WO2003091321A1 - Matiere polymere poreuse et procede de production associe - Google Patents

Matiere polymere poreuse et procede de production associe Download PDF

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Publication number
WO2003091321A1
WO2003091321A1 PCT/GB2003/001760 GB0301760W WO03091321A1 WO 2003091321 A1 WO2003091321 A1 WO 2003091321A1 GB 0301760 W GB0301760 W GB 0301760W WO 03091321 A1 WO03091321 A1 WO 03091321A1
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WO
WIPO (PCT)
Prior art keywords
hydrophilic polymeric
porous crosslinked
crosslinked hydrophilic
beads
polymeric beads
Prior art date
Application number
PCT/GB2003/001760
Other languages
English (en)
Inventor
Andrew Ian Cooper
Haifei Zhang
Original Assignee
The University Of Liverpool
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The University Of Liverpool filed Critical The University Of Liverpool
Priority to AU2003227879A priority Critical patent/AU2003227879A1/en
Publication of WO2003091321A1 publication Critical patent/WO2003091321A1/fr

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Classifications

    • 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
    • C08J9/16—Making expandable particles
    • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
    • 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
    • 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
    • C08J2201/028—Foaming by preparing of a high internal phase emulsion
    • 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

  • Crosslinked porous polymeric materials have been used for a variety of
  • sensing-device carriers Other uses include affinity chromatography, immobilisation of enzymes,
  • W/O water-in-oil
  • HIPEs high internal phase emulsions
  • oil to water is typically greater than 70% (P. Hainey, et al, Macromolecules 1991, 24, 117; N.
  • the HIPEs comprise a combination of a substantially water-insoluble monomer and a
  • substantially water-insoluble crosslinker as the continuous phase e.g., styrene/divinylbenzene
  • the emulsions comprise of less than 70% internal oil
  • the materials disclosed are either hydrophobic or hydrophilic in nature. In general,
  • W/O HIPEs comprising substantially oil-soluble monomers lead to hydrophobic HIPE
  • droplets is that particles are produced with a relatively broad size range.
  • size distribution of the beads so produced may be very narrow because the droplets are spatially
  • 100% of the material is in the form of substantially spherical beads with narrow bead size
  • polymeric beads have a porous structure, characterized by cavities joined
  • interconnecting pores a HIPE structure
  • the present invention overcomes or alleviates the problems associated with current
  • crosslinked hydrophilic polymeric beads comprising;
  • the average bead diameter of the hydrophilic beads ranges
  • hydrophilic beads of the present invention possess many of the desirable properties
  • hydrophilic beads are characterized by having a low
  • the nominal void volume in the hydrophilic beads is at least about 70%, preferably in
  • the bead size distribution is relatively narrow with the standard deviation in the average
  • bead diameter ranging from about 0.1% to about 50%. In a preferred embodiment of this
  • the standard deviation in the average bead diameter ranges from about 0.5% to about
  • bead diameter ranges from about 1% to about 10%.
  • beads are substantially spherical.
  • porous crosslinked hydrophilic polymeric beads described above have a total pore
  • ml/g still more preferably from about 1.8 ml/g to about 2.8 ml/g.
  • porous crosslinked hydrophilic polymeric beads comprising;
  • the HIPE may be an O/W HIPE, in which case the aqueous continuous phase preferably
  • the monomer may be self cross-
  • the aqueous continuous phase may comprise a substantially
  • the aqueous continuous phase may additionally comprise a
  • the sedimentation medium in this case is preferably non-aqueous.
  • the droplets are only partially polymerized during sedimentation.
