WO2007102993A1 - Materiaux a architecture regulee - Google Patents

Materiaux a architecture regulee Download PDF

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Publication number
WO2007102993A1
WO2007102993A1 PCT/US2007/004577 US2007004577W WO2007102993A1 WO 2007102993 A1 WO2007102993 A1 WO 2007102993A1 US 2007004577 W US2007004577 W US 2007004577W WO 2007102993 A1 WO2007102993 A1 WO 2007102993A1
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Prior art keywords
block
block copolymer
composition
active agent
surface active
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PCT/US2007/004577
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English (en)
Inventor
Ryan E. Marx
James M. Nelson
Matthew J. Pinnow
Matthew J. Schmid
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3M Innovative Properties Company
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Publication of WO2007102993A1 publication Critical patent/WO2007102993A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • 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
    • C08F214/00—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 a halogen
    • C08F214/18—Monomers containing fluorine

Definitions

  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • m is from 0 to 25.
  • Rf2, Rfj, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • n is from 2 to 25, and m is from 0 to 25.
  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • n is from 2 to 25, and m is from 0 to 25.
  • A is a carbonyloxy or carbonylimino group
  • Rf] is a Cl to ClO perfluoroalkyl
  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • n is from 2 to 25, and m is from 0 to 25.
  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • n is from 2 to 25, and m is from 0 to 25.
  • the present invention relates to an article comprising the polymerized foam composition.
  • An example of an article is a pressure sensitive adhesive tape.
  • the present invention relates to a block copolymer comprising at least one block comprising a fluorinated monomer having the general formula:
  • CH 2 CR 1 CO 2 CH 2 CH 2 S-[X] 3 -R l wherein X is Rfl O(Rf2 ⁇ ) n (R ⁇ O) m (Rf4)AQC(R)CH 2 , wherein
  • A is a carbonyloxy or carbonylimino group
  • RfI is a Cl to ClO perfluoroalkyl
  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • each Rl is any group derived from an initiator, including those functional groups 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 s is selected from 1 to 25.
  • group derived from an initiator it is meant a group, such as 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, or another organic or inorganic group, that is used to initiate the oligomerization of the RflO(Rf2 ⁇ ) n (Rf3 ⁇ ) m (Rf4)AQC(R)CH2 segment in the preparation of the macromonomer
  • CH 2 CR 1 CO 2 CH 2 CH 2 S-[X] n -R 1 .
  • 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,jfor example, -AB is a di- block copolymer comprised of an A block and a B block that are compositionally different and ABC is a tri-block copolymer comprised of A, B, and C blocks, each compositionally different;
  • Graft-block copolymer means a
  • 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.
  • This invention is a new class of block copolymers wherein at least one of the block copolymer contains a fluorinated monomer.
  • A carbonyloxy or carbonylimino
  • RfI is a Cl to ClO perfluoroalkyl
  • Rf2, Rf3, and Rf4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino. n if from 2 to 25, and m is from 0 to 25.
  • Rl is H or a Cl to C4 alkyl group
  • R2 is A(Rf4)(Rf3 ⁇ ) m (Rf2 ⁇ ) n Rfi, where A, RfI , Rf2, RO, and Rf4 are as described above, and R3 is H, or any 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 monomer 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 monomer 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 monomer 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 monomer as low as 10 to 20% by weight.
  • the block copolymers of the present invention provide utility in surfactancy 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 monomer described herein, are also within the scope of this invention. Some embodiments of block copolymers include di-block copolymers, trt-block copolymers, random block copolymers, graft-block copolymers, star- branched copolymers or hyper-branched copolymers. Additionally, block copolymers may be end functionalized (that is, have end functional groups).
  • Rf 2 , Rf3, and Rf 4 are each independently a Cl to ClO perfluoroalkyl
  • R is an H or a Cl to C4 alkyl
  • Q is a divalent linking group.
  • divalent linking groups include alkylene, hydroxy substituted alkylene, heteroalkylene, hydroxy substituted heteroalkylene, arylene, hydroxy substituted arylene, carbonyl, carbonyloxy, carbonylimino, oxy, and/or imino.
  • n is from 2 to 25, and m is from 0 to 25.
  • the block copolymers comprising HFPOMA 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, ethyl ene-butylene copolymers, polyether ester and the like as for example the copo
  • Useful polymeric resins for substrates 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(propyl vinyl ether)); and combinations thereof.
