WO2007102991A1

WO2007102991A1 - Controlled architecture materials

Info

Publication number: WO2007102991A1
Application number: PCT/US2007/004530
Authority: WO
Inventors: Ryan E. Marx; James M. Nelson; Matthew J. Pinnow; Matthew J. Schmid
Original assignee: 3M Innovative Properties Company
Priority date: 2006-03-08
Filing date: 2007-02-20
Publication date: 2007-09-13

Abstract

A block copolymer; a method of reducing the surface tension of a liquid comprising adding to said liquid less than 10 wt % of a surface active agent derived from the block copolymer; a method for modifying the surface chemistry of a polymeric substrate comprising adding less than 10 wt % of a surface active agent derived from the block copolymer; a polymerized foam composition made from a mixture containing one or more of monomers, oligomers, and polymers, the mixture comprising less than 10 wt % of a surface active agent derived from the block copolymer and an article comprising the polymerized foam. A block copolymer comprising at least one block having a quaternary ammonium ion.

Description

CONTROLLED ARCHITECTURE MATERIALS

SUMMARY

In one aspect, the present invention relates to a block copolymer comprising at least one block comprising a fluorinated monomer having a general formula selected from the group comprising:

CH₂=CHCO₂CH₂CHO₂CNH(CoH₄)CH₂(CgH₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉ ("C4-MDI- HEA); and

CH₂=CR¹ CO₂CH₂CH₂S-[X]_n-R¹ (Oligomer of C4-MDI-HEA); wherein X is CH₂CHCO₂CH₂eHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C2H₄N(CH3)SO₂C₄F9, wherein each Rl is independently selected from the group consisting of H₅ 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. In another aspect, the present invention relates to a block copolymer comprising at least one block having a quaternary ammonium ion, with the proviso that at least one block comprises a fluorinated monomer selected from the group consisting of: CH₂=CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉;

CH₂=CR¹CO₂CH₂CH₂S-[X]_n-R¹; CH₂=CHCO₂CH₂CHO₂CN(⁺)(R)₂(C₆H₄)CH₂(C₆H₄)N(⁺)(R)₂CO₂C₂H₄N(CH₃)SO₂C₄F₉; and .

CH₂=CR 1 CO₂CH₂CH₂S-[Z]_n-R 1 wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉, Z is

CH₂CHCO₂CH₂CHO₂CN(+)(R)₂(C₆H₄)CH₂(C₆H₄)N(⁺)(R)₂CO₂C₂H₄N(CH₃)SO₂C₄F₉, wherein each R¹ 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, and wherein each R is independently selected from H, an alkyl, and an aralkyl. In yet another aspect, the present invention relates to a method of reducing the surface tension of a liquid comprising adding to said liquid from 0.0025 to 10 wt % of a surface active agent derived from a block copolymer comprising at least one block comprising a fluorinated monomer having a general formula selected from the group comprising: CH2=CHCO2CH2CHO2CNH(C6H4)CH₂(C6H4)NHCO2C2H4N(CH3)SO2C4F₉; and

CH₂=CR¹CC^CH₂CH₂S-[X]_n-Rl wherein X is CH2CHCO2CH₂CHO₂CNH(C₆H4)CH2(C₆H4)NHCO₂C₂H4N(CH₃)SO₂C₄F9, wherein each R¹ 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.

In a further aspect, the present invention relates to a method for modifying the surface chemistry of a polymeric substrate comprising adding from 0.1 to 10 wt % of a surface active agent derived from a block copolymer comprising at least one block comprising a fluorinated monomer having a general formula selected from the group comprising:

CH₂=CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉; and

CH₂=CR 1 CO₂CH₂CH₂S-[X]_n-R 1 wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉, wherein each R¹ 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.

Another aspect of the present invention relates to a polymerized foam composition made from a mixture containing one or more of monomers, oligomers, and polymers, the mixture comprising from 0.1 to 10 wt % of a surface active agent derived from a block copolymer comprising at least one block comprising a fluorinated monomer having a general formula selected from the group comprising:

CH₂=CR 1 CO₂CH₂CH₂S-[X]_n-R¹ wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉, 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.

