WO2014123775A1 - Copolymère polysiloxane-polyamide, et ses procédés de fabrication et d'utilisation - Google Patents

Copolymère polysiloxane-polyamide, et ses procédés de fabrication et d'utilisation Download PDF

Info

Publication number
WO2014123775A1
WO2014123775A1 PCT/US2014/014082 US2014014082W WO2014123775A1 WO 2014123775 A1 WO2014123775 A1 WO 2014123775A1 US 2014014082 W US2014014082 W US 2014014082W WO 2014123775 A1 WO2014123775 A1 WO 2014123775A1
Authority
WO
WIPO (PCT)
Prior art keywords
polysiloxane
copolymer
nhc
polyamide
block copolymer
Prior art date
Application number
PCT/US2014/014082
Other languages
English (en)
Inventor
William Blackwood
Kimmai Thi Nguyen
Ryan Christopher THOMAS
Kenneth Edward Zimmerman
Original Assignee
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Publication of WO2014123775A1 publication Critical patent/WO2014123775A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • Polyamide based resins, or nylons are an important class of thermoplastic resins in a variety of industries such as textiles, coatings, molded parts, and the like.
  • a variety of methods and techniques have been developed to improve the physical properties of nylons for certain applications. Typically, such improvements are based on the addition of certain components to the nylon, either during the processing of the nylon resin, or as a postprocessing additive.
  • Silicones, or organopolysiloxanes have been used as additives in nylon compositions and processing to affect physical properties. However, when silicones, such as polydimethylsiloxanes, are added to nylons during fiber production, the silicone can migrate within the nylon fiber and negatively impact certain physical properties.
  • the present invention provides a polysiloxane-polyamide block copolymer including the repeating unit -[M 1 -M 2 ]DPI -.
  • the variable M 1 is a divalent polydiorganosiloxane.
  • the variable M 2 is a divalent polyamide.
  • the variable DP1 is about 1 -200.
  • the present invention provides a polysiloxane-polyamide block copolymer including the repeat unit -[SiR 1 R 2 -[OSiR 1 R 2 ] DP2 -R 3 -C(0)[NH-R 4 - NHC(0)-R 5 -C(0)] D p 3 NH-R 4 -NHC(0)-R 3 -] DP 1 -.
  • R 3 , R 4 , and R 5 can be independently at each occurrence at least one of straight-chain, branched, and cyclic, divalent (C-
  • the variable DP2 can be about 1 -500. Also, the variable
  • DP3 can be about 0-50.
  • the present invention provides a polysiloxane-polyamide block copolymer having the structure E 1 -[SiR 1 R 2 -[OSiR 1 R 2 ] DP2 -R 3 -C(0)[NH-R 4 -
  • the variable E 1 can be HR 3 -
  • variable E 2 can be -SiR 1 R 2 -
  • the variable R ⁇ can be an n-undecylene group. Each of R 4 and R ⁇ can independently be a straight chain (C4_-
  • the variable DP1 can be about 2-20.
  • the variable DP2 can be about 10 to about 200.
  • the variable DP3 can be about 0-10.
  • the present invention provides a method of making the polysiloxane-polyamide block copolymer.
  • the method includes obtaining or providing a mixture that includes an Si-H-terminated polydiorganosiloxane having the formula
  • the mixture also includes an alkenyl-terminated polyamide having the formula R6-C(0)[NH-R 4 -NHC(0)-R5-
  • the variable R ⁇ at each occurrence can be independently a monovalent (C-
  • Each of R 4 and R ⁇ can be independently a divalent (C-
  • the variable DP3 can be about 0-50.
  • the mixture also includes a hydrosilylation catalyst. The method also includes subjecting the mixture to reaction conditions to give the polysiloxane-polyamide block copolymer.
  • the present invention provides a personal care
  • the present invention provides a thermoplastic composition including the polysiloxane- polyamide block copolymer and at least one organic polymer, and also provides a thermoplastic film including the thermoplastic composition and methods of forming the film.
  • the present invention provides a coated substrate wherein the coating includes a composition that includes the polysiloxane-polyamide block copolymer, and also provides methods of coating substrates with the composition.
  • the present invention provides an article of manufacture that includes the polysiloxane-polyamide block copolymer such as at least one of sheet product, a molded article, a fiber, a spun yarn, a textile, and a nonwoven fabric.
  • the polysiloxane has a higher melting point than other polysiloxane polymers and copolymers, including as compared to diamide-polysiloxane block copolymers.
  • the higher melting point of various embodiments can allow for more facile use as a surface modifier in various applications, such as plastics applications.
  • Some polysiloxane polymers and copolymers for example diamide-polysiloxane block copolymers, have a melting point that is so different from the melting point of other thermoplastic materials that it is difficult to use the polysiloxane polymer or copolymer as a surface treatment, for example, due to difficulty in applying the polysiloxane polymer or copolymer uniformly.
  • the melting point of the polysiloxane-polyamide block copolymer can be closer to the melting point of some organic thermoplastic polymers, making it easier to use the polysiloxane-polyamide block copolymer as a surface treatment for the
  • thermoplastic polymers for example, easier to apply the polysiloxane-polyamide block copolymer uniformly.
  • the polysiloxane-polyamide block copolymer can be more hydrophobic due at least to the presence of the polysiloxane units in the polymer. The increased
  • hydrophobicity of various embodiments can result a lower contact angle with water, and can give advantages such as less moisture pick up in fabrics, lower coefficients of friction, improved softening, and improved water repellency.
  • the increased hydrophobicity can result in advantages in the fiber production, processing, and weaving process. For example, in the production of nylon fibers by extrusion, extruder pressure can be reduced for polyamides and polyamide compositions having a reduced hydrophilic nature, which can result in easier processing, faster throughput, and ultimately a lower cost of production.
  • the reduced hydrophilic nature of various embodiments can reduce or eliminate the use of sizing finishes in fiber weaving production.
  • the reduced hydrophilic nature of various embodiments can result in greater resiliency to adhesion by soiling materials such as dirt and aqueous solutions or suspensions of soiling material.
