispersions of colloidal hollow latex particles C may be obtained by emulsion polymerization as described in EP-A 1 904 544 or EP 2 143 742.
  • Hollow latex particles are a particular variety of core/shell particles composed in dried form of an air-filled cavity surrounded by a hard shell. This construction gives them the particular property of scattering light, which is the reason for their use as a white pigment in paints, paper coatings, and cosmetics, suncreams for example.
  • the hollow latex particles comprise before drying an aqueous phase as core and at least one shell.
  • the shell of the hollow latex particles comprises 90% to 99.9%, preferably 95% to 99.9% by weight of at least one nonionically ethylenically unsaturated monomer, and 0.1 % to 10%, preferably 0.1 % to 5% by weight of at least one hydrophilic monoethylenically unsaturated monomer.
  • the nonionically ethylenically unsaturated monomers comprehend styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, (Ci-C2o)alkyl or (C3-C2o)alkenyl esters of acrylic or methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, ste
  • (meth)acrylate hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, ricinoleic acid, palmitoleic acid, oleic acid, elaidinic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, and clupanodonic acid, preferably styrene, acrylonitrile, methacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2- ethylhexyl methacrylate.
  • the monoethylenically unsaturated hydrophilic monomers comprehend acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloyloxypropionic acid, acryloyloxyacetic acid, methacryloyloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, monomethyl itaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, and itaconic acid monomethyl ester.
  • the hard shell encloses the core.
  • the shell polymer possesses a glass transition temperature T g (hard shell) calculated according to the Fox equation (John Wiley & Sons Ltd., Baffins Lane, Chichester, England, 1997) of between -40°C to 180°C, preferably between 55°C to 120°C.
  • the final average particle size of the hollow latex particles preferably is between 300 to 800 nm.
  • Bi- or multi-modale particle size distribution may be advanteageous to minimize interstitial volume.
  • the hollow latex particles C comprise polymerized acrylic monomers and/or vinylaromatic monomers.
  • Preferred monomers are methyl methacrylate, n-butyl methacrylate, allyl methacrylate, methacrylic acid, acrylonitrile and styrene.
  • Suitable colloidal dispersions of hollow particles are commercially available, such as for example Ultra E from Dow Chemical or AQACell DS 6273 from BASF SE.
  • one or more further shells may be polymerized on the hollow latex particles C from the nonionically ethylenically unsaturated monomers and monoethylenically unsaturated hydrophilic monomers described under step a).
  • the one or more further shells formed optionally in step b) also comprises polymerized acrylic monomers and/or or vinylaromatic monomers but in a ratio which results in a lower glass transition temperature T g of the outer shell as of the hard shell of the hollow latex particle.
  • Preferred monomers are methyl methacrylate, n-butyl methacrylate, methacrylic acid and styrene.
  • the soft shell formed in step b) has a glass transition temperature Tg (soft shell) calculated according to the Fox equation in the range of -60°C to 50°C.
  • Tg (soft shell) is from 5°C to 50°C lower than Tg (hard shell)
  • Cross-linked polymer latex particles produced by emulsion polymerization are optionally swollen by addition of a suitable mixture of monomers, crosslinking agents and initiator.
  • Coagulation or formation of gel in step d) is done by suitable destabilization of the original aqueous dispersion.
  • This destabilization step is carefully controlled e.g. by adding a specific amount of salt, changing temperature, changing pH of the aqueous phase or applying shear.
  • the destabilization of the dispersion is performed in such a way that "controlled" aggregation of the particles is achieved.
  • controlled means that the aggregation conditions are such to develop a very open structure, with clusters of primary particles as large as the vessel containing the swollen latex, thus forming a so-called physical gel. At this stage, the particles are connected to each other by weak Van der Waals forces.
  • post-polymerization an additional reactive step (so called “post-polymerization") is carried out by increasing the temperature.
  • residual monomers and residual initiator or monomers and initiator introduced during the swelling step fully react and "freeze” the porous structure of the aggregate while imparting significant mechanical strength to the final monolith.
  • steps c) to e) are known as "reactive gelation” and preferably carried out in the way as described in WO 2009/043191.