  • the droplets are only partially polymerized during sedimentation.
  • polymerization should proceed during sedimentation to an extent sufficient to prevent
  • the method for producing the porous crosslinked hydrophilic polymeric beads may be any method for producing the porous crosslinked hydrophilic polymeric beads.
  • average diameter of the hydrophilic bead can be controlled by variation of experimental factors
  • the aqueous continuous phase In a preferred process according to the invention, the aqueous continuous phase
  • the non-aqueous solution includes a monomer, a crosslinker, an initiator and an emulsifier.
  • discontinuous phase may comprise light mineral oil and the sedimentation medium may
  • the monomer can be selected from a wide range of substantially water-soluble
  • monomers include, for example, acrylamide; acrylic acid; sodium acrylate; methacrylic acid;
  • the monomer component is preferably present in the continuous phase in an
  • the crosslinker can be selected from a wide range of substantially water-soluble polyfunctional vinyl monomers or mixtures of two or more thereof. Suitable crosslinkers
  • NN'-methylene bisacrylamide include, for example, NN'-methylene bisacrylamide; NN'-diallyl acrylamide; diallylamine;
  • diallyl methacrylamide diallyl phthalate; diallyl malate; diallyl phosphate; divinyl sulfone;
  • crosslinkers of this type can be used singly or as mixtures.
  • the crosslinker component is
  • the amount of the crosslinker component is more preferably from about 1%> to about
  • the initiator can be selected from a wide range of substantially water-soluble free-radical
  • Suitable initiators include, for example, ammonium,
  • component is present in the continuous phase in an amount of from about 0.1% to about 5%> by
  • the amount of the initiator component is more
  • a redox initiation promoter may also be added (for example, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylethyldiamine)
  • the emulsifier can be any nonionic, cationic, anionic, or amphoteric emulsifier, or
  • polyvinylalcohol constitutes the emulsifier.
  • the emulsifier component is present in the
  • the amount of the emulsifier component is more preferably from about 2% to about 40% by weight, most
  • the oil discontinuous phase can be any substantially water-immiscible fluid that has a
  • alkanes and mixtures of two or more thereof.
  • the boiling point of the oil phase is greater than
  • hydrophilic beads of the present invention are prepared from a HIPE, which comprises an
  • discontinuous phase is in the range of from about 60% to about 96%>, more preferably from about
  • the HIPE is injected into a heated sedimentation medium in the form of discrete, uniformly sized droplets. It is an aspect of the present invention that the boiling point of the oil phase is greater than about 50 °C, more preferably greater than about 70 °C, most
  • the sedimentation rate can be decreased by addition of a high molecular weight linear polymer
  • the modifier can be any substantially water-insoluble natural or synthetic polymer that is miscible with the sedimentation medium.
  • the sedimentation rate can be reduced by
  • the HIPE can be prepared by utilising any of the methods outlined in the prior art, for
  • the HIPE is prepared using a type Rwl 1 Basic IKA paddle stirrer.
  • the HIPE is injected into a vertically-
  • the HIPE is injected continuously through a 0.6 mm x 25 mm nozzle at a constant rate
  • the droplet size can be varied by varying
  • the nozzle diameter the HIPE viscosity, and the injection rate.
  • the injection rate the injection rate
  • Partial polymerization of the HIPE droplets occurs during sedimentation.
  • the droplets are sufficiently rigid to prevent
  • the crosslinker is NN'-methylene
  • the free radical initiator is ammonium persulphate and the droplets are heated at 90 °C for a period of 2 h.
  • the polymerization stage converts the HIPE droplets into solid beads.
  • the beads can be
