EP1228108A1 - Couches photosolubilisables - Google Patents

Couches photosolubilisables

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Publication number
EP1228108A1
EP1228108A1 EP00972502A EP00972502A EP1228108A1 EP 1228108 A1 EP1228108 A1 EP 1228108A1 EP 00972502 A EP00972502 A EP 00972502A EP 00972502 A EP00972502 A EP 00972502A EP 1228108 A1 EP1228108 A1 EP 1228108A1
Authority
EP
European Patent Office
Prior art keywords
polymer
acid
composition
compound
poly
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00972502A
Other languages
German (de)
English (en)
Inventor
Alain Beristain
Michele J. Regimbald-Krnel
Juan C. Scaiano
Roger Sinta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luzchem Research Inc
University of Ottawa
Canadian Space Agency
Original Assignee
Luzchem Research Inc
University of Ottawa
Canadian Space Agency
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 Luzchem Research Inc, University of Ottawa, Canadian Space Agency filed Critical Luzchem Research Inc
Publication of EP1228108A1 publication Critical patent/EP1228108A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

  • This invention relates to a photosensitive and photosoluble polymeric material capable of forming a liquid-impermeable membrane, and to compositions for producing the material.
  • a layer of material that, when either placed on a solid support (i.e., porous or dialysis membrane, well plate, biological material such as skin) or as a self-supporting film can keep two aqueous solutions and/or media (i.e., solid/liquid, liquid/gas, solid/gas, liquid/vapour phase) separate for a given period of time, and be photosolubilized, preferably in aqueous media to allow mixing/contact of the two solutions/media.
  • a solid support i.e., porous or dialysis membrane, well plate, biological material such as skin
  • media i.e., solid/liquid, liquid/gas, solid/gas, liquid/vapour phase
  • Polymeric membranes are used in a variety of applications. Membranes can be used to prevent the mixing of components that are located on either side. Permselective membranes, those which allow selective transport of a molecular species, are found in both man-made (e.g. desalination units) and biological systems (e.g. cell membranes). Many of the latter systems are also selectively turned on and off by some sort of external stimuli (e.g. swelling). There are few examples of membranes which completely disappear allowing both sides to mix completely. Normally such mixing is achieved via mechanical means.
  • US Patent 5,071,731 describes a photosensitive element adapted for the preparation of colored images, the element having a photosolubilizable layer that comprises an acid- labile polymer and a photoacid generator (PAG) substance.
  • PAG photoacid generator
  • a polymer membrane/coating that can be photosolubilized in aqueous media has been developed in order to have the following properties.
  • the polymer membrane/coating should be able to keep two aqueous solutions/media separate for the specified time in a given application.
  • the polymer membrane/coating should be compatible with the various solutes in the aqueous media such as biological materials (e.g. proteins), chemical reagents, labeled materials, and pharmaceutical drugs.
  • biological materials e.g. proteins
  • chemical reagents e.g. proteins
  • labeled materials e.g.
  • pharmaceutical drugs e.g., a solutes in the aqueous media
  • the polymer membrane/coating Upon irradiation, the polymer membrane/coating must dissolve in the aqueous media thus allowing the two solutions/media to be in contact and/or mix.
  • the photoinduced solubilization does not require heat or any mechanical means to be achieved.
  • a photosoluble composition comprising: a polymer that is soluble upon de-crosslinking, preferably soluble in water or an aqueous solution, a multifunctional crosslinking compound, and a compound generating an acid upon irradiation.
  • the polymer comprises protic functional groups e.g. carboxylic acid and/or hydroxyl functional groups
  • the crosslinking compound is a multi-functional vinyl ether.
  • a method of manufacturing a photosoluble material comprising the steps of: a) mixing a polymer soluble upon de-crosslinking with a multifunctional crosslinking compound and a compound generating an acid upon irradiation, b) providing a layer of the mixture of step a), and c) simultaneously or subsequently, heating said layer at a temperature and for a time effective to produce a liquid- impermeable barrier.
  • the composition may comprise a sensitizing compound in order to promote decrosslinking of the polymer at longer wavelengths with said crosslinking compound.
  • a method of solubilizing the photosoluble material comprising irradiating the material with a radiation in the visible or ultraviolet range for a time sufficient to effect decrosslinking of the constituent polymer and solubilization of the material.
  • Fig. 1 illustrates various examples of use of the photosensitive material of the invention.
  • polymers with carboxylic acid groups (-CO 2 H) or hydroxyls (-OH) can be rendered insoluble in water by crosslinking with multifunctional vinyl ethers (Scheme 1).
  • the polymer may be a homopolymer, a random or block co-polymer, terpolymer or higher polymer of various monomers containing pendent carboxylic acid and/or hydroxyl functional groups.
