WO2007102984A1 - Matériaux à architecture contrôlée - Google Patents

Matériaux à architecture contrôlée Download PDF

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Publication number
WO2007102984A1
WO2007102984A1 PCT/US2007/004426 US2007004426W WO2007102984A1 WO 2007102984 A1 WO2007102984 A1 WO 2007102984A1 US 2007004426 W US2007004426 W US 2007004426W WO 2007102984 A1 WO2007102984 A1 WO 2007102984A1
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Prior art keywords
block
block copolymer
active agent
surface active
composition
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English (en)
Inventor
Ryan E. Marx
James M. Nelson
Matthew J. Pinnow
Matthew J. Schmid
Rudolf J. Dams
Johan E. De Witte
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3M Innovative Properties Co
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3M Innovative Properties Co
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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers

Definitions

  • the present invention relates to a block copolymer comprising at least one block comprising a fluorinated macromonomer ("OLIGOC4") having the general formula:
  • each R ⁇ is independently selected from the group consisting of H, an alkyl, an alkyloxy, a halogen, a phenyl, a benzyl, a benzoyl, a hydroxyl, a carboxyl, an amine, an amide, a sulfide, a sulfoxide, a sulfate, a phosphate, a phosphate ester, a nitroxide, a thioester, and a carbonyl; and n is selected from 1 to 25.
  • the present invention relates to a block copolymer comprising at least one block having a quaternary ammonium ion and at least one block comprising a fluorinated macromonomer having the general formula:
  • CH2 CR 1 C ⁇ 2CH2CH 2 S- ⁇ CH2-CH(C ⁇ 2CH2CH2N(CH3)S ⁇ 2C4F9)) n -Rl wherein each R ⁇ is independently selected from the group consisting of H, an alkyl, an alkyloxy, a halogen, a phenyl, a benzyl, a benzoyl, a hydroxyl, a carboxyl, an amine, an amide, a sulfide, a sulfoxide, a sulfate, a phosphate, a phosphate ester, a nitroxide, a thioester, and a carbonyl; and n is selected from 1 to 25.
  • the present invention relates to a block copolymer comprising at least one block having a -CO 2 CH 2 CH 2 S-(CH2-CH(C ⁇ 2CH2CH2N(CH3)S ⁇ 2C4F9)) n -R 1 group, wherein the block copolymer is a comb-like block copolymer and wherein each R ⁇ is independently selected from the group consisting of H, an alkyl, an alkyloxy, a halogen, a phenyl, a benzyl, a benzoyl, a hydroxyl, a carboxyl, an amine, an amide, a sulfide, a sulfoxide, a sulfate, a phosphate, a phosphate ester, a nitroxide, a thioester, and a carbonyl; and n is selected from 1 to 25.
  • the following terms used in this description are defined as follows:
  • block refers to a portion of a block copolymer, comprising many monomeric units, that has at least one feature which is not present in the adjacent block or blocks;
  • Block copolymer means a polymer having at least two compositionally discrete segments, for example a di-block copolymer, a tri-block copolymer, a random block copolymer, a graft-block copolymer, a star-branched block copolymer or a hyper-branched block copolymer;
  • Random block copolymer means a copolymer having at least two distinct blocks wherein at least one block comprises a random arrangement of at least two types of monomer units;
  • Di-block copolymers and “Tri-block copolymers” means a polymer in which all the neighboring monomer units (except at the transition point) are of the same identity, for example, -AB is a di- block copolymer comprised of an A block and a B block that are compositionally different
  • Start-branched block copolymer or “Hyper-branched block copolymer” means a polymer consisting of several linear block chains linked together at one end of each chain by a single branch or junction point, also known as a radial block copolymer;
  • End functionalized means a polymer chain terminated with a functional group on at least one chain end.
  • the block copolymers of the present invention comprise at least one block comprising a fluorinated macromonomer having the general formula:
  • CH2 CR 1 CO 2 CH 2 CH2S-(CH2-CH(C ⁇ 2CH2CH2N(CH3)S ⁇ 2C4F9)) n -Rl wherein each R* is independently selected from the group consisting of H, a Cl to C4 alkyl, and a functional group deriyed from an initiator; and n is selected from 1 to 25.