In another aspect, the invention relates to an article comprising the polymerized foam composition. An example of an article is a pressure sensitive adhesive tape.

For purposes of the present invention, 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

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 polymer consisting of a side-chain polymers grafted onto a main chain. The side chain polymer can be any polymer different in composition from the main chain copolymer;

"Star-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. DETAILED DESCRIPTION

The block copolymers of the present invention comprise at least one block comprising a fluorinated monomer having a general formula selected from the group comprising: CH₂=CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉; and

CH₂=CR ! CO₂CH₂CH₂S-[X]_n-R¹ wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉, wherein each R¹ a group derived from an initiator. Exemplary R¹ groups include, for instance, 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 nitrόxide, a thioester, and a carbonyl; and n is selected from 1 to 25.

By "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 CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉ segment in the preparation of the macromonorher CH₂=CR¹ CO₂CH₂CH₂S-[X]_n-R¹.

In some embodiments, specific structures illustrating the block copolymers described herein may be illustrated by the following fluorinated copolymer structures:

wherein in this context, each R* is independently selected from the group consisting of H and Cl to C4 alkyl, R.2 is O-X— N(R)SO2C4F9, Rβ is selected from the group consisting of H, an alkyl substituent, and an aryl substituent, and X is -C2^H4°2CNH(C6H4)CH2C6H4NHCθ2C2H4θ-.

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. Because 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). In other embodiments, block copolymers of the present invention may form ordered morphologies at the molecular level. Such 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.

Furthermore, 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.

Furthermore, in some embodiments, 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). In some embodiments, block copolymer compositions according to the present invention can provide nearly the same level of surface energy reduction as fluorqmethacrylate homopolymers, where the block copolymers described herein incorporate levels of fluorinated monomer as low as 10 to 20% by weight. In yet further embodiments, 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 instace, 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, tri-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).

Some embodiments of the present invention comprise a block copolymer comprising at least one block having a quaternary ammonium ion, with the proviso that at least one block comprises a fluorinated monomer selected from the group consisting of: CH₂=CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(CeH₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉;

CH₂=CR¹CO₂CH₂CH₂S-[X]_n-R¹ ;

CH₂=CHCO₂CH₂CHO₂CN(⁺)(R)₂(C₆H₄)CH₂(C₆H₄)N(⁺)(R)2CO₂C₂H₄N(CH3)SO₂C₄F9; and CH₂=CR¹ CO₂CH₂CH₂S-[Z]_n-R¹ wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉, Z is CH₂CHCO₂CH₂CHO₂CN(⁺)(R)₂(C₆H₄)CH₂(C₆H₄)N(⁺)(R)₂CO₂C₂H₄N(CH3)SO₂C₄F₉, 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, and wherein each R is independently selected from H, an alkyl, and an aralkyl.

In some embodiments of the present invention, the block copolymers comprising C4-MDI- HEA or the oligomer can modify the surfaces of polymeric substrates and plasties when a small amount is blended into the substrate. When 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 %.

Useful 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 poly ethylenes, polysulfϊde 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(styrene-butadiene- styrene) block copolymer manufactured by Shell Chemical Company under the trade name of "KRATON". Copolymers and/or mixtures of these aforementioned polymers can also be used