  • the sedimentation medium can be any suitable sedimentation medium.
  • the sedimentation medium can be any suitable sedimentation medium.
  • the beads are washed with a solvent that is suitable
  • hydrophilic beads can be washed in acetone.
  • the hydrophilic beads can be washed in acetone.
  • hydrophilic bead product was washed ten times with acetone.
  • the discontinuous oil phase can be
  • discontinuous oil may be removed by washing with any suitable solvent.
  • the discontinuous oil may be removed by washing with any suitable solvent.
  • phase was removed from the hydrophilic bead product by continuous extraction using
  • the discontinuous oil is supercritical carbon dioxide (200 bar, 35 °C).
  • the discontinuous oil is supercritical carbon dioxide (200 bar, 35 °C).
  • Figure la is an optical microscope image of example 1.
  • Figure lb is an optical microscope image of example 2.
  • Figure lc is an optical microscope image of example 4.
  • Figure Id is an optical microscope image of example 5.
  • Figure 2 illustrates an electron micrograph of the internal structure of one bead in
  • Figure 3 illustrates an electron micrograph of the bead surface of example 7.
  • Figure 4 illustrates an electron micrograph of the bead surface of example 8.
  • Figure 5 illustrates an electron micrograph of internal structure of the bead in example
  • Figure 6 is an optical image of the beads produced in example 6.
  • Figure 7 is an optical image of the beads produced in example 7.
  • Figure 8 is an optical image of the beads produced in example 8.
  • Hydrophilic HIPE beads were prepared by continuous sedimentation polymerisation of a HIPE comprising an aqueous continuous phase (containing the monomer) and an oil discontinuous
  • a glass sedimentation column (53 cm in length, outside diameter 5.6 cm, internal diameter 4.6 cm) was used. Light mineral oil and vegetable oil (1 :10 v/v) was added and this
  • the level of the oil was 5 cm from the top of
  • the sedimentation medium was heated to 90 °C.
  • the HIPE was injected using
  • the collected beads were washed ten times with acetone and allowed to dry in air at room temperature.
  • the internal oil phase was removed by Soxhlet extraction with cyclohexane for 15
  • the beads have a skeletal density very similar to that of the equivalent non-porous cross-
  • Figure 1 shows an optical microscope image of a range of beads relating to examples 1,
  • the total pore volume in figure lb is 2.14 ml/g.
  • the mean bead diameter of figure lc is 1.20 mm and the standard deviation in bead diameter is 12.60%>.
  • the mean bead diameter of figure Id is 1.63 mm and a standard deviation in bead diameter is 10.75%)
  • Figure 2 shows an electron micrograph of a fractured bead, showing the internal structure
  • the total pore volume (or intrusion volume) as measured by mercury intrusion porosimetry was 2.51 ml/g.
  • Figure 3 illustrates an electron micrograph of the bead surface of example 7.
  • Figure 7 is
  • Figure 4 illustrates an electron micrograph of the bead surface of example 8
  • Figure 5 shows the internal structure of the bead in example 8
  • Figure 8 is an optical microscope image
  • example 8 which has a mean bead diameter of 2.24 mm and a standard deviation in bead
  • Figure 6 is an optical microscope image of example 6, which has a mean bead diameter of 1.51mm and a standard deviation in bead diameter of 8.86%>.
  • Figure 7 is an optical microscope image of example 7, beads of which had a mean bead diameter of 2.19 mm and a standard deviation in bead diameter of 12.23%
  • Exemplary preferred FIIPE beads were prepared according to the following general protocol. The details of specific examples are set forth in Table 2-8.
  • the discontinuous oil phase was added with mechanical stirring to form a HIPE.
  • the beads were dried in a vacuum oven at 50 °C overnight.
  • N,N,N,N-Tetramethylethylenediamine 50 ⁇ L
  • Vegetable oil 770 ml
  • Light mineral oil 70 ml
  • Heavy mineral oil 200 ml
  • Heavy mineral oil 200 ml