  • group derived from an initiator it is meant a group, such as an alkyl radical, an alkoxy radical, a halogen, or another organic or inorganic group that is used to initiate the oligomerization of the -(CH2-CH(C ⁇ 2CH 2 CH2N(CH3)S ⁇ 2C4F9) n - segment in the preparation of the macromonomer.
  • R.2 is — CH2CH2S-(CH2- CH(CO2CH2CH2NMESO2C4F9) n -Rl
  • R3 is an alkyl or aryl substituent.
  • Block copolymers according to the present invention can be synthesized using any suitable living polymerization technique, including living anionic or living radical methods.
  • the block copolymers described in this invention have many potential applications as a result of their unique chemical structure, morphology, and molecular topology.
  • the block copolymers described herein are fluorinated materials, typically having very low surface energies.
  • the block copolymers may function effectively as surface modifiers, surfactants, compatibilizers, rheology modifiers, or other polymer additives.
  • these materials can contain a block of a non-fluorinated material, it is possible to tailor the solubility of the block copolymers described herein in a variety of polymers and solvents, thus improving the dispersibility either of the block copolymers themselves, or some other additive to the polymer or solvent (that is, wherein the block copolymer acts as a dispersing agent for the other additive in the polymer or solvent).
  • block copolymers of the present invention may form ordered morphologies at the molecular level.
  • ordered morphology block copolymers could be applied for a variety of applications related to nano-engineering, including the functions of dispersion, encapsulation, transport, delivery, and separation.
  • block copolymers produced from the macromonomer described herein may possess a higher concentration of fluorine atoms per side chain than, for instance, similar block copolymers produced from the monomer 2-(N-methylperfluorobutanesulfonamido) ethyl methacrylate (MeFBSEMA).
  • the higher concentration of fluorine atoms may enhance the repellant (oil, water) properties of block copolymers and materials containing block copolymers described herein over block copolymers and materials containing block copolymers produced from the monomer MeFBSEMA.
  • the fluorinated macromonomer described herein may be incorporated into a block copolymer composition containing other inexpensive, readily available hydrocarbon monomers, such as methacrylate monomers.
  • Such block copolymers may display substantially improved oil and water repellency over the same compositions of free radically polymerized polymers (that is, copolymers of the fluorinated macromonomer and a hydrocarbon monomer, that is not a block copolymer).
  • block copolymer compositions according to the present invention can provide nearly the same level of surface energy reduction as fluoromethacrylate homopolymers, where the block copolymers described herein incorporate levels of fluorinated macromonomer as low as 10 to 20% by weight.
  • the block copolymers of the present invention provide utility in surface activity and surface modification applications, even where the overall block copolymer has very low fluorine content, for instance, less than 50% by weight, less than 30% by weight, less than 20% by weight, or even less than 10% by weight, based on the weight of the block copolymer.
  • the block copolymers according to the present invention include di-block copolymers, as well as those having more complex molecular architectures, such as, for instance, triblock, multiblock, star, graft, and comb-like architectures. Materials where at least one of the blocks constitutes a copolymer of multiple monomers, for instance the fluorinated macromonomer described herein, are also within the scope of this invention. Some embodiments of block copolymers include di-block copolymers, tri-block copolymers, random block copolymers, graft- block copolymers, star-branched copolymers or hyper-branched copolymers. Additionally, block copolymers may be end functional ized (that is, have end functional groups).
  • OLIGOC4 fluorinated macromonomer
  • the block copolymers comprising OLIGOC4 can modify the surfaces of polymeric substrates and plastics when a small amount is blended into the substrate.
  • a block copolymer of the present invention is added into a polymeric material or plastic using standard compounding processes (for example melt extrusion), the resulting surface properties of the plastic can be * modified. This can potentially provide unique surface attributes to the substrate including: antifouling, scratch resistance, lubrication, printability, and others.
  • the amount of fluorinated polymer added to a substrate is preferably less than 10 wt %, more preferably less than 5 wt %, and most preferably less than 1 wt %.