Useful polymeric resins for substrates also include fluoropolymers, that is, at least partially fluorinated polymers. Useful fluoropolymers include, for example, those that are preparable (for example, by free-radical polymerization) from monomers comprising chlorotrifluoroethylene, 2- chloropentafluoropropene, 3-chloropentafluoropropene. vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, 1 -hydropentafluoropropene, 2-hydropentafluoropropene, 1,1- dichlorofluoroethylene, dichlorodifluoroethylene, hexafluoropropylene, vinyl fluoride, a perfluorinated vinyl ether (for example, a perfluoro(alkoxy vinyl ether) such as CF3θCF2CF2CF2θCF=CF2, or a perfluoro(alkyl vinyl ether) such as perfluoro(methyl vinyl ether) or perfluoroφropyl vinyl ether)), cure site monomers such as for example nitrile containing monomers (for example, CF₂=CFO(CF2) L^CN _> CF2=CFO[CF2CF(CF₃)O]q(CF₂O)_yCF(CF3)CN, CF2=CF[OCF₂CF(CF3)]rO(CF2)_tCN, or CF2=CFO(CF₂)_UOCF(CF3)CN where L = 2-12; q = 0-4; r = 1-2; y = 0-6; t = 1-4; and u = 2-6), bromine containing monomers (for example, Z-Rf-O_x- CF=CF2, wherein Z is Br or I, Rf is a substituted or unsubstituted C]-Ci₂ fluoroalkylene, which may be perfluorinated and may contain one or more ether oxygen atoms, and x is 0 or 1); or a combination thereof, optionally in combination with additional non-fluorinated monomers such as, for example, ethylene or propylene; Specific examples of such 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.

In some embodiments, the present invention may provide a method for stabilizing cellular polymeric membranes when a block copolymer comprising C4-MDI-HEA is added into various monomeric and/or polymeric systems (for example, curable acrylic monomer/polymer mixtures including froths that comprise gas and polymerizable material). For instance, 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.

In multi-component compositions the block copolymers of the present invention may interact with fillers through functional moieties. For instance, 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.

Useful 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'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'- diphenyl methane diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, toluidine diisocyanate, hexamethylene diisocyanate, or 4,4'-diisocyanatodiphenylmethane with linear long-chain diols such as poly(tetramethylene adipate), poly(ethylene adipate), poly(l,4- butylene adipate), poly(ethylene succinate), poly(2,3-bufylenesuccinate), polyether diols and the like; polycarbonates such as poly(methane bis(4-phenyl) carbonate), po Iy(I₅I -ether bis(4-phenyl) carbonate), poly(diphenylmethane bis(4-phenyl)carbonate), poly(l ,l-cyclohexane bis(4- phenyl)carbonate), or poly(2,2-(bis(4-hydroxyphenyl) propane) carbonate; polysulfones; polyether ether ketones; polyamides such as, for example, poly(4-aminobutyric acid), poly(hexamethylene - adipamide), poly(6-aminohexanoic acid), poly(m-xylylene adipamide), poly(p-xylylene sebacamide), poly(metaphenylene isophthalamide), and poly(p-phenylene terephthalamide); polyesters such as, for example, poly(ethylene azelate), poly(ethylene-l ,5-naphthalate), poly(ethylene-2,6-naphthalate), poly(l ,4-cyclohexane dimethylene terephthalate), poly(ethylene oxybenzoate), poly(para-hydroxy-benzoate), poly(l,4-cyclohexylidene-dimethylene terephthalate) (cis), poly(l ,4-cyclohexylidene-dimethylene terephthalate) (trans), polyethylene terephthalate, and polybutylene terephthalate; poly(arylene oxides) such as, for example, poly(2,6-dimethyl-l,4- phenylene oxide) and poly(2,6-diphenyl-l,lphenylene oxide); poly(arylene sulfides) such as, for example, polyphenylene sulfide; polyetherimides; vinyl polymers and their copolymers such as, for example, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, polyvinylidene chloride, and ethylene-vinyl acetate copolymers; acrylic polymers such as , for example, poly(ethyl acrylate)., poly(n-butyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(n-propyl methacrylate), polyacrylamide, polyacrylonitrile, polyacrylic acid, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers; acrylonitrile copolymers (for example, poly(acrylonitrile-co-butadiene-co-styrene) and poly(styrene-co-acrylonitrile)); styrenic polymers such as, for example, polystyrene, poly(styrene-co maleic anhydride) polymers and their derivatives, methyl methacrylate-styrene copolymers, and methacrylated butadiene-styrene copolymers; polyolefins such as, for example, polyethylene, polybutylene, polypropylene, chlorinated low density polyethylene, poly(4-methyl-l-pentene); ionomers; poly(epichlorohydrins); polysulfones such as, for example, the reaction product of the sodium salt of 2,2-bis(4- hydroxyphenyl) propane and 4,4'-dichlorodiphenyl sulfone; furan resins such as, for example, pόly(furan); cellulose ester plastics such as, for example, cellulose acetate, cellulose acetate butyrate, and cellulose propionate; protein plastics; polyarylene ethers such as, for example, . polyphenylene oxide; polyimides; polyvinylidene halides; polycarbonates; aromatic polyketones; polyacetals; polysulfonates; polyester ionomers; and polyolefin ionomers. Copolymers and/or combinations or blends of these aforementioned polymers can also be used.