  • the polysiloxane-polyamide block copolymer can have a softer feel than other polyamide polymers and copolymers, due at least to the presence of the polysiloxane units in the polymer.
  • the advantageous properties of the polysiloxane-polyamide block copolymer make it valuable as a surface modification agent, such as for use as a coating on various materials, such as on organic thermoplastic polymers, nylons, and the like, or on any material for which reduced adhesion of water or soiling materials is desired.
  • the polysiloxane-polyamide block copolymer can be blended with various materials to produce compositions with valuable and advantageous properties.
  • Various embodiments can advantageously be used as gellants for personal care applications.
  • FIG. 1 illustrates the normalized response versus time for various polysiloxane- polyamide block copolymers, in accordance with various embodiments.
  • FIG. 2 illustrates the percent moisture weight gain for fabric samples having varying amounts of polysiloxane-polyamide copolymer thereon, in accordance with various embodiments.
  • substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.
  • organic group refers to but is not limited to any carbon- containing functional group.
  • an oxygen-containing group such as alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur-containing group such as alkyl and aryl sulfide groups; and other heteroatom-containing groups.
  • Non-limiting examples of organic groups include OR', OC(0)N(R') 2 , CN, CF 3 , OCF 3 , R', C(O), methylenedioxy, ethylenedioxy, N(R') 2 , SR', SOR', S0 2 R', S0 2 N(R') 2 , S0 3 R', C(0)R',
  • N(R')N(R')C(0)OR' N(R')N(R')CON(R') 2 , N(R')S0 2 R', N(R')S0 2 N(R') 2 , N(R')C(0)OR',
  • R' can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can itself be further substituted; for example, wherein R' can be hydrogen (in examples that include other carbon atoms), alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, wherein any alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, or R' can be independently mono- or multi-substituted with J; or wherein two R' groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl, which can be mono- or independently multi-substit
  • substituted refers to an organic group as defined herein or molecule in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.
  • functional group or “substituent” as used herein refers to a group that can be or is substituted onto a molecule, or onto an organic group.
  • substituents or functional groups include, but are not limited to, a halogen (e.g., F, CI, Br, and I); an oxygen atom in groups such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups.
  • a halogen e.g., F, CI, Br, and I
  • an oxygen atom in groups such as
  • Non-limiting examples of substituents J that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR', OC(0)N(R') 2 , CN, NO, N0 2 , ON0 2 , azido, CF 3 , OCF 3 , R', O (oxo), S (thiono),
  • alkyl refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • alkyl encompasses n- alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl.
  • Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
  • alkenyl refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms.
  • alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms.
  • alkynyl refers to straight and branched chain alkyl groups, except that at least one triple bond exists between two carbon atoms.
  • alkynyl groups have from 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to -C ⁇ CH, -C ⁇ C(CH 3 ), -C ⁇ C(CH 2 CH 3 ), -CH 2 C ⁇ CH, -CH 2 C ⁇ C(CH 3 ), and
  • acyl refers to a group containing a carbonyl moiety wherein the group is bonded via the carbonyl carbon atom.
  • the carbonyl carbon atom is also bonded to another carbon atom, which can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like.
  • the group is a "formyl” group, an acyl group as the term is defined herein.
  • An acyl group can include 0 to about 12-20 or 12-40 additional carbon atoms bonded to the carbonyl group.
  • An acyl group can include double or triple bonds within the meaning herein.
  • An acryloyl group is an example of an acyl group.
  • An acyl group can also include heteroatoms within the meaning here.
  • a nicotinoyl group (pyridyl-3-carbonyl) group is an example of an acyl group within the meaning herein.
  • Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups and the like.
  • the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a "haloacyl" group.
  • An example is a trifluoroacetyl group.
  • cycloalkyl refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7.
  • Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein.
  • Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6- disubstituted cyclohexyl groups or mono-, di- or tri-substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
  • cycloalkenyl alone or in combination denotes a cyclic alkenyl group.
  • aryl refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • aryl groups contain about 6 to about 14 carbons in the ring portions of the groups.
  • Aryl groups can be unsubstituted or substituted, as defined herein.
  • Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substituted naphthyl groups, which can be substituted with carbon or non-carbon groups such as those listed herein.
  • aralkyi refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein.
  • Representative aralkyi groups include benzyl and phenylethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl.
  • Aralkenyl group are alkenyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein.
  • heterocyclyl refers to aromatic and non-aromatic ring compounds containing 3 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S.
  • a heterocyclyl can be a cycloheteroalkyi, or a heteroaryl, or if polycyclic, any combination thereof.
  • heteroaryl refers to aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S; for instance, heteroaryl rings can have 5 to about 8-12 ring members.
  • a heteroaryl group is a variety of a heterocyclyl group that possesses an aromatic electronic structure.
  • heterocyclylalkyl refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group as defined herein is replaced with a bond to a heterocyclyl group as defined herein.
  • Representative heterocyclyl alkyl groups include, but are not limited to, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-yl methyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl.
  • heteroarylalkyl refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined herein.
  • alkoxy refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein.
  • linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like.
  • branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like.
  • cyclic alkoxy examples include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
  • An alkoxy group can include one to about 12-20 or about 12- 40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms.
  • an allyloxy group is an alkoxy group within the meaning herein.
  • a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structures are substituted therewith.
  • amine refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)3 wherein each group can independently be H or non-H, such as alkyl, aryl, and the like.
  • Amines include but are not limited to R-NH2, for example, alkylamines, arylamines, alkylarylamines; R2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like.
  • R-NH2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like
  • R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like.
  • amine also includes ammonium ions as used herein.
  • amino group refers to a substituent of the form -NH2, - NHR, -NR2, -NR3+, wherein each R is independently selected, and protonated forms of each, except for -NR3+, which cannot be protonated. Accordingly, any compound substituted with an amino group can be viewed as an amine.
  • An “amino group” within the meaning herein can be a primary, secondary, tertiary or quaternary amino group.
  • alkylamino includes a monoalkylamino, dialkylamino, and trialkylamino group.