  • Step e) can be carried out optionally with a 10% to 50% volume reduction once the mold is filled with the coagulate or gel and/or drying.
  • Step e) may be carried out at ambient pressure (101 ,3 KPa) or at reduced pressure (1 - 100 KPa). The post-polymerization conditions can be adjusted to minimize such volume reduction if necessary.
  • nanoporous particles, inorganic particles, especially aerogel particles, especially nanoporous particles having an average pore size less than 1 ⁇ are preferably not added.
  • the process according to the invention consists of the steps:
  • the process according to the invention consists of the steps a) to e).
  • the inner surfaces of the mold are moisture-permeable and hydrophobic. This can be accomplished for example by superposing metal sieves and suitable polymeric foils or membranes.
  • the invention provides also a nanoporous composite material obtainable by the process described above.
  • the density of the nanoporous composite material is preferably in the range from 10 to
  • 300 kg/m 3 more preferably in the range from 20 to 250 kg/m 3 , specifically in the range from 50 to 200 kg/m 3 and more specifically in the range from 50 to 150 kg/m 3 .
  • the nanoporous composite materials of the present invention have thermal conductivities at atmospheric pressure between 10 and 50 mW/(m K), preferably in the range from 10 to
  • nanoporous composite materials according to the present invention is their homogeneous and smooth surface.
  • the composite materials are also particularly simple to work/machine by sawing, sanding or cutting.
  • the composite material may comprise effective amounts of further addition agents such as, for example, dyes, pigments, fillers, flame retardants, synergists for flame retardants, antistats, stabilizers, plasticizers and IR opacifiers.
  • the total amount of additives is in the range of from 0 to 25% by volume, more preferable in the range from 1 to 10% by volume, most preferably in the range from 0.1 to 5 % by volume.
  • the nanoporous composite does not contain nanoporous particles, inorganic particles, especially aerogel particles, especially nanoporous particles having an average pore size less than 1 ⁇ .
  • the composites may comprise IR opacifiers such as, for example, metal oxides, non-metal oxides, metal powders (e.g., aluminum powder), carbon (e.g., carbon black, graphite, diamond) or organic dyes and dye pigments, which are advantageous for uses at high temperatures in particular. Particular preference is given to carbon black, titanium dioxide, iron oxides or zirconium dioxide.
  • IR opacifiers such as, for example, metal oxides, non-metal oxides, metal powders (e.g., aluminum powder), carbon (e.g., carbon black, graphite, diamond) or organic dyes and dye pigments, which are advantageous for uses at high temperatures in particular.
  • Particular preference is given to carbon black, titanium dioxide, iron oxides or zirconium dioxide.
  • the aforementioned materials can be used in each case not only singly but also in combination, i.e., in the form of a mixture of two or more materials.
  • the composite material can further be advantageous for the composite material to comprise fibers.
  • fiber material there may be used organic fibers such as, for example, polypropylene, polyester, nylon or melamine-formaldehyde fibers and/or inorganic fibers, for example glass, mineral and also SiC fibers and/or carbon fibers.
  • the volume fraction of fibers should be 0.1 to 30%, preferably 1 to 10%, and the thermal conductivity of fiber material should be ⁇ 1 W/(m K), preferably below 0,5 W/(m K), more preferably below 0,1 W/(m K)
  • fiber diameter and/or material can effectively reduce the radiative contribution to thermal conductivity and increase mechanical strength.
  • fiber diameter should preferably be in the range from 0.1 to 30 ⁇ .
  • the radiative contribution to thermal conductivity can be particularly reduced when using carbon fibers or carbon-containing fibers.
  • Mechanical strength can further be influenced by fiber length and distribution in the composite material. Preference is given to using fibers between 0.5 and 10 cm in length. Fabrics woven from fibers can also be used for plate-shaped articles.
  • the composite material may additionally comprise further auxiliary materials, for example
  • Tylose, starch, polyvinyl alcohol and/or wax emulsions are used in the prior art on large industrial scale in the shaping of ceramic compositions.