  • the co-polymers and higher polymers may also contain monomers without carboxylic acid or hydroxyl functionalities (e.g. vinyl carboxylic acid esters such as vinyl acetate) or may contain monomers with pendent vinyl ether units, photoacid generating units (such as ester of strong acids) or sensitizing units.
  • the material is provided in a form of a membrane or coating and consists of a base polymer with carboxylic acid and/or hydroxyl functionalities [such as poly(acrylic acid), poly(vinyl alcohol), water-soluble cellulosic derivatives] that have been crosslinked with multifunctional vinyl ethers to give acid labile acetal ester and/or acetal linkages.
  • carboxylic acid and/or hydroxyl functionalities such as poly(acrylic acid), poly(vinyl alcohol), water-soluble cellulosic derivatives
  • the membrane/coating is stable to ordinary water as well as various aqueous buffered salt solutions in the dark in a pH range of approx. 4 to 9.
  • a photoacid generator is included in the membrane/coating that can release a strong acid upon irradiation, either by direct excitation or by sensitization in which case a sensitizer is also included in the membrane/coating), in order to reverse the acetal linkages. Dissolution of the polymer membrane/coating is thus achieved by photochemical means only.
  • the polymer may be a homopolymer, a random or block co-polymer, terpolymer or higher polymer of various monomers containing pendent protic functional groups such as carboxylic acid, sulfonic acids, amines and/or hydroxyl functional groups.
  • the protic groups may be attached directly to the polymer backbone or be present as substituents in the side chains.
  • Examples of polymers containing carboxylic acid groups include poly(acrylic acid), poly(methacrylic acid), poly(itanconic acid), poly(citraconic acid), poly(benzoic acid), polymeric derivatives of half carboxylic esters of malonates, and salts and copolymers thereof.
  • polymers and copolymers containing sulfonic acid groups e.g. poly(styrenesulfonic acid) and salts and copolymers thereof, can be used.
  • Hydroxyl containing polymers include poly(vinyl alcohol) and its various derivatives, cellulose esters and ethers, poly(hydroxyalkylmethacrylates), poly(hydroxyalkylacrylates), poly(saccharides) and copolymers thereof.
  • Suitable crosslinkers are multi (i.e., di, tri, poly) functional molecules capable of reacting with polymers containing protic groups, such as vinyl ethers, blocked isocyanates, or aldehydes.
  • Multivinyl ethers such as tri(ethylene glycol) divinyl ether (3), tetra(ethylene glycol) divinyl ether (4), trimethylolpropane trivinyl ether (5), and tris[4-(vinyloxy)butyl] trimellitate (6) (Chart 1), or protic polymers modified with vinyl ether derivatives such as 2-chloroethyl vinyl ether (7-9) (Chart 1).
  • the crosslinking process is achieved by heating a mixture of base polymer (e.g.
  • the base polymer already containing pendent vinyl ether units is crosslinked by heating with no additional crosslinker being necessary (Scheme lc).
  • a thermally stable photoacid generator or a PAG and a sensitizer, or a PAG with a sensitizing moiety covalently tethered to it are added to the mixture of base polymer and crosslinker or to the base polymer with vinyl ether units prior to heating.
  • the PAG and/or sensitizer may be covalently tethered to the base polymer.
  • the PAG produces a catalyst (acid) upon irradiation only, either by direct excitation or by sensitization at other wavelengths where the PAG does not absorb (Scheme 2).
  • PAGs include onium salts (i.e., sulfonium, iodonium, phosphonium, selenonium salts) of complex metal halides or sulfonates (such as triflate), iminosulfonates, esters of strong acids (e.g. nitrobenzyl sulfonate esters, N- hydroxyimide or N-hydroxyamides sulfonate esters), sulfones, disulfones and halogen compounds particularly, but not exclusively vicinal dibromides and trichlorotriazines.
  • onium salts i.e., sulfonium, iodonium, phosphonium, selenonium salts
  • complex metal halides or sulfonates such as triflate
  • iminosulfonates such as triflate
  • esters of strong acids e.g. nitrobenzyl sulfonate esters, N- hydroxyimide or
  • Such PAGs may need to be suitably derivatized (with suitable substitution) for incorporation into membrane/coating formulation and for subsequent solubilization in media when complete dissolution of coating/membrane is required for the intended application (i.e., protein crystallization device).
  • sensitizers such as dyes, phenothiazine, ketones (such as benzophenone, xanthone, thioxanthone, fluorenone, anthraquinone, benzanthrone), polycyclic aromatic hydrocarbons (such as pyrene, anthracene, naphthalene, perylene, rubrene, coronene) with suitable substitution for incorporation may be added to membrane/coating formulation and for subsequent solubilization in media when complete dissolution of coating/membrane is required for the intended application (i.e., protein crystallization device).
  • sensitizing moieties may be added to the formulation or covalently tethered to the PAG and/or base polymer.
  • Scheme 2 Irradiation Step
  • acetal ester and acetal linkages are thus hydrolyzed under acid catalysis and the crosslinking process is reversed (Scheme 3) leading to the dissolution of the membrane/coating.