  • the present invention may provide a method for stabilizing cellular polymeric membranes when a block copolymer comprising at least one block comprising HFPOMA is added into various monomeric and/or polymeric systems (for example, curable acrylic monomer/polymer mixtures including froths that comprise gas and polymerizable material).
  • 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.
  • PSA pressure-sensitive adhesive
  • 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(pivalolactone) 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'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4' ⁇ biphenyl diisocyanate, 4,4'- diphenylisopropylidene diisocyanate, 3,3 l -dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyI-4 3 4'- diphenylmethane diisocyanate, 3,3'-dime
  • 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(propyl 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 400G”, “THV 500G”, “THV 815”, and “THV 610X”), “PVDF”, “PFA”,”HTE”, “ETFE”, and “FEP”; those marketed by Atochem North America, Philadelphia, Pennsylvania under the trade designation “KYNAR” (for example, “KYNAR 740”); those marketed by Ausimont, USA, Morristown, New Jersey under the trade designations "HYLAR” (for example, “HYLAR 700”) and “HALAR ECTFE”.
  • 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 publication No. U.S.
  • acrylates and methacrylates for example, 2-hydroxyethyl acrylate
  • acrylamide and rnethacrylarnide N-substituted and N 5 N- disubstituted acrylamides
  • N-t-butylacrylamide N,N-(dimethylamino)ethyl- acrylamide, N,N-dimethyl-acrylamide, N,Ndimethylmeth-acrylamide
  • aliphatic amines for example, 3-dimethylaminopropyl amine, N,N-dimethylethylened
  • 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.
  • R is hydrogen, Cl to ClO alkyl, or C6- ClO aryl; and
  • X is a divalent connecting group.
  • 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(HFPOMA-block-methacrylic acid)), poly(HFPOMA-block-t-butyl methacrylate), poly(styrene-block-t-butyl methacrylate-block-HFPOMA), poly(styrene-block-methacrylic anhydride-block-HFPOMA), poly(styrene-block- methacrylic acidblock-HFPOMA), poly(styrene- block-(methacrylic anhydride-co-methacrylic acid)-block-HFPOMA)), poly(styrene-block- (methacrylic anhydride-co-methacrylic acid-co-HFPOM A)), poly(styrene-block-(t-butyl methacrylate-co-HFPOMA)), poly(styrene-block-isoprene-block-t-butyl methacrylate-block- HFPOMA),
  • 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 10 milliliters (mL) of tetrahydrofuran (THF) to form a mixture. The mixture was filtered using a 0.2 micron polytetrafluoroethylene (PTFE) syringe filter. Then about 150 microliters ( ⁇ L) of the i filtered solution was injected into a Plgel-Mixed B column (available from Polymer Laboratories,
  • Amherst, MA that was part of a GPC system also having a Waters® 717 Autosampler and a Waters® 590 Pump (available from Waters Corporation, Milford, MA).
  • the system operated at room temperature, with a THF eluent that moved at a flow rate of approximately 0.95mL/min.
  • An Erma ERC-7525A Refractive Index Detector (available from JM Science Inc. Grand Island, NY)
  • 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 P(I-O-HFPOMA) block copolymer was synthesized by sequential anionic polymerization according to the methods outlined in U.S. Patent 6,969,491.
  • a solution containing a .living sample of DPE-modified PI in toluene (200 g) was collected from the end of the STR and stored in an inert atmosphere.
  • 50 g of HFPOMA was added and the resultant 2 phase system was agitated for 20 minutes, resulting in a homogeneous dispersion.
  • the polymerization was quenched by adding 10 ml of isopropanol. Tables 2-3 detail the experimental conditions, temperature profile and polymer analytical data for the P(I- ⁇ -HFPOMA) block copolymer respectively.
  • the temperature profile in each zone was, by zone, Tl (40 0 C); T2 (50 0 C); T3 (50°C); T4 (10°C); T5 (10 0 C).
  • the Polymer analytical data for the P(I- ⁇ -HFPOMA) block copolymer showed a composition in mole % (wt %) of: 1,2 PI 1.2% (0.7); 1,4 PI 68.6% (40.1); and PHFPOMA 5.2%
  • the number average molecular weight was 9.6 x 10 ⁇ g/mol and the polydispersity index was 3.3.
  • the P(S- ⁇ -HFPOMA) block copolymer was synthesized by sequential anionic polymerization.
  • a "living" polystyrene polymer was synthesized in a 0.94 L stirred tubular reactor (STR) according to the methods outlined in US 6,969,491.
  • the "living" polystyrene-DPE polymer was synthesized continuously in the STR and collected under nitrogen in a separate vessel.
  • 30.5 g of HFPOMA was added to 1000 g of the "living" polymer solution and the solution was shaken vigorously to form the P(S- ⁇ -HFPOMA) block copolymer.
  • Tables 3-5 detail the experimental conditions, temperature profile and polymer analytical data for the P(S- ⁇ -HFPOMA) block copolymer, respectively.
  • the temperature profile in each zone was, by zone, Tl (70°C); T2 (50°C); T3 (50°C); T4 (2O 0 C); T5 (20°C).
  • the Polymer analytical data for the P(S- ⁇ -HFPOMA) block copolymer showed a composition in mole % of: Styrene (96.1); and PHFPOMA (3.9).
  • the number average molecular weight was 2.8 x 10 ⁇ g/mol and the polydispersity index was 1.7.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