  • the composite material may further comprise added substances used in its method of making and/or formed in its method of making, for example slip agents for compression molding, such as zinc stearate, or the reaction products of acidic or acid-detaching cure accelerants in the event of using resins.
  • the material When the material is used in the form of sheet bodies, for example plates or mats, it may have been laminated on at least one side with at least one covering layer in order that the properties of the surface may be improved, for example to increase the robustness, turn it into a vapor barrier or guard it against easy soiling.
  • the covering layers can also improve the mechanical stability of the composite material molding. When covering layers are used on both faces, these covering layers can be identical or different.
  • Useful covering layers include any materials known to a person skilled in the art. They can be aporous and hence act as vapor barrier, for example polymeric foils, preferably metal foils or metalized polymeric foils that reflect thermal radiation. But it is also possible to use porous covering layers which allow air to penetrate into the material and hence lead to superior acoustical insulation, examples being porous foils, papers, wovens or nonwovens.
  • Lamination may further be carried out for example, with substantial retention of the acoustical properties, using so-called "open” systems, as for example perforated plates.
  • the covering layers may themselves also consist of two or more layers.
  • the covering layers can be secured with the binder with which the fibers and the aerogel particles are bonded to and between each other, but it is also possible to use some other adhesive.
  • the surface of the composite material can also be closed and consolidated by incorporating at least one suitable material in a surface layer.
  • suitable materials include, for example,
  • thermoplastic polymers e.g., polyethylene and polypropylene, or resins such as melamine- formaldehyde resins for example.
  • the composite materials of the present invention are combined with other foams, for example polyurethane and/or polystyrene foams.
  • the composite material of the present invention can be laminated with expanded polystyrene or admixed with polystyrene or polyurethane foams, more particularly expanded polystyrene.
  • the mixing ratio is easily adapted to the particular requirements and can be for example in a volume ratio of 10:90 to 90:10.
  • the nanoporous composite materials of the present invention can be used in a very wide variety of fields. Examples thereof are the thermal insulation of buildings, motorcars, aircraft or trains, fuel boilers, cooling appliances, baking ovens, heating pipes, district heating lines, liquid gas containers, night storage ovens and also vacuum insulation in technical appliances of various kinds.
  • the composite materials of the present invention are useful for internal insulation to achieve a low-energy standard, for external insulation, optionally combined with cementitious and inorganic adhesives, and also as part of a combination of base render, reinforcing mortar and top render, for roof insulation, and also in technical applications in refrigerators, transportation boxes, sandwich elements, pipe insulation and technical foams.
  • alkylpolyglycolethersulfate (Disponil FES 993, 30 wt.-% in water, BASF SE)
  • alkylpolyalkylenoxidphosphate (20 wt.-% in water, Lutensit A-EP A, BASF SE),
  • Ultra-pure grade water for chromatography has been prepared by Millipore Synergy (Millipore, Billerica, MA, USA).
  • Deionized water for synthesis has been stripped of oxygen by degassing under vacuum and subsequent saturation with nitrogen gas.
  • a Hitachi L-7100 pump (Hitachi, Tokyo, Japan) was used for the semi-batch latex preparation, Lambda Vit-Fit programmable syringe pump was used for continuous feeding of initiator in reaction.
  • Tga and Tgb glass transition temperature of polymer "a" and "b"
  • W a and Wb weight fraction of polymer "a" and "b"
  • the particle sizes were determined using a Coulter M4+ (Particle Analyzer) or by means of photon correlation spectroscopy, also known as quasielastic light scattering or dynamic light scattering (ISO 13321 standard) using an HPPS (High Performance Particle Sizer) from
  • Dynamic light scattering measurements were done on a Zetasizer nano ZS 3600 (Malvern Instruments, Malvern, Worcestershire, UK).
  • BET measurement was made via nitrogen absorption according to ISO 9277 using a Nova 2000e (Quantachrome GmbH & Co. KG).
  • Method B thermal conductivity measurement according to DIN EN 12667 with a hot plate apparatus, metering area was 30 x 30 mm.