  • Complete dissolution of the membrane/coating can also be achieved (i.e. when PAA and/or PNA are used as base polymers) which may be necessary in a given application such as protein crystallization where no residual nucleation centers should be present.
  • the polymer materials can be coated on various substrates using different approaches, i.e., spin-coating, dip-coating, spraying, draw-down coating technique, slot coating, lamination or calendering technique.
  • the films/coatings can be prepared as single or multiple coatings of the same or of different polymer materials using conventional multilayer coating techniques. Free standing films/membranes can be prepared using various approaches, i.e., extrusion process, calendering technique, lamination, or by isolating/stripping the film from a support after casting.
  • a baking step is preferable.
  • the baking is effected at sufficiently high temperatures and for a time effective to allow solvent evaporation as well as crosslinking leading to aqueous insolubilization of the polymer material.
  • the baking temperature must be such that the degree of crosslinking achieved can be sufficiently reversed in order for solubilization of the membrane/coating to occur when so desired.
  • polymer formulations and films/coatings/membranes must be protected from the specific wavelength range of light they are sensitive to (once prepared and incorporated into device as well as during their preparation and incorporation into device) until dissolution is desired for the given application.
  • a small amount of base (such as amines) may be incorporated in polymer formulations in order to neutralize any traces of acid formed by stray radiation, thus avoiding early dissolution of polymer material.
  • the polymeric materials of the invention in the form of films/coatings/membranes, as illustrated in Fig. 1, may have numerous applications such as separation, i.e., acting to divide materials/media/solutions for containment and/or prevention of mixing, the films/coatings/membranes being photoremovable when containment/prevention of mixing is no longer necessary.
  • separation i.e., acting to divide materials/media/solutions for containment and/or prevention of mixing
  • the films/coatings/membranes being photoremovable when containment/prevention of mixing is no longer necessary.
  • a photosensitive membrane could be incorporated in a device that would allow protein crystallization to be carried out in space.
  • the membrane would allow two aqueous solutions to be separated until the proper microgravity conditions have been achieved (this may typically require between 2 and 10 days from the time of sample preparation).
  • the membrane would have to be stable to the test solutions, which typically are buffered salt solutions in a pH range of 4 to 9 and may contain long hydrophilic polymers.
  • irradiation of the membrane would be done at wavelengths in the UNA region (320- 400 nm) in order to avoid protein structural damage but allow complete dissolution of the membrane (no residual nucleation centers), leading to the mixing of the two solutions (liquid-liquid diffusion technique).
  • These polymer materials could also be coated on permeable/semi-permeable/porous substrates (e.g. dialysis membrane) leading to photoactivated (dialysis) membranes.
  • these membranes could be used in surface protection applications.
  • these coatings/membranes can serve to prevent exposure/damage from unwanted media such as moisture or water. They could also be used to protect from light or filtered light in a given wavelength range with the use of appropriate sunscreen agents incorporated into the protective coating, whilst still being photoremovable when activated in a different region of the light spectrum. This could include windows and biological surfaces such as skin (i.e., treating burns), that could then be deprotected on demand.
  • the protection and/or sealing of images as well as art and archeological pieces are also envisaged.
  • photosensitive membranes could be used for light and radiation sensor devices.
  • Applications in gathering, storage and usage of solar energy may also be envisioned.
  • This example illustrates the preparation of single-coated thin films using PAA as a base polymer, the crosslinking with both di- and trifunctional vinyl ethers, and the comparison of light (254 nm) versus dark dissolution rates in water.
  • a methanol solution was prepared with the following three components:
  • the solution was spin-coated (3000 rpm for 20 s) onto a substrate (for example quartz disk) to give a thin film ( ⁇ 2.5 ⁇ m).
  • a substrate for example quartz disk
  • the disk was then placed into an oven at ⁇ 115 °C for 3 minutes in order to remove any excess solvent (methanol) as well as to achieve crosslinking of PAA with the vinyl ether.
  • a methanol solution was prepared as follows:
  • the films were prepared as described in example 1 except that they were baked for 8 minutes. When such a film was exposed to 350 nm radiation (8 rayonet lamps at a power of 0.9 mW/cm 2 ) for 1.5 hrs and then was submerged in water, complete and instantaneous dissolution of the film was observed. The amount of time necessary for these films to solubilize when submerged in water was determined to be 9 hours in the dark compared to 1 hour when exposed to 350 nm radiation.