  • halo or halogen or halide, as used herein, by themselves or as part of another substituent mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom, preferably, fluorine, chlorine, or bromine.
  • haloalkyl group includes mono-halo alkyl groups, poly- halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro.
  • haloalkyl examples include trifluoromethyl, 1 ,1 -dichloroethyl, 1 ,2-dichloroethyl, 1 ,3- dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.
  • the term "monovalent” as used herein refers to a substituent connecting via a single bond to a substituted molecule.
  • a substituent is monovalent, such as, for example, F or CI, it is bonded to the atom it is substituting by a single bond.
  • hydrocarbon refers to a functional group or molecule that includes carbon and hydrogen atoms.
  • the term can also refer to a functional group or molecule that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups.
  • polysiloxane material of any viscosity that includes at least one siloxane monomer that is bonded via a Si-O-Si bond to three or four other siloxane monomers.
  • the polysiloxane material includes T or Q groups, as defined herein.
  • solvent refers to a liquid that can dissolve a solid, liquid, or gas.
  • solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
  • coating refers to a continuous or discontinuous layer of material on the coated surface, wherein the layer of material can penetrate the surface and can fill areas such as pores, wherein the layer of material can have any three-dimensional shape, including a flat or curved plane.
  • a coating can be formed on one or more surfaces, any of which may be porous or nonporous, by immersion in a bath of coating material.
  • room temperature refers to a temperature of about 15 °C to 28 °C.
  • number-average molecular weight refers to the ordinary arithmetic mean of the molecular weight of individual molecules in a sample. It is defined as the total weight of all molecules in a sample divided by the total number of molecules in the sample.
  • M n the number average molecular weight
  • the number average molecular weight can be measured by a variety of well-known methods including gel permeation chromatography, spectroscopic end group analysis and osmometry.
  • weight-average molecular weight refers (M w ), which is equal to ⁇ Mj 2 nj / ZMjtij , where nj is the number of molecules of molecular weight Mj.
  • the weight average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.
  • hydrocarbyl refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, such as an alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or a combination thereof.
  • the present invention provides a polysiloxane-polyamide block copolymer including the repeating unit -[M 1 - ⁇ 2 ] ⁇ -.
  • the variable M 1 can be a divalent polydiorganosiloxane.
  • the variable M 2 can be a divalent polyamide.
  • the variable DP1 can be about 1 -1000, 1 -200, 2-200, 2-100, 2-50, or about 2-20.
  • the copolymer can be terminated by any suitable functional group or combination of functional group.
  • the copolymer can include any other suitable unit, such as any other suitable repeating unit, in addition to the repeating unit -[M 1 - ⁇ 2 ] ⁇ -.
  • Embodiments of the present invention encompass a plurality of block copolymers including the repeating unit -[M 1 - ⁇ 2 ] ⁇ -, a single block copolymer including the repeating unit -[M 1 - ⁇ 2 ] ⁇ -, and any composition including the same.
  • polysiloxane-polyamide block copolymer can have the following structure E ⁇ -[M ⁇ -M 2 ]DPI -E 2 .
  • the variable E ⁇ can be Y- or X-M 2 -.
  • the variable E 2 can be -X or -M ⁇ -Y.
  • the variable X is a monovalent polydiorganosiloxane
  • X is divalent polysiloxane M 1 having an -H substituent at one of the locations of valency.
  • X is -H.
  • the variable Y is a monovalent polyamide corresponding to M 2 ; Y is a divalent amide having an -H substituent at one of the locations of valency.
  • Y is M 2 -H.
  • polysiloxane-polyamide block copolymer has the structure Y-[M 1 - ⁇ 2 ] ⁇ -X, Y-[M 1 -
  • the polysiloxane-polyamide block copolymer can have any suitable molecular weight.
  • the copolymer has a molecular weight of about 5,000 Daltons to 500,000 Daltons, 10,000 Daltons - 100,000 Daltons, or about 15,000 Daltons to 90,000 Daltons.
  • the polysiloxane-polyamide block copolymer can have any suitable properties, consistent with the structure as described herein.
  • the block copolymer can have any suitable polydispersity.
  • the block copolymer can have a polydispersity relative to polystyrene strands in THF of about 1 to 20, 2 to 10, or about 2.7 to 7.
  • the block copolymer can have any suitable melt viscosity.
  • the block copolymer can have a melt viscosity at about 190 5 C of about 1 ,000 cP to 50,000 cP, 5,000 cP - 20,000 cP, or about 7,500 to 18,000 cP.
  • the block copolymer can have any suitable melting point.
  • the block copolymer can have a melting point of about 100 Q C to about 300 5 C, 130 Q C - 220 5 C, or about 140 Q C to 200 °-C.
  • the polysiloxane units can have any suitable polysiloxane structure consistent with the properties of the block copolymer described herein.
  • the divalent polysiloxane in the polysiloxane-polyamide block copolymer, can have the structure -SiPJ R 2 -[OSiRl R 2 ]DP2 _ - Each of and R 2 at each occurrence can be an organic functional group.
  • the variable DP2 can be about 1 to about 500, or 10-200, or about 20-120.
  • each of R 1 and R 2 can be at each occurrence independently at least one of straight chain, branched, and cyclic, substituted or unsubstituted (C-
  • Each of R 1 and R 2 can be at each occurrence independently at least one of straight chain and branched unsubstituted (C-
  • the polyamide units can have any suitable polyamide structure consistent with the properties of the block copolymer described herein.
  • the divalent polyamide M 2 can have the structure -R 3 -C(0)[NH-R 4 -NHC(0)-R 5 - C(0)]DP3NH-R 4 -NHC(0)-R 3 -.