  • thermoplastic elastomeric polymeric resins for substrates include, for example, polybutadiene, polyisobutylene, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, sulfonated ethylene-propylene-diene terpolymers, polychloroprene, poly(2,3- dimethylbutadiene), poly(butadiene-co-pentadiene), chlorosulfonated polyethylenes, polysulfide elastomers, block copolymers, made up of segments of glassy or crystalline blocks such as polystyrene, poly(vinyltoluene), poly(t-butylstyrene), polyester and the like and the elastomeric blocks such as polybutadiene, polyisoprene, ethylene-propylene copolymers, ethylene-butylene copolymers, polyether ester and the like as for example the copolymers in poly(
  • Useful polymeric resins for substrates also include fluoropolymers, that is, at least partially fluorinated polymers.
  • fluoropolymers include polyvinyl idene fluoride; terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride; copolymers of tetrafluoroethylene, hexafluoropropylene, perfluoropropyl vinyl ether, and vinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymers; tetrafluoroethylene- perfluoro(alky! vinyl ether) copolymers (for example, tetrafluoroethylene-perfluoro(propyl vinyl ether)); and combinations thereof.
  • the block copolymer may be added in an amount less than 10 wt%, less than 5 wt %, or even less than 1 wt % of a surface-active agent derived from a block copolymer of the present invention.
  • These materials provide for and control the formation of a large number of small cells or voids in the membrane, which leads simultaneously to the formation of a cellular membrane with low density and an opaque, uniform appearance.
  • the properties and methods of making cellular pressure-sensitive adhesive (PSA) membranes of this type are described in U.S. Pat. No. 4,415,615 (Esmay).
  • Cellular PSA membranes or foam tapes can be made not only by forming a cellular polymeric membrane that has PSA properties, but also by applying a layer of PSA to at least one major surface of a cellular polymeric membrane.
  • Block copolymers according to the present invention may be formed by sequentially polymerizing different monomers.
  • Useful methods for forming block copolymers include, for example, anionic, cationic, coordination, and free radical polymerization methods.
  • the block copolymers of the present invention may interact with fillers through functional moieties.
  • the block copolymers of the present invention may be useful as a dispersing agent in a composition comprising a host polymer, a filler, and a block copolymer according to the present invention.
  • Suitable host polymers include, for instance, any of a number of thermoplastic polymers and thermoplastic elastomeric polymers, which may be fluorinated or non-fluorinated.
  • thermoplastic polymer resins include polylactones such as, for example, poly(pivalo lactone) and poly(caprolactone); polyurethanes such as, for example, those derived from reaction of diisocyanates such as 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m- phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl- 4,4 1 -diphenylmethane diisocyanate, 3.3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'- diphenylisopropylidene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, 3,3'-dimethoxy-4
  • thermoplastic elastomeric polymeric resins include, for example, polybutadiene, polyisobutylene, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, sulfonated ethylene-propylene-diene terpolymers, polychloroprene, poly(2,3-dimethylbutadiene), poly(butadiene-co-pentadiene), chlorosulfonated polyethylenes, polysulfide elastomers, block copolymers, made up of segments of glassy or crystalline blocks such as polystyrene, poly(vinyltoluene), poly(t-butylstyrene), polyester and the like and the elastomeric blocks such as polybutadiene, polyisoprene, ethylene-propylene copolymers, ethylene-butylene copolymers, polyether ester and the like as for example the copolymers in poly(st
  • Useful polymeric resins also include fluoropolymers, that is, at least partially fluorinated polymers.
  • fluoropolymers include polyvinylidene fluoride; terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride; copolymers of tetrafluoroethylene, hexafluoropropylene, perfluoropropyl vinyl ether, and vinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymers; tetrafluoroethylene- perfluoro(alkyl vinyl ether) copolymers (for example, tetrafluoroethylene-perfluoro ⁇ ropyl vinyl ether)); and combinations thereof.
  • thermoplastic fluoropolymers include, for example, those marketed by Dyneon LLC under the trade designations "THV” (for example, “THV 220", "THV
  • Suitable fillers include, for instance, carbon black, carbon nanotubes, clay, and any conventional filler or additive utilized, for instance, in melt processing compositions.