Useful 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(styrene-butadiene-styrene) block copolymer, manufactured by Shell Chemical Company under the trade name of "KRATON". Copolymers and/or combinations or blends of these aforementioned polymers can also be used

Useful polymeric resins also include fluoropolymers, that is, at least partially fluorinated polymers. Useful fluoropolymers include, for example, those that are preparable (for example, by free-radical polymerization) from monomers comprising chlorotrifluoroethylene, 2- chloropentafluoropropene, 3-chloropentafluoropropene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, 1-hydropentafluoropropene, 2-hydropentafluoropropene, 1,1- dichlorofluoroethylene, dichlorodifluoroethylene, hexafluoropropylene, vinyl fluoride, a perfluorinated vinyl ether (for example, a perfluoro(alkoxy vinyl ether) such as CF3θCF2CF2CF2θCF=CF2, or a perfluoro(alkyl vinyl ether) such as perfiuoro(methyl vinyl ether) or perfluoro(propyl vinyl ether)), cure site monomers such as for example nitrile containing monomers (for example, CF2=CFO(CF₂) LCN, CF2=CFO[CF2CF(CF3)O]_q(CF2θ)_yCF(CF3)CN, CF2=CF[OCF₂CF(CF3)]_rO(CF₂)tCN₅ or CF2=CFO(CF₂)uOCF(CF₃)CN where L = 2-12; q = 0-4; r = 1-2; y = 0-6; t = 1-4; and u = 2-6), bromine containing monomers (for example, Z-Rf-O_x- CF=CF₂, wherein Z is Br or I, Rf is a substituted or unsubstituted Ci-C₁₂ fluoroalkylene, which may be perfluorinated and may contain one or more ether oxygen atoms, and x is 0 or 1); or a combination thereof, optionally in combination with additional non-fluorinated monomers such as, for example, ethylene or propylene. Specific examples of such 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(alkyl vinyl ether) copolymers (for example, tetrafluoroethylene-perfluoro(propyl vinyl ether)); and combinations thereof.

Useful commercially available 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", "PFA¹Y¹HTE", ¹¹ETFE", and ¹¹FEP"; 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'¹ (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. In particular, 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. Examples of polymers with reactive or polar groups include, but are not limited to, polyamides, polyimides, functional polyolefins, polyesters, polyacrylates and methacrylates.

In one embodiment, 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. Non-limiting examples of 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. In particular, 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); -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. 2004/0024130 A 1 (Nelson et al.)); acrylates and methacrylates (for example, 2-hydroxyethyi acrylate), acrylamide and methacrylamide, N-substituted and N,N disubstituted acrylamides (for example, N-t-butylacryl amide, N,N-(dimethylamino)ethylacrylamide, N,N-dimethylacrylamide, N₅Ndimethyl-methacrylamide), N-ethyl-acrylamide, N-hydroxyethyl- acrylamide, N-octyl-acrylamide, Nk-butyl-acrylamide, N,N-dimethyl-acrylamide, N,N-diethyl- acrylamide, and N-ethyl-N-dihydroxyethyl-acrylamide), aliphatic amines (for example, 3- dimethylaminopropyl amine, N,N-dimethylethylenediamine); and heterocyclic monomers (for example, 2-vinylpyridine, 4-vinylpyridine, 2-(2-aminoethyl)pyridine, l-(2-aminoethyl)pyrrolidine, 3-aminoquinuclidine, N-vinylpyrrolidone, and N-vinylcaprolactam).