  • R 3 , R 4 , and R 5 at each occurrence can be independently at least one of straight-chain, branched, and cyclic, divalent (C-
  • variable DP3 can be about 0-50, 0-10. 0-5, or about 0-1. In some examples, the variable DP3 can be about 1 -50, 1 -10, 1 -5, or about 1 . Various embodiments provide a plurality of the copolymers wherein DP3 has an average value of about 0-50, 0.001 -10, 0.01 -5, or about 0.1 -1 . In some examples, each of R 3 , R 4 , and R5 is independently a divalent (C-
  • the divalent polyamide can correspond to a nylon-6,6 structure, a nylon-4,6 structure, a nylon-6,9 structure, a nylon-4,9 stucture, a nylon-9,4 structure, or a nylon-6,4 structure.
  • Various embodiments of the present invention provide a method of making the polysiloxane-polyamide block copolymer.
  • the method can be any suitable chemical synthetic method that produces the polysiloxane-polyamide block copolymer.
  • the method includes combining an Si-H terminated polydiorganosiloxane with a polyamide having terminal groups that include at least one aliphatic unsaturated carbon- carbon bond in the presence of a hydrosilylation catalyst, and subjecting the mixture to conditions suitable for hydrosilylation, thereby forming the block copolymer.
  • the method can include obtaining or providing a mixture that includes an Si-H-terminated polydiorganosiloxane having the formula HSiR ⁇ R 2 - [OSiR 1 R 2 ]DP2H.
  • Each of R 1 and R 2 at each occurrence can be an organic functional group.
  • the variable DP2 can be about 1 to about 500.
  • the mixture also includes an alkenyl-terminated polyamide having the formula R 6 -C(0)[NH-R 4 -NHC(0)-R 5 -
  • variable R ⁇ at each occurrence can be independently a monovalent (C-
  • R 4 and R ⁇ can be independently a divalent (C-
  • the variable DP3 can be about 0-50.
  • the mixture also can include a hydrosilylation catalyst.
  • the method also can include subjecting the mixture to reaction conditions to give the polysiloxane-polyamide block copolymer.
  • the hydrosilylation catalyst can be any suitable hydrosilylation catalyst.
  • the hydrosilylation catalyst can be any hydrosilylation catalyst including a platinum group metal or a compound containing a platinum group metal.
  • Platinum group metals can include platinum, rhodium, ruthenium, palladium, osmium and iridium.
  • hydrosilylation catalysts include the complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, such as the reaction product of chloroplatinic acid and 1 ,3-divinyl-1 ,1 ,3,3- tetramethyldisiloxane; microencapsulated hydrosilylation catalysts including a platinum group metal encapsulated in a thermoplastic resin, as exemplified in U.S. Pat. No.
  • hydrosilylation catalysts such as platinum(ll) bis(2,4-pentanedioate), as exemplified in U.S. Patent No. 7,799,842.
  • An example of a suitable hydrosilylation catalyst can include a platinum(IV) complex of 1 ,3- diethenyl-1 ,1 ,3,3-tetramethyldisiloxane.
  • the hydrosilylation catalyst can be at least one photoactivated hydrosilylation catalyst. The suitability of a particular hydrosilylation catalyst for use in a reaction mixture of the present invention can be readily determined by routine experimentation.
  • the concentration of the hydrosilylation catalyst can be sufficient to catalyze hydrosilylation of the polysiloxane having terminal Si- H groups and the polyamide having terminal unsaturated aliphatic carbon-carbon bond- containing groups.
  • the concentration of the hydrosilylation catalyst is sufficient to provide from about 0.1 to about 1000 ppm of a platinum group metal, from about 0.5 to about 500 ppm of a platinum group metal, and more preferably from about 1 to about 100 ppm of a platinum group metal, based on the total weight of the uncured composition.
  • the rate of cure can be very slow below about 0.1 ppm of platinum group metal.
  • the use of more than 1000 ppm of platinum group metal is possible, but is generally undesirable because of catalyst cost.
  • Compositions including the copolymer are examples of the copolymer.
  • compositions that include one or more of the polysiloxane-polyamide copolymers described herein.
  • the composition that includes that copolymer can be any suitable composition that is used for any suitable purpose consistent with the properties of the copolymer or composition including the same.
  • the present invention provides a personal care composition including the polysiloxane-polyamide block copolymer.
  • the personal care composition can be any suitable personal care composition, such as a cosmetic composition or a deodorant composition.
  • the present invention provides a thermoplastic composition including the polysiloxane-polyamide block copolymer and at least one organic polymer.
  • the organic polymer can be any organic polymer that can be suitably combined with the block copolymer, such that it is useful for its intended use.
  • the organic copolymer can be a thermoplastic nylon resin.
  • the nylon resin can be any high molecular weight solid homopolymer, copolymer or terpolymer having recurring amide units within the polymer chain (e.g. polyamides or copolymers thereof) having thermoplastic properties.
  • the nylon resin can be crystalline or amorphous.
  • the nylon resin can have a melting point greater than about 25 5 C. In copolymer and terpolymer systems, more than 50 mole percent of the repeat units can be amide-containing units. Examples of suitable
  • polyamides include polylactams such as nylon 6, polyenantholactam (nylon 7),
  • polycapryllactam nylon 8
  • polylauryllactam nylon 12
  • homopolymers of aminoacids such as polypyrrolidinone (nylon 4); copolyamides of dicarboxylic acid and diamine such as nylon 6,6, polyhexamethyleneazelamide (nylon 6,9), polyhexamethylene- sebacamide (nylon 6,10), polyhexamethyleneisophthalamide (nylon 6, IP),
  • polyhexamethylenedodecanoic acid nylon 6,12 and the like; aromatic and partially aromatic polyamides; copolyamides such as copolymers of caprolactam and
  • hexamethyleneadipamide nylon 6,6/6
  • a terpolyamide e.g., nylon 6,6/6,6
  • block copolymers such as polyether polyamides; or mixtures thereof.
  • siloxane-based polyamides useful in the compositions of the present invention are disclosed in U.S. Pat. No. 6,051 ,216 and U.S. Pat. No. 6,353,076 B1 , which are hereby incorporated by reference.
  • compositions of the present invention can be prepared by melt mixing the polysiloxane-polyamide block copolymer with the organic polymer.
  • the organic polymer can be melted and then the polysiloxane-polyamide block copolymer can be mixed with the organic polymer melt.