  • This example illustrates the light versus dark dissolution rates of crosslinked PAA/XL4 single-coated thin films using iodonium PAGs that generate different acids (Chart 2).
  • a methanol solution was prepared as follows:
  • the films were prepared as described in example 1 except that the temperature of the oven varied between 100 - 110 °C during the baking step.
  • Table 2 compares the aqueous dark and photoinduced solubilization times for these films.
  • This example illustrates the preparation of single-coated and multiple-coated thin films using PVA as a base polymer, the crosslinking with a difunctional vinyl ether, and the comparison of light (254 nm) versus dark dissolution rates in water.
  • a single-coated thin film ( ⁇ 1.5 ⁇ m) was prepared as described in example 1 except that a temperature of -170 °C was used for the crosslinking step.
  • Another coat was prepared by spin-coating more solution (of the same composition) on top of the film (already crosslinked) followed by another baking period to achieve crosslinking of the top layer.
  • a multiple-coated film was thus obtained.
  • This example illustrates the preparation of a multiple-coated thin film using PAA as a base polymer for the first coat and PVA as a base polymer for the second coat, the crosslinking of each coat with a difunctional vinyl ether, and the comparison of light (254 nm) versus dark dissolution rates in water.
  • the amount of time necessary for the PAA-PVA film to solubilize in water was determined to be over 33 hours in the dark compared to 3 hours when exposed to 254 nm radiation.
  • This example illustrates the derivatization of a trifunctional alcohol (trimethylolpropane) with vinyl ether units to give crosslinker 15, its crosslinking with PAA polymer and the comparison of light (254 nm) versus dark dissolution rates in water.
  • a methanol solution was prepared as follows:
  • the films were prepared as described in example 1 except that the temperature of the oven varied between 100 - 110 °C during the baking step.
  • the amount of time necessary for these films to solubilize when submerged in water was determined to be 2 hours when exposed to 254 nm radiation (8 rayonet lamps at a power of 0.9 mW/cm 2 ). When left in the dark whilst submerged in water, the films were still present after more than 6 days.
  • This example illustrates the derivatization of a preformed polymer (PVA) with vinyl ether units, its crosslinking and subsequent insolubility in water.
  • PVA preformed polymer
  • a 25% (w/v) solution of the modified polymer in water was then spin-coated (3000 rpm for 20 s) onto a silicon wafer and analyzed by IR spectroscopy.
  • the film was then submerged in water and remained intact for more than one week.
  • This example illustrates the preparation of capillary plugs using PAA as a base polymer, the crosslinking with a difunctional vinyl ether, and their dark stability in buffered salt solutions.
  • a methanol solution is prepared as follows:
  • PAA in a 1 : 1 (w/v) proportion with methanol (e.g. 1.0 g of PAA in 1 mL of methanol) 25 to 50% (w/w) of crosslinker (XL 4) with respect to PAA
  • methanol e.g. 1.0 g of PAA in 1 mL of methanol
  • crosslinker XL 4
  • Aqueous insolubilization of such plugs were tested by introducing a buffered salt solution on both sides of the plug. Blue food coloring was added to the buffered solution on one side of the plug only. The time necessary for the blue dye to migrate to the other side of the plug (in the dark) was then determined.
  • the buffered salt solutions are prepared in water with the following components:
  • a methanol solution was prepared as follows:
  • PVA-PAA-PVA plugs were prepared by introducing the PAA/XL4/PAG 10 solution in a quartz capillary (1 mm in internal diameter, 3mm in length). An initial baking of the capillary was done on a hot plate ( ⁇ 100 °C) for one hour (with occasional rolling of the capillary) in order to evaporate some methanol. Then, the PVA/XL4/PAG10 solution was syringed into the capillary on either side of the PAA plug. Care must be taken not to introduce any air bubbles which expand upon heating leading the viscous solution to splatter all over the walls of the capillary. The capillary was baked once again on the hot plate at 100 °C (gradually increased to 125 °C) over 2.5 hrs. The average size of the plug after baking was - 1.5 mm in length and 1 mm in internal diameter.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On produit des membranes ou des barrières polymères photosolubles en faisant réagir un polymère sélectionné avec des groupes fonctionnels protiques, par exemple un acide polyacrylique ou un poly(alcool de vinyle), avec un éther vinylique multifonctionnel et un générateur de photoacides. Facultativement, on peut ajouter une substance sensibilisante. Le mélange est durci pour occasionner la réticulation du polymère. On peut éliminer le caractère réticulé de la matière résultante imperméable à l'eau et solubiliser ladite matière par rayonnement avec une lumière visible ou contenant des ultraviolets.
EP00972502A 1999-11-02 2000-11-02 Couches photosolubilisables Withdrawn EP1228108A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16307499P 1999-11-02 1999-11-02
US163074P 1999-11-02
PCT/CA2000/001274 WO2001032720A1 (fr) 1999-11-02 2000-11-02 Couches photosolubilisables