Other 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, S, 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. Non- limiting example of useful monomers for introducing such blocks include: hydrocarbon olefins such as ethylene, propylene, isoprene, styrene, and butadiene; cyclic siloxanes such as decamethylcyclopentasiloxane and decamethyltetrasiloxane; fluorinated olefins such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, difluoroethylene, and chlorofluoroethylene; nonfluorinated alkyl acrylates and methacrylates such as butyl acrylate, isooctyl methacrylate lauryl acrylate, stearyl acrylate; fluorinated acrylates such as perfluoroalkylsulfonamidoalkyl acrylates and methacrylates having the formula H2C=C(R.2)C(O)O- X-N(R)Sθ2Rf wherein: Rf is -C6^F13_> -C4F9, or-C3Fy; 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.

Other non-limiting examples of useful block copolymers having functional moieties include poly(C4-MDI-HEA-block-methacrylic acid)), poly(C4-MDI-HEA-block-t-butyl methacrylate), poly(styrene-block-t-butyl methacrylate-block- C4-MDI-HEA), p61y(styrene-block-methacrylic anhydride-block- C4-MDI-HEA), poly(styrene-block- methacrylic acidblock- C4-MDI-HEA), poly(styrene-block-(methacrylic anhydride-co-methacrylic acid)-block- C4-MDI-HEA)), poly(styrene-block-(methacrylic anhydride-co-methacrylic acid-co- C4-MDI-HEA)), poly(styrene- block-(t-butyl methacrylate-co- C4-MDI-HEA)), poly(styrene-block-isoprene-block-t-butyl methacrylate-block- C4-MDI-HEA), poly(styrene-isoprene-block-methacrylic anhydride-block- C4- MDI-HEA), poly(styrene-isoprene-block-methacrylic acid-block- C4-MDI-HEA), poly(styrene- block-isoprene-block- (methacrylic anhydride-co-methacrylic acid)-block- C4-MD1-HEA), poly(styrene-block-isoprene-block-(methacrylic anhydride-comethacrylic acid-co- C4-MDI-HEA)), poly(styrene-block-isoprene-block-(t-butyl methacrylateco- C4-MDI-HEA)), poly(C4-MDI-HEA - block-methacrylic anhydride), poly(C4-MDI-HEA -block-(methacrylic acid-co-methacrylic anhydride)), poly(styrene-block-(t-butyl methacrylateco- C4-MDI-HEA)), and hydrogenated forms of poIy(butadiene-block-C4-MDI-HEA), and poly(butadiene-block-methacrylic acid-block- C4-

MDI-HEA).

EXAMPLES Test Methods

Molecular Weight and Polydispersity

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 (μL) of the 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) 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 MHzNMR Spectrometer available from Varian Inc., Palo Alto, California. Block concentrations were calculated from relative areas of characteristic block component spectra.

Material Description

Example 1

^' Synthesis of P(BA-δ-C4-MDI-HEA) block copolymer via continuous polymerization:

The P(BA-Z>-C4-MDI-HEA) block copolymer was synthesized by sequential atom transfer radical polymerization in toluene at 90⁰C using CuBr/2-bromoisobutyrate/2,2'-dipyridyl as an initiator system. Behenyl acrylate (35g) was mixed with CuBr (0.85g) and 2-bromoisobutyrate in toluene (50_.0ml) ahd heated to 90°C. Once this mixture reached 90°C₃ 2,2'-dipyridyl (1.87g) was added and the mixture was stirred at 90°C for one hour. After one hour, C4-MDI-HEA (25g) monomer was added to this mixture and stirred at 90°C for an additional one hour. The resultant P(BA-ό-C4-MDI-HEA) block copolymer was isolated as a white powder, after column chromatographic purification using basic alumina, followed by precipitation in methanol and filtration. The molecular weight and composition of these materials were determined by GPC and

¹H NMR.