  • the mixing can occur via any known mixing techniques in the art for processing and mixing thermoplastic resins at elevated
  • the components may be mixed in a twin screw extruder, a Banbury mixer, a two roll mill or a single screw extruder, with or without a mixing gear.
  • the mixing can occur in an extrusion process.
  • the amount of the polysiloxane-polyamide block copolymer used per 100 parts of the organic polymer can be about 0.1 to 20 weight parts, 0.2-20 weight parts, 0.5-10 weight parts, or about 0.5-5 weight parts of the polysiloxane- polyamide block copolymer per 100 weight parts of the organic polymer.
  • Other components such as those commonly added to nylon compositions or processes, can be added to the melt mixture. In some examples, the additional components are not equal to or exceed 20 weight percent of the total composition.
  • the other components can be, but not limited to, processing additives, fillers, flame retardants, UV stabilizers, antioxidants, antiblock agents, catalyst stabilizers, lubricants, colorants, impact modifiers, foaming agents, mold release agents, matt/gloss additives, plasticizers, and combinations thereof.
  • compositions can be further compounded or mixed with additional components.
  • additional components can be illustrated by, but not limited to, reinforcing fillers for polyamide resins, such as glass fibers and carbon fibers; extending fillers such as quartz, calcium carbonate, and diatomaceous earth; pigments such as iron oxide and titanium oxide, electrically conducting fillers such as carbon black and finely divided metals, heat stabilizers such as hydrated cerium oxide, antioxidants, flame retardants such as halogenated hydrocarbons, alumina trihydrate, magnesium hydroxide, organophosphorous compounds and other fire retardant (FR) materials; adhesion promotors; and combinations thereof.
  • reinforcing fillers for polyamide resins such as glass fibers and carbon fibers
  • extending fillers such as quartz, calcium carbonate, and diatomaceous earth
  • pigments such as iron oxide and titanium oxide
  • electrically conducting fillers such as carbon black and finely divided metals
  • heat stabilizers such as hydrated cerium oxide, antioxidants, flame retardants such as halogen
  • the composition can be a mixture of adhesion promotor and the polysiloxane-polyamide copolymer having any suitable amount of adhesion promotor present, such as about 0.001 wt% or less, about 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 6 wt%, 8 wt%, 9 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, or about 50 wt% or more of the polysiloxane-polyamide copolymer composition.
  • Embodiments of the composition including the polysiloxane-polyamide block copolymer can have any suitable application.
  • a thermoplastic composition can be extruded and blown into sheet products or molded or cast into articles of manufacture. In other examples, they can be drawn into fiber and made into nonwoven fabrics or spun to produce yarns from which fabrics may be woven.
  • the compositions can be used to coat or treat the surface of another material, such as a nylon- based material (e.g. a film) or any suitable material.
  • Article of manufacture including the copolymer.
  • the present invention provides an article of manufacture including the polysiloxane-polyamide copolymer described herein.
  • the article of manufacture can be any suitable article of manufacture that can benefit from the inclusion of the copolymer.
  • the article of manufacture can be at least one of a sheet product (e.g., a film), a molded article, a fiber, a spun yarn, a textile, and a nonwoven fabric.
  • the article of manufacture can include the copolymer alone or as a component of a mixture of other components.
  • the article of manufacture is a thermoplastic film that includes a composition that includes the copolymer.
  • the article of manufacture can include a coating or surface treatment that includes the copolymer or that includes a composition that includes the copolymer.
  • the article of manufacture can include any suitable substrate that is coated with the polysiloxane-polyamide copolymer, such as a coated fiber, a coated film, a coated spun yarn.
  • the article of manufacture can include any suitable amount of the copolymer, or of a composition including the copolymer, such as about 0.001 -1000 g/m 2 , or about 20-200 g/m 2 .
  • the article of manufacture can include an adhesion promotor underneath a coating or treatment of the polysiloxane-polyamide copolymer, or the article of manufacture can include a coating of a composition including the polysiloxane-polyamide copolymer and an adhesion promotor.
  • the present invention provides a method of using the copolymer, or a method of using a composition that includes the copolymer, or a method of using an article of manufacture that includes the copolymer.
  • the method can be any suitable method of using the copolymer consistent with the structure and properties of the block copolymer and compositions including the same as described herein.
  • some embodiments provide a method of coating a substrate.
  • the method can include obtaining or providing a substrate.
  • the method also can include coating the substrate with a composition including the polysiloxane-polyamide block copolymer.
  • the coating can be performed using any suitable method, such as knife-over- air or knife-over-roller.
  • the substrate can include a fiber, a film, and the like.
  • the method can include applying any suitable amount of the copolymer, such as about 0.001 -1000 g/m 2 , or about 20-200 g/m 2 .
  • the present invention provides a method of forming a film.
  • the method can include obtaining or providing a thermoplastic composition including the polysiloxane-polyamide block copolymer.
  • the method can also include forming the thermoplastic composition into a film.
  • the method of forming a film includes generating a film, and then coating or otherwise treating at least some part of the surface of the film with the copolymer or with a composition including the copolymer.
  • the present invention can be better understood by reference to the following examples which are offered by way of illustration. The present invention is not limited to the examples given herein. In the Examples, "DP" refers to degree of polymerization. [0065] General. The 244 fluid used was a mixture of about 85-100 wt% octamethylcyclotetracyclosiloxane and ⁇ 0.5% hexamethylcyclotrisiloxane.
  • Syloff 4000 Pt catalyst used was about 85-100 wt% dimethylvinyl-terminaed dimethylsiloxane, 5-10 wt% tetramethyldivinyldisiloxane, and 1 -5 wt% diethylenyl tetramethyl disiloxane platinum complex.
  • the samples were prepared in certified grade THF, filtered with a 0.45 ⁇ PTFE syringe filter, and analyzed against polystyrene standards.
  • the relative calibration (third order fit) used for molecular weight determination was based on 16 polystyrene standards ranging in molecular weights from 580 to 2,320,000 Daltons.