  • fillers may also include pigments, carbon fibers, hindered amine light stabilizers, anti-block agents, glass fibers, aluminum oxide, silica, mica, cellulosic materials, or one or more polymers with reactive or polar groups.
  • polymers with reactive or polar groups include, but are not limited to, polyamides, polyimides, functional polyolefins, polyesters, polyacrylates and methacrylates.
  • the filler is a cellulosic material.
  • Cellulosic materials are commonly utilized in melt processable compositions to impart specific physical characteristics to the finished composition.
  • Cellulosic materials generally include natural or wood materials having various aspect ratios, chemical compositions, densities, and physical characteristics.
  • Non-limiting examples of cellulosic materials include wood flour, wood fibers, sawdust, wood shavings, newsprint, paper, flax, hemp, rice hulls, kenaf, jute, sisal, peanut shells.
  • Combinations of cellulosic materials, or cellulosic materials with other interfering components, may also be used in the melt processable composition.
  • the block copolymers of the present invention may also be used as part of a composition for melt processing.
  • melt processes amenable to this invention include methods such as extrusion, injection molding, batch mixing and rotomolding.
  • the block copolymers of the present invention may also be suitable for use as a polymer processing aid or as a coupling agent improve the melt processability of polymer composite systems containing conventionally known fluoropolymer, particularly fluoroplastic and fluoroelastomeric processing aids.
  • the present invention may improve the melt processability of compositions containing fillers, particularly interfering components that may have a strong interfacial tension with host polymers.
  • the block copolymers may enable a significant reduction in the interfacial tension between the host polymer and the fillers, thus resulting in an improved efficacy of the block copolymer either as a polymer processing aid or as an additive to improve the performance of a fluoropolymer processing aid.
  • the resulting processed material may exhibit a significant reduction in melt fracture as well as improved physical characteristics such as water uptake, flexural modulus, or tensile strength.
  • the block copolymers of the present invention may comprise functional blocks, typically having one or more polar moieties such as, for example, acids (for example, -CO2H, -SO3H, -
  • PO3H PO3H
  • -OH -SH
  • primary, secondary, or tertiary amines ammonium
  • N-substituted or unsubstituted amides and lactams N-substituted or unsubstituted thioamides and thiolactams
  • anhydrides linear or cyclic ethers and polyethers; isocyanates; cyanates; nitriles; carbamates; ureas; thioureas; heterocyclic amines (for example, pyridine or imidazole)).
  • Useful monomers that may be used to introduce such groups include, for example, acids (for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and including methacrylic acid functionality formed via the acid catalyzed deprotection of t-butyl methacrylate monomeric units as described in U.S. patent applicatioin publication No. U.S.
  • acrylates and methacrylates for example, 2-hydroxyethyl acrylate
  • acrylamide and methacrylamide for example, N- substituted and N,N disubstituted acrylamides
  • aliphatic amines for example, 3-dimethylaminopropyl amine, N,N-dimethylethylenediamine
  • heterocyclic monomers for example, 3-dimethylaminopropyl amine, N,N
  • suitable blocks may have one or more hydrophobic moieties such as, for example, aliphatic and aromatic hydrocarbon moieties such as those having at least 4, 8, 12, or even 18 carbon atoms; fluorinated aliphatic and/or fluorinated aromatic hydrocarbon moieties, such as for example, those having at least 4, 8, 12, or even 18 carbon atoms; and silicone moieties.
  • hydrophobic moieties such as, for example, aliphatic and aromatic hydrocarbon moieties such as those having at least 4, 8, 12, or even 18 carbon atoms; fluorinated aliphatic and/or fluorinated aromatic hydrocarbon moieties, such as for example, those having at least 4, 8, 12, or even 18 carbon atoms; and silicone moieties.
  • the block copolymers according to the present invention may also have blocks selected from the group consisting of vinyl aromatics, styrenics, dienes, vinyl pyridines, acrylates, methacrylates, epoxides, oxiranes, cyclic sulfides, lactones, lactides, cyclic carbonates, lactams, cyclosiloxanes, acrylonitrile, [n]metallocenophanes, fluorinated acrylates, fluorinated methacrylates and anionically-polymerizable polar monomers.