The Polymer analytical data for the P(BA-ό-C4-MDI-HEA) block copolymer showed a composition in mole % (wt %) of: BA 76.2% (63.1); and C4-MDI-HEA 23.8% (36.9). The number average molecular weight was 2.7 x 1(P and the polydispersity index was 1.8.

Claims

We claim:

1. A block copolymer comprising at least one block comprising a fluorinated monomer having a general formula selected from the group comprising: CH₂=CHCO₂CH₂CHO₂CNH(COH₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉; and

CH₂=CR¹ CO₂CH₂CH₂S-[X]_n-R¹ wherein X is CH₂CHCO₂CH₂CHO₂CNH(CgH₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄Fg, wherein each R¹ 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.

2. The composition of claim 1 wherein the block copolymer is a star-branched block copolymer.

3. The composition of claim 1 wherein the block copolymer is a di- or tri-block copolymer having AB, ABA, or ABC architecture.

4. The composition of claim 1 wherein at least one of the blocks is a random copolymer of at least two monomeric species.

5. The composition of claim 1 wherein at least one of the blocks comprises a monomer that is 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.

6. The composition of claim 1 wherein at least one of the blocks comprises a hydrogenated polydiene block.

7. The composition of claim 1 wherein the block copolymer contains at least three blocks wherein each block is selected from the group consisting of a hydrophilic block, a lipophilic block, and a fluorophilic block.

8. The composition of claim 1 having acid or anhydride functionality in at least one block.

9. The composition of claim 1 wherein the block copolymer is end-functionalized with a single reactive group.

10. A block copolymer comprising at least one block having a quaternary ammonium ion, with the proviso that at least one block comprises a fluorinated monomer selected from the group consisting of: CH₂=CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(CeH₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉;

CH₂=CRlCO₂CH₂CH₂S-[X]_n-R' ; CH₂=CHCO₂CH₂CHO₂CN(⁺)(R)₂(C₆H₄)CH₂(C₆H₄)N(⁺)(R)₂CO₂C₂H₄N(CH₃)SO₂C₄F₉; and

CH₂=CR¹ CO₂CH₂CH₂S-[Z]_n-R¹ wherein X is CH₂CHCO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SO₂C₄F₉₅ Z is

CH₂CHCO₂CH₂CHO₂CN(⁺)(R)₂(C₆H₄)CH₂(C₆H₄)N(+)(R)₂CO₂C₂H₄N(CH₃)SO₂C₄F₉, wherein each R¹ is independently selected from the group consisting of H₅ 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; n is selected from 1 to 25, and wherein each R is independently selected from H, an alkyl, and an aralkyl.

1 1. A method of reducing the surface tension of a liquid comprising adding to a liquid a surface active agent in an amount of from 0.0025 to 10 % by weight of the surface active agent, based on the total weight of the liquid and surface active agent, wherein the surface active agent comprises the block copolymer of claim 1.

12. The method of claim 11 wherein the liquid is in the form of a froth comprising a gas and a polymerizable monomer.

13. A method for modifying the surface chemistry of a polymeric substrate comprising adding to a polymer a surface active agent in an amount of from 0.1 to 10% by weight of the surface active agent, based on the total weight of the polymer and surface active agent, wherein the surface active agent comprises the block copolymer of claim 1.

14. A polymerized foam composition made from a mixture containing one or more of monomers, oligomers, and polymers, the mixture comprising from 0.1 to 10% by weight of a surface active agent, based on the total weight of the mixture, wherein the surface active agent comprises the block copolymer of claim 1.

15. An article comprising the polymerized foam composition of claim 14.

16. The article of claim 15 wherein the article is a pressure sensitive adhesive tape.

17. A block copolymer comprising at least one block having a

- CO₂CH₂CHO₂CNH(C₆H₄)CH₂(C₆H₄)NHCO₂C₂H₄N(CH₃)SC^F₉ 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, hydroxyl, carboxyl, amine, amide, sulfide, sulfoxide, sulfate, phosphate, nitroxide, thioester, carbonyl; and n is selected from 1 to 25.