  • Example 1 Hollow Particle Dispersion C1 Dispersion A1 (Seed)
  • the initial charge consisting of 1 172.5 g of water, 70 g of Disponil LDBS 20 and also 22.19 g of the pre-emulsion, was heated to a temperature of 80°C under a nitrogen atmosphere in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels and, following the addition of 67.2 g of a 2.5 wt.-% strength solution of sodium peroxodisulfate, polymerization was run for 15 minutes. Then the remainder of the preemulsion was metered in over the course of 60 minutes at 80°C. Subsequently polymerization was continued for 15 minutes and the reaction mixture then cooled to 55°C over the course of 20 minutes. For depletion of residual monomers, 3.5 g of a 10% strength solution of tert-butyl hydroperoxide and 2.19 g of a 10 wt.-% strength solution of sodium
  • Particle size (PSDA, volume median diameter): 34 nm
  • Dispersion B1 (swell core) The initial charge, consisting of 1958.8 g of water and 14.54 g of Dispersion A1 (Seed), was heated to a temperature of 82°C under a nitrogen atmosphere in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels and, following the addition of 26.68 g of a 7 wt.-% strength solution of sodium peroxodisulfate, polymerization was run for 2 minutes. Then a mixture from 0.62 g allylmethacrylate and 217.34 methyl methacrylate was metered in over the course of 90 minutes together with a solution from 9.34 g
  • alkylpolyalkylenoxidphosphate (20 % strength, Lutensit A-EP A), 9.34 g of sodium dodecyl sulfonate (Disponil LDBS 20, 15% strength) and 166 g methacrylic acid in 562 g water.
  • 10 minutes after finishing of the addition 92.55 g of a 1.5 wt.-% strength solution of sodium peroxodisulfate was metered in together with a mixture from 62 g n-butyl methacrylate and 345,86 g methyl methacrylate and a solution from 2.49 g Disponil LDBS 20 and 8.38 g methacrylic acid in 276,89 g of water over the course of 75 minutes. Finally the feed vessel was rinsed with 33 g water and polymerization was continued for 30 minutes.
  • Solids content 21 .8 wt.%
  • Particle size (PSDA, volume median diameter): 186 nm
  • Dispersion C1 (Hollow particles): The initial charge, consisting of 261 g of water and 273.21 g of dispersion B1 , was heated to a temperature of 81 °C under a nitrogen atmosphere in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels and, following addition of 25.2 g of a 1 1 .4% strength solution of sodium peroxodisulfate. Then preemulsion 1 , consisting of 132 g of water, 13.6 g of Disponil LDBS 20, 4.08 g of methacrylic acid, 17.5 g of methyl methacrylate, 10.88 of acrylnitril.
  • preemulsion 2 consisting of 98.44 g of water, 7g of Disponil LDBS 20, 0.28 g of methacrylic acid and 78 g divinylbenzene was added within 15 minutes.
  • 5.64 g of a 10% strength solution of tert-butyl hydroperoxide was added and 31 g of a 3 wt.-% aqueous solution of Rongalit C was metered in over the course of 20 minutes.
  • 30 minutes after the end of the feed 9.16 g of a 10% strength solution of tert-butyl hydroperoxide and 5.1 g of a 3 wt.-% aqueous solution of Rongalit C were metered in parallel into the reaction mixture over the course of 60 minutes.
  • Particle size (PSDA, volume median diameter): 389
  • Dispersion B2 (swell-core) with in-situ seed:
  • the initial charge consisting of 526 g of water, in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 82°C.
  • pre-emulsion 2 (consisting of 236 g of water, 18.63 g of Disponil FES 993, 250 g of methyl methacrylate and 144.31 g of methacrylic acid) was metered in at 85°C over 120 min. Finally, the feed vessel was rinsed with 10 g of water and polymerization was continued for a further 15 min.