Publications (1)

Publication Number Publication Date
EP1228108A1 true EP1228108A1 (fr) 2002-08-07

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EP00972502A Withdrawn EP1228108A1 (fr) 1999-11-02 2000-11-02 Couches photosolubilisables

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EP (1) EP1228108A1 (fr)
JP (1) JP2003513163A (fr)
AU (1) AU1122501A (fr)
CA (1) CA2388920A1 (fr)
WO (1) WO2001032720A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000644A1 (fr) * 2001-06-21 2003-01-03 The Institute Of Cancer Research Esters photolabiles et leurs utilisations
ITTO20020362A1 (it) * 2002-04-30 2003-10-30 Metlac S P A Sistema multirivestimento con proprieta' di barriera ai gas, fotoreticolabile mediante radiazione uv particolarmente idoneo per la protezion
US7332477B2 (en) * 2003-07-10 2008-02-19 Nitto Denko Corporation Photocleavable DNA transfer agent
EP1667732B1 (fr) 2003-09-29 2010-04-21 Nitto Denko Corporation Polyacetals biodegradables pour administration de polynucleotides in vivo
US7674452B2 (en) 2005-03-16 2010-03-09 Nitto Denko Corporation Polymer coating of cells
GB2515560B (en) * 2013-06-28 2016-12-14 Kalliopuska Juha Method and related arrangement for devulcanization of vulcanized rubber

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3473359D1 (de) * 1983-06-29 1988-09-15 Fuji Photo Film Co Ltd Photosolubilizable composition
JPH06230574A (ja) * 1993-02-05 1994-08-19 Fuji Photo Film Co Ltd ポジ型感光性組成物
DE19624990A1 (de) * 1996-06-22 1998-01-08 Gluesenkamp Karl Heinz Dr Verfahren zur chemischen kontrollierten Modifizierung von Oberflächen sowie von Acyl- und/oder Hydroxyl-Gruppen tragenden Polymeren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0132720A1 *

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CA2388920A1 (fr) 2001-05-10
JP2003513163A (ja) 2003-04-08
AU1122501A (en) 2001-05-14
WO2001032720A1 (fr) 2001-05-10

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