Landscapes

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

Abstract

L'invention concerne une matière polymère poreuse et un procédé de production associé, pour lequel une majorité, par exemple 80 % ou plus, ou même 100 % de la matière se présente sous forme de billes sensiblement sphériques à composition granulométrique limitée. Lesdites billes polymères présentent une structure poreuse, caractérisée par des cavités jointes par des pores d'interconnexion (structure à émulsions à phase interne élevée), certaines étant reliées à la surface de la bille.
PCT/GB2003/001760 2002-04-24 2003-04-23 Matiere polymere poreuse et procede de production associe WO2003091321A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003227879A AU2003227879A1 (en) 2002-04-24 2003-04-23 Porous polymer material and method of production thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0209315.1 2002-04-24
GB0209315A GB0209315D0 (en) 2002-04-24 2002-04-24 Porous polymer material and method of production thereof

Publications (1)

Publication Number Publication Date
WO2003091321A1 true WO2003091321A1 (fr) 2003-11-06

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AU (1) AU2003227879A1 (fr)
GB (1) GB0209315D0 (fr)
WO (1) WO2003091321A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073296A2 (fr) * 2004-01-28 2005-08-11 Unilever Plc Materiaux poreux et procede de production associe
WO2005075547A1 (fr) * 2004-01-28 2005-08-18 Unilever Plc Corps poreux et procede de production de ceux-ci
FR2874824A1 (fr) * 2004-09-09 2006-03-10 Oreal Composition de coiffage comprenant l'association d'un materiau polymerique hydrophile de haute porosite et polymere fixant
CN111995711A (zh) * 2020-03-25 2020-11-27 武汉纺织大学 吸附处理印染废水的亲水性中空多孔微球树脂及其制备方法和应用
CN113024704A (zh) * 2021-03-15 2021-06-25 华东理工大学 一种珠状多孔材料及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111467984B (zh) * 2020-03-07 2022-03-04 中国科学院大学温州研究院(温州生物材料与工程研究所) 一种基于硅油和植物油的双元高内相乳液组合物

Citations (1)

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US5863957A (en) * 1994-06-06 1999-01-26 Biopore Corporation Polymeric microbeads

Patent Citations (1)

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US5863957A (en) * 1994-06-06 1999-01-26 Biopore Corporation Polymeric microbeads

Non-Patent Citations (1)

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Title
RUCKENSTEIN E ET AL: "Sedimentation polymerization", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 36, no. 14, 1995, pages 2857 - 2860, XP004025717, ISSN: 0032-3861 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1922248B (zh) * 2004-01-28 2011-06-15 荷兰联合利华有限公司 多孔材料和其生产方法
WO2005073296A2 (fr) * 2004-01-28 2005-08-11 Unilever Plc Materiaux poreux et procede de production associe
AU2004315405B2 (en) * 2004-01-28 2008-06-05 Unilever Plc Porous bodies and method of production thereof
WO2005073296A3 (fr) * 2004-01-28 2005-09-29 Unilever Plc Materiaux poreux et procede de production associe
AU2005209476B9 (en) * 2004-01-28 2008-10-16 Unilever Plc Porous materials and method of production thereof
WO2005073300A1 (fr) * 2004-01-28 2005-08-11 Unilever Plc Corps poreux et procede de production desdits corps
AU2005209475B2 (en) * 2004-01-28 2008-05-15 Unilever Plc Porous bodies and method of production thereof
US7544720B2 (en) 2004-01-28 2009-06-09 Conopco, Inc. Porous polymeric materials and method of production thereof
WO2005075547A1 (fr) * 2004-01-28 2005-08-18 Unilever Plc Corps poreux et procede de production de ceux-ci
US8242182B2 (en) 2004-01-28 2012-08-14 Iota Nanosolutions Limited Porous bodies and method of production thereof
AU2005209476B2 (en) * 2004-01-28 2008-06-05 Unilever Plc Porous materials and method of production thereof
CN1914263B (zh) * 2004-01-28 2011-06-08 荷兰联合利华有限公司 多孔体和其生产方法
EP1634580A1 (fr) 2004-09-09 2006-03-15 L'oreal Composition de coiffage comprenant l'association d'un materiau polymerique hydrophile de haute porosite et d'un polymere fixant
FR2874824A1 (fr) * 2004-09-09 2006-03-10 Oreal Composition de coiffage comprenant l'association d'un materiau polymerique hydrophile de haute porosite et polymere fixant
CN111995711A (zh) * 2020-03-25 2020-11-27 武汉纺织大学 吸附处理印染废水的亲水性中空多孔微球树脂及其制备方法和应用
CN111995711B (zh) * 2020-03-25 2022-05-13 武汉纺织大学 吸附处理印染废水的亲水性中空多孔微球树脂及其制备方法和应用
CN113024704A (zh) * 2021-03-15 2021-06-25 华东理工大学 一种珠状多孔材料及其制备方法和应用

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GB0209315D0 (en) 2002-06-05
AU2003227879A1 (en) 2003-11-10

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