  • the chromatographic equipment included a Waters 2695 Separations Module equipped with a vacuum degasser, a Waters 2410 differential refractometer and two (300 mm x 7.5 mm) Polymer Laboratories Mixed C columns (molecular weight separation range of 200 to 3,000,000) preceded by a guard column.
  • Example 1 Adipic Acid Diamide, 1 1 .1 mol%.
  • HMDA hexamethylenediamine
  • HMDA hexamethylenediamine
  • the mixture was allowed to cool down to 175°C and then the vacuum was broken with nitrogen.
  • the hot mixture was poured off thinly into dry ice-cooled aluminum foil- covered trays.
  • the material was allowed to cool sufficiently prior to handling and characterization.
  • the melt point was determined to be 170-175°C according to the Fisher- Johns melt point apparatus.
  • the mixture was neutralized with 43.7 g of sodium bicarbonate and cooled to room temperature. Once the materials cooled, the materials were pressure filtered using 0.45 ⁇ filter paper and celite filtration aid. [0077] The filtered siloxane was loaded into a 12 liter three-neck round bottom flask equipped with thermocouple, electrical stirrer, condenser, and nitrogen sweep in a vacuum strip setup. The flask was purged for 5 minutes with nitrogen, and then mixing was turned on and heating to 100°C was initiated. Once at temperature, gradually full vacuum was applied (20 mmHg) and then the temperature was incrementally ramped up to 150°C. The temperature was held at 150°C under full vacuum for five hours.
  • the reaction was allowed to cool to less than 100°C prior to breaking the vacuum with nitrogen.
  • the material was allowed to cool down to room temperature prior to characterization.
  • the stripped siloxane was poured into a plastic lined container, from which 270 g of overheads (8.9 wt%) was collected.
  • the SiH concentration of the stripped siloxane was determined to be 321 ppm using FT-IR, which corresponds to approximately an 84 DP terminal SiH siloxane.
  • the mixing rate was increased to 300 rpm and the reaction was catalyzed with three doses of Syloff 4000 Pt catalyst (0.21 g, 0.24 g, 0.07 g, respectively) over a 15 minute time frame. Following the third does of catalyst, the reaction was held at 190°C for 2 hours and then poured off hot into a glass tray. The material was allowed to cool to room temperature prior to handling and characterization.
  • the melt point was determined to be 142-144°C according to a Fisher- Johns melt point apparatus, and the molecular weight (M w ) was determined to be 81 ,000 Daltons with a polydispersity of 5.03 relative to polystyrene standards in THF using conventional GPC analysis.
  • Example 5 Nylon 6,6 Modified Diamide, 16.75 mol%.
  • Example 6 Nylon 6,6 Modified Diamide, 25.0 mol%.
  • the mixture was allowed to cool down to 175°C and then the vacuum was broken with nitrogen.
  • the hot mixture was poured off thinly into dry ice-cooled aluminum foil- covered trays.
  • the material was allowed to cool sufficiently prior to handling and characterization.
  • the melt point was determined to be 188.8°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • Example 7 Nylon 6,6 Modified Diamide, 27.5 mol%.
  • HMDA hexamethylenediamine
  • the flask was purged with nitrogen for a minimum of 5 minutes prior to heating or adding other reagents to ensure an inert atmosphere.
  • the mixing apparatus was turned on 12.81 g of adipic acid was added to the flask. The highest temperature observed due to exotherm was observed, then the mixture was heated to 60°C. The mixture was held at 60°C until it became transparent
  • the mixture was allowed to cool down to 175°C and then the vacuum was broken with nitrogen.
  • the hot mixture was poured thinly into dry ice-cooled aluminum foil-covered trays.
  • the material was allowed to cool sufficiently prior to handling and characterization.
  • the melt point was determined to be 199.9°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • the mixture was neutralized with 120 g of sodium bicarbonate and the reaction mixture was cooled to room temperature. Once the reaction kettle temperature had sufficiently cooled, the contents were processed through a pressure filter using 0.45 ⁇ filter paper and celite filtration aid to remove excess sodium bicarbonate, salts, and other particulates.
  • the filtered siloxane was loaded into a 12 liter three-neck round bottom flask equipped with thermocouple, electrical stirrer, condenser, and nitrogen sweep in the vacuum strip setup.
  • the flask was purged for 5 minutes with nitrogen, the mixing was turned on, and the mixture was heated to 100°C. Once at temperature, gradually full vacuum was applied ( ⁇ 20 mmHg) and then incrementally the temperature was ramped up to 150°C. The temperature was held at 150°C under full vacuum for five hours.
  • the reaction was allowed to cool to less than 100°C prior to breaking the vacuum with nitrogen.
  • the material was allowed to cool down to room temperature prior to decanting and characterization.
  • the stripped siloxane was poured off into a plastic lined container.
  • the overheads removed during the stripping process were 910 g which was 10.1 1 wt% of the batch size.
  • the SiH concentration of the stripped siloxane was determined to be 327 ppm using FT-IR, which corresponds to approximately an 83 DP terminal SiH siloxane.
  • Example 9 Siliconized Nylon 6,6.
  • a 2L resin kettle was equipped with a thermocouple, motorized stirrer, condenser, and nitrogen sweep.
  • the kettle was purged with nitrogen for a minimum of 5 minutes prior to heating to ensure an inert atmosphere.
  • the mixture was mixed at 100 rpm and the temperature was increased to 195°C. Once the kettle reached the desired temperature and the diamide was fully melted, the mixing rate was increased to 300 rpm.
  • the reaction was then catalyzed with two doses of Syloff 4000 Pt catalyst (0.53 g + 0.31 g) over a 10 minute time frame to ensure the catalyst was active. Following the second dose of catalyst, the reaction was held at 195-200°C for 2 hours. After the 2 hour hold time, the silicone polyamide was decanted at temperature into a glass tray. The material was allowed to cool to room temperature prior to handling, processing, and characterization.
  • the material hardened into a straw colored solid gellant.
  • the melt point was determined to be 160-165°C according to the Fisher-Johns melt point apparatus.
  • the molecular weight (M w ) was 66,800 Daltons with a polydispersity of 3.247 relative to polystyrene standards in THF using conventional GPC analysis.