  • Particle size 130 nm Dispersion C2 (Hollow particles):
  • the initial charge consisting of 429 g of water and 80.13 g of dispersion B2 in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 78°C and, following admixture of 18 g of a 2.5 wt% sodium peroxodisulfate solution, incipiently polymerized for 5 min. Then pre-emulsion 1
  • pre-emulsion 2 (consisting of 1 18 g of water, 7 g of Disponil LDBS 20, 2 g of linseed oil fatty acids, 0.9 g of allyl methacrylate and 296.1 g of styrene) was added over 75 min together with 9 g of a 2.5 wt% sodium
  • peroxodisulfate solution starting at 80°C; during the feed the internal temperature was raised to 82°C. On completion of the feeds the internal temperature was raised to 93°C and the system was stirred for 15 min before 18 g of omethylstyrene were added. After a further 40 min of stirring, the temperature was lowered to 87°C. On attaining the temperature, the system was stirred for 15 min before 228 g of a 1.7 wt% ammonia solution were added over 30 min. After a renewed 15 min of stirring, pre-emulsion 3 (consisting of 51 g of water, 1.2 g of Disponil
  • LDBS 20 0.2 g of methacrylic acid and 41.8 g of divinylbenzene was added over 30 min.
  • 6 g of a 10 wt% aqueous solution of feri-butyl hydroperoxide were admixed together with 25 g of water, while 31 g of a 3.3 wt% aqueous Rongalit C solution were added over 60 min.
  • Particle size (PSDA, volume median): 387 nm
  • Example 3 Hollow Particle Dispersion C3: Dispersion B3 (swell-core) with in-situ seed: The initial charge, consisting of 478,53 g of water, 1 .64 g of Disponil FES 993 and 13.27 of
  • EFKA 3031 in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 82°C. This was followed by admixing pre-emulsion 1 (consisting of 80.68 g of water, 0.27 g of Disponil FES 993, 27.88 g of methyl methacrylate and 0.33 g of methacrylic acid) and 15.88 g of a 7 wt% aqueous sodium peroxodisulfate solution and polymerization for 30 min during which the temperature within the polymerization vessel was adjusted to 85°C.
  • pre-emulsion 1 consisting of 80.68 g of water, 0.27 g of Disponil FES 993, 27.88 g of methyl methacrylate and 0.33 g of methacrylic acid
  • 15.88 g of a 7 wt% aqueous sodium peroxodisulfate solution for 30 min during which the temperature within the poly
  • pH 2.9 particle size (PSDA, volume median): 188 nm
  • Dispersion C3 (Hollow particles): The initial charge, consisting of 354 g of water and 180 g of dispersion B3, in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 81 °C.
  • PSD particle size
  • Example 4 Hollow Particle Dispersion C4: Dispersion (swell-core) B4 with in-situ seed:
  • the initial charge consisting of 521 g of water and 1 .64 g of Disponil FES 993, in a
  • polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 82°C. Then pre-emulsion 1 consisting of 15.19 g of water, 0.27 g of Disponil FES 993, 27.88 g of methyl methacrylate and 0.33 g of methacrylic acid and 1 1 .43 g of a 10 wt% sodium peroxodisulfate solution was added before polymerizing for 30 min during which the temperature within the polymerization vessel was adjusted to 85°C.
  • pre-emulsion 2 consisting of 485.67 g of water, 27.22 g of Disponil FES 993, 334.22 g of methyl methacrylate, 9 g of allyl methacrylate and 228.82 g of methacrylic acid was added over 120 min at 85°C. Finally, the feed vessel was rinsed with 10 g of water and the system was postpolymerized for a further 15 min.
  • Particle size (PSDA, volume median): 189 nm
  • Dispersion C4 (Hollow particles): The initial charge, consisting of 354.16 g of water and 179.94 g of dispersion B4, in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 81 °C.
  • Particle size (PSDA, volume median): 398 nm
  • Example 5 Hollow Particle Dispersion C5: Seed dispersion A2:
  • a pre-emulsion was prepared from 123.85 g of water, 0.35 g of Disponil FES 993, 182 g of n- butyl acrylate, 163.45 g of methyl methacrylate and 4.55 g of methacrylic acid.
  • the initial charge consisting of 1 190.9 g of water, 24.97 g of Disponil FES 993 and also 22.19 g of the pre-emulsion, in a polymerization vessel equipped with an anchor stirrer, a reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 80°C and incipiently polymerized for 15 min by addition of 67.2 g of a 2.5 wt% sodium peroxodisulfate solution.