La présente invention concerne un copolymère séquencé; un procédé de réduction de la tension superficielle d'un liquide comprenant l'addition audit liquide de moins de 10 % en poids d'un agent tensioactif dérivé du copolymère séquencé; un procédé de modification de la chimie de surface d'un substrat polymère comprenant l'addition de moins de 10 % en poids d'un agent tensioactif dérivé du copolymère séquencé; une composition de mousse polymérisée faite à partir d'un mélange contenant un ou plusieurs monomères, oligomères et polymères, le mélange comprenant moins de 10 % en poids d'un agent tensioactif dérivé du copolymère séquencé et un article comprenant la mousse polymérisée. La présente invention concerne également un copolymère séquencé comprenant au moins une séquence ayant un ion ammonium quaternaire.
PCT/US2007/004577 2006-03-08 2007-02-20 Materiaux a architecture regulee WO2007102993A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013017470A1 (fr) 2011-08-04 2013-02-07 Solvay Specialty Polymers Italy S.P.A. Compositions de fluoropolymères ionisables
WO2016150942A1 (fr) 2015-03-26 2016-09-29 Solvay Specialty Polymers Italy S.P.A. Compositions non aqueuses de polymère fluoré réticulable
US9683151B2 (en) 2012-12-13 2017-06-20 Solvay Specialty Polymers Italy S.P.A. Non-aqueous fluoropolymer compositions

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US6395821B1 (en) * 1999-03-29 2002-05-28 Asahi Glass Company, Limited Water-dispersible water-and-oil repellant composition
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WO2005061638A1 (fr) * 2003-12-17 2005-07-07 3M Innovative Properties Company Compositions de revetement comportant des copolymeres fluores reactifs ayant des groupes perfluoropolyether lateraux

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US3553179A (en) * 1968-05-06 1971-01-05 Du Pont Acrylate-type esters of perfluoropoly-oxa-alkaneamidoalkyl alcohols and their polymers
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US6395821B1 (en) * 1999-03-29 2002-05-28 Asahi Glass Company, Limited Water-dispersible water-and-oil repellant composition
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WO2005061638A1 (fr) * 2003-12-17 2005-07-07 3M Innovative Properties Company Compositions de revetement comportant des copolymeres fluores reactifs ayant des groupes perfluoropolyether lateraux

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Publication number Priority date Publication date Assignee Title
WO2013017470A1 (fr) 2011-08-04 2013-02-07 Solvay Specialty Polymers Italy S.P.A. Compositions de fluoropolymères ionisables
CN103842398A (zh) * 2011-08-04 2014-06-04 索尔维特殊聚合物意大利有限公司 可电离氟聚合物的组合物
US9090772B2 (en) 2011-08-04 2015-07-28 Solvay Specialty Polymers Italy S.P.A. Compositions of ionisable fluoropolymers
CN103842398B (zh) * 2011-08-04 2016-08-17 索尔维特殊聚合物意大利有限公司 可电离氟聚合物的组合物
US9683151B2 (en) 2012-12-13 2017-06-20 Solvay Specialty Polymers Italy S.P.A. Non-aqueous fluoropolymer compositions
WO2016150942A1 (fr) 2015-03-26 2016-09-29 Solvay Specialty Polymers Italy S.P.A. Compositions non aqueuses de polymère fluoré réticulable
US10280247B2 (en) 2015-03-26 2019-05-07 Solvay Specialty Polymers Italy S.P.A. Non-aqueous cross-linkable fluoropolymer compositions

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