  • useful block copolymers having functional moieties include poly(OLIGOC4-block-methacrylic acid)), poly(OLIGOC4-block-t-butyl methacrylate), poly(styrene-block-t-butyl methacrylate-block- OL1GOC4), poly(styrene-block-methacrylic anhydride-block-OLlGOC4), poly(styrene-block- methacrylic acidblock-OLIGOC4), poly(styrene- block-(methacrylic anhydride-co-methacrylic acid)-block-OLIGOC4)) 5 poly(styrene-block- (methacrylic anhydride-co-methacrylic acid-co-OLIGOC4)), poly(styrene-block-(t-butyl methacrylate-co-OLIGOC4)), poly(styrene-block-isoprene-block-t-butyl methacrylate
  • each material to be analyzed was placed between 0.051 mm thick untreated polyester liners, which in turn were placed between 2 aluminum plates (3.2 mm thick each) to form a stack.
  • Two shims (1 mm thick each) were placed to either side of the stack such that upon pressing the assembled stack the mixture would not come into contact with either shim.
  • Each stack was placed in a heated hydraulic press available under the trade designation "WABASH MPI MODEL G30H-15-LP" from Wabash MPI (Wabash IN). Both the top and bottom press plates were heated at 193 0 C.
  • the stack was pressed for 1 minute at 1500 psi (10 MPa).
  • the hot stack was then moved to a low-pressure water-cooled press for 30 seconds to cool the stack.
  • the stack was disassembled and the liners were removed from both sides of the film disc that resulted from pressing the mixture.
  • the average molecular weight and polydispersity of a sample was determined by Gel Permeation Chromatography (GPC) analysis. Approximately 25 mg of a sample was dissolved in GPC
  • An Erma ERC-7525A Refractive Index Detector (available from JM Science Inc. Grand Island, NY) was used to detect changes in concentration.
  • Number average molecular weight (Mn) and polydispersity index (PDI) calculations were based on a calibration mode that used narrow polydispersity polystyrene controls ranging in molecular weight from 580 to 7.5 x 10 ⁇ . The actual calculations were made with PL Caliber® software available from Polymer Laboratories, Amherst, MA.
  • Block Concentration The concentration of different blocks in a block copolymer was determined by Nuclear Magnetic Resonance (NMR) spectroscopy analysis. A sample was dissolved in deuterated chloroform to a concentration of about 10 weight % and placed in a Unity® 500 MHz NMR Spectrometer available from Varian Inc., Palo Alto, California. Block concentrations were calculated from relative areas of characteristic block component spectra.
  • NMR Nuclear Magnetic Resonance
  • the water repellency of composite samples was measured using a water/isopropyl alcohol test and is expressed in terms of a water repellency rating using a scale of 0 to 10.
  • Composite materials that are resistant to water only are given a rating of 0, whereas composite materials resistant to isopropyl alcohol (the most penetrating of the test solutions) are given a rating of 10.
  • Intermediate values are determined by the use of other water/isopropyl alcohol mixtures, in which percentage amounts of water and isopropyl alcohol are each multiples of 10.
  • the repellency rating corresponds to the amount of isopropyl alcohol in the most penetrating mixture that does not penetrate or wet the composite samples after 10 seconds contact.
  • a rating of 2 reflects that the most penetrating mixture that does not penetrate or wet the composite sample after 10 seconds of contact contains 20% isopropyl alcohol and 80% water.
  • the P(I-6-OLIGOC4) block copolymer was synthesized by sequential anionic polymerization using a stirred tubular reactor (STR) according to the methods outlined in U.S. Patent 6,969,491. The polymerization was quenched with isopropanol.
  • Table 1 details the experimental conditions, temperature profile and polymer analytical data for the P(I- ⁇ -OLIGOC4) block copolymer respectively. Flow rates were varied as in Table 1 to produce Examples la-Id, shown in Table 2.
  • the temperature profile in each zone was, by zone, Tl (10 0 C); T2 (70 0 C); T3 (15°C); T4 (OX); T5 (0°C).