  • Particle size (PSDA, volume median): 50 nm Dispersion B5 (swell-core)
  • the initial charge consisting of 1822.6 g of water and 169 g of seed dispersion A2, in a polymerization vessel equipped with an anchor stirrer, reflux condenser and two feed vessels was heated in a nitrogen atmosphere to a temperature of 82°C.
  • Particle size (PSDA, volume median): 190 nm Dispersion C5 (Hollow particles):
  • the initial charge consisting of 261 g of water and 273.21 g of dispersion B5, in a
  • a soft shell was formed on the hollow particles C1 , where the hollow particles were used as seed latex.
  • the shell of thickness of around 20 nm was formed around the hollow particles using 1wt% cross-linking reagent (DVB). This step was carried out in a semi-batch condition in order to avoid inhomogeneity during shell formation as the monomers (styrene and DVB) used in shell formation have different reactivity ratios.
  • the reaction was carried out in three-neck round bottom flask under nitrogen atmosphere.
  • the round bottom flask was charged initially (IC) with seed latex (30 wt %) as shown in Table 1 .
  • the temperature of the reaction was set to 40 °C using an oil bath and the mixture was stirred at 300 rpm.
  • Redox initiator, t-BHP was added already in the initial feed when reaction temperature was reached.
  • an emulsion of styrene, DVB, SDS and water was prepared and kept emulsified using stirrer. This emulsion was fed continuously (CF) at 0.15g/min to the round bottom flask when reaction temperature was reached.
  • CF continuously
  • While feeding emulsion another part of the initiator Rongalit C (dissolved in water) was also fed at 0.062 ml/min, separately and simultaneously using a syringe pump.
  • swollen latex was mixed with right concentration and amount of the sodium chloride salt. Salt concentration which can lead to the gel formation in 20-25 minutes will be selected as right concentration. Therefore, different salt concentrations were mixed with latex in 1 :1 ratio until the desired aggregation speed was obtained. After selecting right concentration of salt (which was 0.45M NaCI in this case), a desired amount of latex was mixed with that particular concentration of salt in 1 :1 ratio under vigorous stirring using a vortex mixer. After mixing with salt, the mixture was filled immediately in 1 1 cm x 6 cm x 2 cm rectangular teflon box in order to make polymer slabs of that particular size.
  • right concentration of salt which was 0.45M NaCI in this case
  • the above produced gel was then post-polymerized and hardened in an oven at 70 °C for 24 hours, leading to shrinking of the gel. Obtained gel, was then washed in a water bath several times by renewing the water in water bath over a period of one day. After the washing step, gel was dried under the fume hood at room temperature and ambient pressure over a period of 14 days.
  • Pore size distribution was measured via Hg-intrusion from 50 nm to 10 ⁇ with an average pore size of 500 nm
  • Example 8 Nanoporous composite material from dispersion C3
  • the hollow particle latex C3 was filtered through a 10 ⁇ filter. Then 150 g of the filtered latex were mixed with 9.64 g of a Styrene/AIBN mixture (9.18 g Styrene, 0.46 g AIBN). Then 1 16 g of de-ionized water was added to the latex/monomer mixture in order to set the virtual solid content of the system to the value of 20 wt%. The mixture was left under agitation for 4 h on an orbital shaker at 200 rpm in order to perform swelling of the latex particles with the monomers for enabling the post-polymerization process afterwards.
  • the wet monolith was transferred now from the mould into a container filled with de-ionized water. Washing of the monolith was carried out by replacing daily the washing water with fresh water for 5 days, in order to remove salt and non-gelated particles or aggregates from the monolith.
  • the washed wet monolith was then dried at ambient conditions under still air for 10 days and after that for 2 days in a vacuum oven at 40°C and a pressure of 1 mbar.