  • Example 10 Nylon 4,6-Modified Diamide, 25.0 mol%.
  • reaction temperature of 175°C was held for 1 hour, and then vacuum was applied and the temperature was increased to 220°C to remove excess UDA from the product.
  • a reaction temperature of 220°C was maintained while under full vacuum ( ⁇ 20 mmHg) for at least 2 hours.
  • the mixture was allowed to cool down to 200°C and then the vacuum was broken with nitrogen.
  • the hot mixture was poured thinly into dry ice-cooled aluminum-foil covered trays.
  • the material was allowed to cool sufficiently prior to handling and characterization.
  • the melt point was determined to be 199.9°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • Example 1 1 . Nylon 6,9-Modified Diamide, 25.0 mol%.
  • the mixture was cooled to 175°C and the vacuum was broken with nitrogen.
  • the hot mixture was decanted thinly into dry ice-cooled aluminum foil-covered trays.
  • the material was allowed to cool sufficiently prior to handling and characterization.
  • the melt point was determined to be 162.2°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • Example 12 Nylon 6,9-Containinq Silicone Polvamide Gellant with 80 DP Si Block.
  • a 500 mL resin kettle was equipped with a thermocouple, motorized stirrer, condenser, and nitrogen sweep.
  • the kettle was purged with nitrogen for a minimum of 5 minutes prior to heating to ensure an inert atmosphere.
  • the kettle was mixed at 100 rpm and the temperature was increased to 175°C. Once the kettle reached the desired temperature and the diamide was fully melted, the mixing rate was increased to 300 rpm.
  • reaction was catalyzed with two doses of Syloff 4000 Pt catalyst (0.30 g + 0.20 g, respectively) over a 10 minute time frame to ensure the catalyst was active. Following the second dose of catalyst, the reaction was held at 195-200°C for 2 hours. After the 2 hour hold time, the silicone polyamide was decanted at temperature into a glass tray. The material was allowed to cool to room temperature prior to handling, processing, and characterization.
  • the material hardened into a straw colored solid gellant.
  • the pharmacopeia melt point was determined to be 172.6°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • the molecular weight (M w ) was 63,700 Daltons with a polydispersity of 6.67 relative to polystyrene standards in THF using conventional GPC analysis.
  • Example 13 Nylon 6,9-Containinq Silicone Polvamide Gellant with 50 DP Si Block.
  • a 500 mL resin kettle was equipped with a thermocouple, motorized stirrer, condenser, and nitrogen sweep.
  • the kettle was purged with nitrogen for a minimum of 5 minutes prior to heating to ensure an inert atmosphere.
  • the kettle was mixed at 100 rpm and the temperature was increased to 180°C. Once the kettle reached the desired temperature and the diamide was fully melted, the mixing rate was increased to 300 rpm.
  • reaction was catalyzed with two doses of Syloff 4000 Pt catalyst (0.33 g + 0.13 g, respectively) over a 10 minute time frame to ensure the catalyst was active. Following the second dose of catalyst, the reaction was held at 195-200°C for 2 hours. After the 2 hour hold time, the silicone polyamide at temperature was decanted into a glass tray. The material was allowed to cool to room temperature prior to handling, processing, and characterization.
  • the material hardened into a straw colored solid gellant.
  • the pharmacopeia melt point was determined to be 174.2°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • the molecular weight (M w ) was 37,800 Daltons with a polydispersity of 4.96 relative to polystyrene standards in THF using conventional GPC analysis.
  • Example 14 Nylon 6,9-Containinq Silicone Polyamide Gellant with 20 DP Si Block.
  • a 500 mL resin kettle was equipped with a thermocouple, motorized stirrer, condenser, and nitrogen sweep.
  • the kettle was purged with nitrogen for a minimum of 5 minutes prior to heating to ensure an inert atmosphere.
  • the kettle was mixed at 100 rpm and the temperature was increased to 180°C. Once the kettle reached the desired temperature and the diamide was fully melted, the mixing rate was increased to 300 rpm.
  • reaction was catalyzed with two doses of Syloff 4000 Pt catalyst (0.24 g + 0.09 g, respectively) over a 10 minute time frame to ensure the catalyst was active. Following the second dose of catalyst, the reaction was held at 180°C for 2 hours. After the 2 hour hold time, the silicone polyamide was decanted at temperature into a glass tray. The material was allowed to cool to room temperature prior to handling, processing, and
  • the material hardened into a straw colored solid gellant.
  • the pharmacopeia melt point was determined to be 171 .3°C based upon measurements obtained using a Buchi Melting Point M-565 instrument.
  • the molecular weight (M w ) was 16,000 Daltons with a polydispersity of 3.66 relative to polystyrene standards in THF using conventional GPC analysis.
  • Table 1 shows the number average molecular weight, weight average molecular weight, and the polydispersity for the products of Examples 12, 13, and 14.
  • FIG. 1 illustrates the normalized response versus time for Examples 12, 13, and 14.
  • FIG. 1 is a GPC spectrum for various polysiloxane-polyamide block copolymers.
  • the Normalized response is also referred to as the intensity, which is directly related to the elution volume of the material.
  • the elution volume is plotted vs. time to yield the spectrum.
  • Samples of treated polyester fabric were prepared using the polysiloxane- polyamide copolymer of Example 9.
  • trimethoxysilane was added to the polysiloxane-polyamide copolymer in a concentration of 0.2 wt%.
  • the copolymer mixture was applied to the fabric using conventional techniques, followed by curing in a conventional oven.
  • a polyethylene tetephthalate (PET)-material was modified with the polysiloxane- polyamide copolymer compound of Example 9.
  • the adhesion promotor was added to the copolymer prior to the modification of the PET-material in a concentration of about 0.2 wt%.