  • the Polymer analytical data for the P(I-6-OLIGOC4) block copolymer is shown below. 1,2- polyisoprene, 1,4- polyisoprene, 3,4- polyisoprene, and OLIGOC4 are incorporated into the block copolymer, OLIGOC4 monomer is residual monomer in the block copolymer:
  • High density polyethylene was compounded with P(I-£-OLIGOC4) using a 19 mm, 15:1 L:D, Haake Rheocord Twin Screw Extruder (commercially available from Haake Inc., Newington, NH) equipped with a conical counter- rotating screw and an Accurate open helix dry material feeder (commercially available from Accurate Co. Whitewater, WI).
  • the extrusion parameters were controlled and experimental data recorded using a Haake RC 9000 control data computerized software (commercially available for Haake Inc., Newington, NH). Materials were extruded through a standard 0.05 cm diameter, 4-strand die (commercially available from Haake Inc., Newington, NH).
  • HDPE was first pre-dried in a vacuum oven for 16 hr at 80 0 C (ca. 1 mraHg). Oligomeric additive samples were cryogenically ground prior to compounding. HDPE/additives were then dry mixed in a plastic bag until a relatively uniform mixture was achieved. The material was flood fed into the extruder and was processed at 180 0 C. Injection molded plaques were prepared as described above (Injection Molding), for CE-Ia and Ex-2b, as shown in Table 3. For Ex-2b ⁇ HDPE was compounded with P(I- ⁇ -OLIGOC4) produced from Example Ia. CE-Ia was prepared as in Ex-2b, without the P(I-6-OLIGOC4).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un copolymère séquencé, un procédé de réduction de la tension superficielle d'un liquide consistant à ajouter audit liquide moins de 10% en poids d'un agent de surface dérivé du copolymère séquencé; un procédé de modification de la chimie de surface d'un substrat polymère consistant à ajouter moins de 10% en poids d'un agent de surface dérivé du copolymère séquencé; une composition de mousse polymérisée préparée à partir d'un mélange contenant un ou plusieurs éléments sélectionnés parmi des monomères, des oligomères et des polymères, le mélange comprenant moins de 10% en poids d'un agent de surface dérivé du copolymère séquencé et un article comprenant la mousse polymérisée. L'invention concerne également un copolymère séquencé comprenant au moins une séquence présentant un ion ammonium quaternaire.
PCT/US2007/004426 2006-03-08 2007-02-20 Matériaux à architecture contrôlée Ceased WO2007102984A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8710151B2 (en) * 2007-12-25 2014-04-29 Nippon Soda Co., Ltd. Onium salt-containing polymer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5211854A (en) * 1991-04-25 1993-05-18 Betz Laboratories, Inc. Water soluble graft copolymers and methods of use thereof
US5276175A (en) * 1991-04-02 1994-01-04 Minnesota Mining And Manufacturing Company Isocyanate derivatives comprising flourochemical oligomers
EP1216275A1 (fr) * 1999-09-24 2002-06-26 3M Innovative Properties Company Composition polymere contenant un oligomere fluorochimique
US6441114B1 (en) * 1999-06-11 2002-08-27 3M Innovative Properties Company Adhesives for use on fluorine-containing or polycarbonate surfaces
US6783850B2 (en) * 1999-12-22 2004-08-31 Soken Chemical & Engineering Co., Ltd. Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5276175A (en) * 1991-04-02 1994-01-04 Minnesota Mining And Manufacturing Company Isocyanate derivatives comprising flourochemical oligomers
US5211854A (en) * 1991-04-25 1993-05-18 Betz Laboratories, Inc. Water soluble graft copolymers and methods of use thereof
US6441114B1 (en) * 1999-06-11 2002-08-27 3M Innovative Properties Company Adhesives for use on fluorine-containing or polycarbonate surfaces
EP1216275A1 (fr) * 1999-09-24 2002-06-26 3M Innovative Properties Company Composition polymere contenant un oligomere fluorochimique
US6783850B2 (en) * 1999-12-22 2004-08-31 Soken Chemical & Engineering Co., Ltd. Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8710151B2 (en) * 2007-12-25 2014-04-29 Nippon Soda Co., Ltd. Onium salt-containing polymer

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