  • Pore size distribution was measured via Hg-intrusion from 40 nm to 10 ⁇ with an average pore size of 400 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé pour produire une matière composite nanoporeuse comprenant au moins les étapes suivantes : a) la fourniture d'une dispersion de particules de latex creuses C comprenant une coque dure, b) la polymérisation facultative d'au moins une coque souple sur les particules de latex creuses C, c) le gonflement facultatif des particules de latex avec un mélange polymérisable d'un ou plusieurs parmi des monomères, des agents de réticulation et des initiateurs, d) la coagulation de la dispersion, et la séparation du coagulant et de la phase d'eau ou la formation d'un gel, e) le remplissage du coagulant ou gel dans un moule, et le durcissement du coagulant à une température comprise dans la plage allant de 20 à 100 °C.
PCT/EP2014/074731 2013-11-22 2014-11-17 Matière composite nanoporeuse ayant une faible densité comprenant des particules creuses WO2015074988A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2797201A (en) 1953-05-11 1957-06-25 Standard Oil Co Process of producing hollow particles and resulting product
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
DE10233702A1 (de) 2002-07-24 2004-02-12 Basf Ag Verfahren zur Herstellung nanozellularer Polymerschäume aus Polymerdispersionen
WO2005095502A1 (fr) 2004-03-22 2005-10-13 Basf Aktiengesellschaft Procede de fabrication de mousses de polymere a base de resines reactives de polycondensation
WO2006128872A1 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Produits de polyaddition de polyisocyanate poreux
EP1904544A1 (fr) 2005-07-14 2008-04-02 Basf Se Procede de fabrication de polymerisats d'emulsion
WO2009043191A2 (fr) 2007-10-05 2009-04-09 Eldgenössische Technische Hochschule Zürich Procédé de production de matériaux macroporeux
EP2143742A1 (fr) 2008-07-08 2010-01-13 Rohm and Haas Company Particules polymériques du type coeur-enveloppe.
US20100104810A1 (en) * 2007-03-14 2010-04-29 Kawamura Institute Of Chemical Research Organic/inorganic composite coating film, structural color film using the same, and preparation methods thereof
WO2012065288A1 (fr) 2010-11-15 2012-05-24 Dow Global Technologies Llc Particules nanoporeuses dans une matrice en latex creuse
WO2012076489A1 (fr) 2010-12-07 2012-06-14 Basf Se Matériau composite contenant des particules nanoporeuses

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2797201A (en) 1953-05-11 1957-06-25 Standard Oil Co Process of producing hollow particles and resulting product
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
DE10233702A1 (de) 2002-07-24 2004-02-12 Basf Ag Verfahren zur Herstellung nanozellularer Polymerschäume aus Polymerdispersionen
WO2005095502A1 (fr) 2004-03-22 2005-10-13 Basf Aktiengesellschaft Procede de fabrication de mousses de polymere a base de resines reactives de polycondensation
WO2006128872A1 (fr) 2005-06-03 2006-12-07 Basf Aktiengesellschaft Produits de polyaddition de polyisocyanate poreux
EP1904544A1 (fr) 2005-07-14 2008-04-02 Basf Se Procede de fabrication de polymerisats d'emulsion
US20100104810A1 (en) * 2007-03-14 2010-04-29 Kawamura Institute Of Chemical Research Organic/inorganic composite coating film, structural color film using the same, and preparation methods thereof
WO2009043191A2 (fr) 2007-10-05 2009-04-09 Eldgenössische Technische Hochschule Zürich Procédé de production de matériaux macroporeux
EP2143742A1 (fr) 2008-07-08 2010-01-13 Rohm and Haas Company Particules polymériques du type coeur-enveloppe.
WO2012065288A1 (fr) 2010-11-15 2012-05-24 Dow Global Technologies Llc Particules nanoporeuses dans une matrice en latex creuse
US20130224464A1 (en) * 2010-11-15 2013-08-29 Dow Global Technologies Llc Nanoporous particles in a hollow latex matrix
WO2012076489A1 (fr) 2010-12-07 2012-06-14 Basf Se Matériau composite contenant des particules nanoporeuses

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Title
"Fox equation", 1997, JOHN WILEY & SONS LTD.
J. H. FLYNN; D. M. LEVIN, THERMOCHIMICA ACTA, vol. 126, 1988, pages 93 - 100

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