  • the copolymer mixture was applied to the material using conventional techniques, and the samples were cured in a
  • Embodiment 1 provides a polysiloxane-polyamide block copolymer comprising the following repeating unit: -[M 1 -M 2 ]D P -
  • Embodiment 2 provides the polysiloxane-polyamide block copolymer of
  • Embodiment 1 wherein the block copolymer has the following structure: E ⁇ -[M ⁇ -M 2 ]DPI -
  • E ⁇ is Y- or X-M 2 -
  • E 2 is -X or -M ⁇ -Y
  • X is a monovalent polydiorganosiloxane corresponding to M 1
  • Y is a monovalent polyamide corresponding to M 2 .
  • Embodiment 3 provides the polysiloxane-polyamide block copolymer of
  • Embodiment 2 wherein the block copolymer has the following structure: Y-[M ⁇ -M 2 ]DPI -X,
  • Embodiment 4 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -3, wherein M 1 is -SiR 1 R 2 -[OSiR 1 R 2 ]DP2" > wherein each of R 1 and R 2 at each occurrence is an organic functional group, and DP2 is about 1 to about 500.
  • Embodiment 5 provides the polysiloxane-polyamide block copolymer of
  • Embodiment 4 wherein each of R 1 and R 2 are at each occurrence independently at least one of straight chain, branched, and cyclic, substituted or unsubstituted (C-
  • R 1 and R 2 do not include an aliphatic unsaturated carbon-carbon bond.
  • Embodiment 6 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 4-5, wherein each of and R 2 are at each occurrence independently at least one of straight chain and branched unsubstituted (C-
  • Embodiment 7 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 4-6, wherein each of and R 2 are methyl.
  • Embodiment 8 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 4-7, wherein DP2 is about 1 0 to about 200.
  • Embodiment 9 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -8, wherein M 2 is -R 3 -C(0)[NH-R 4 -NHC(0)-R 5 -C(0)] DP3 NH-R 4 - NHC(0)-R3-, wherein each of R ⁇ , R 4 , and R ⁇ at each occurrence is independently at least one of straight-chain, branched, and cyclic, divalent (C-
  • Embodiment 10 provides the polysiloxane-polyamide block copolymer of
  • Embodiment 9 wherein each of R ⁇ , R4 and is independently a divalent (C-
  • Embodiment 1 1 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 9-10, wherein R ⁇ is an n-undecylene group.
  • Embodiment 12 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 9-1 1 , wherein each of R ⁇ and R ⁇ is a straight chain alkylene group independently selected from a (C ⁇ alkylene group, a (Cg)alkylene group, and a
  • Embodiment 13 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 9-12, wherein DP3 is about 0-10.
  • Embodiment 14 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -13, wherein the copolymer has a molecular weight of about 5,000 Daltons to about 500,000 Daltons.
  • Embodiment 15 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -14, wherein the copolymer has a molecular weight of about 10,000 Daltons to about 100,000 Daltons.
  • Embodiment 16 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -15, wherein the copolymer has a polydispersity relative to polystyrene strands in THF of about 1 to about 20.
  • Embodiment 17 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -16, wherein the copolymer has a polydispersity relative to polystyrene strands in THF of about 2 to about 10.
  • Embodiment 18 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -17, wherein the copolymer has a melt viscosity at about 190 5 C of about 1 ,000 cP to about 50,000 cP.
  • Embodiment 19 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -18, wherein the copolymer has a melt viscosity at about 190 5 C of about 5,000 cP to about 20,000 cP.
  • Embodiment 20 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -19, wherein the copolymer has a melting point of about 100 5 C to about 300 °-C.
  • Embodiment 21 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -20, wherein the copolymer has a melting point of about 130 5 C to about 220 5 C.
  • Embodiment 22 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -21 , wherein the copolymer comprises the following repeat unit: -
  • Embodiment 23 provides the polysiloxane-polyamide block copolymer of any one of Embodiments 1 -22, wherein the copolymer has the following structure: E ⁇ -[SiR ⁇ R 2 -
  • Embodiment 24 provides a method of making the copolymer of any one of
  • Embodiments 1 -23 the method comprising: obtaining or providing a mixture comprising an
  • Si-H-terminated polydiorganosiloxane having the formula HSiR 1 R 2 -[OSiR 1 R 2 ]QP2H, wherein each of R 1 and R 2 at each occurrence is an organic functional group, and DP2 is about 1 to about 500; an alkenyl-terminated polyamide having the formula R6-C(0)[NH-R 4 - NHC(0)-R 5 -C(0)] DP3 NH-R 4 -NHC(0)-R 6 , wherein R 6 at each occurrence is
  • each of R 4 and R ⁇ is independently a divalent (C-
  • Embodiment 25 provides a personal care composition comprising the copolymer of any one of Embodiments 1 -23.
  • Embodiment 26 provides the personal care composition of Embodiment 25, comprising at least one of a cosmetic or a deodorant.
  • Embodiment 27 provides a thermoplastic composition comprising: the copolymer of any one of any one of Embodiments 1 -23; at least one organic polymer.
  • Embodiment 28 provides a substrate comprising a coating comprising a composition comprising the copolymer of Embodiment 1 .
  • Embodiment 29 provides the coated substrate of Embodiment 28, wherein the substrate comprises a fiber, a film, a spun yarn, or a combination thereof.
  • Embodiment 30 provides a thermoplastic film comprising a composition comprising the copolymer of any one of any one of Embodiments 1 -23.
  • Embodiment 31 provides a method of coating a substrate, comprising: obtaining or providing a substrate; and coating the substrate with a composition comprising the copolymer of any one of Embodiments 1 -23.
  • Embodiment 32 provides the coated substrate of Embodiment 31 , wherein the substrate comprises a fiber, a film, or a spun yarn, or a combination thereof.
  • Embodiment 33 provides a method of forming a film, comprising: obtaining or providing a thermoplastic composition comprising the copolymer of any one of any one of
  • Embodiments 1 -23 and forming the thermoplastic composition into a film.
  • Embodiment 34 provides an article of manufacture, comprising the copolymer of any one of Embodiments 1 -23.
  • Embodiment 35 provides the article of manufacture of Embodiment 34, wherein the article is at least one of sheet product, a molded article, a fiber, a spun yarn, a textile, and a nonwoven fabric.
  • Embodiment 35 provides the apparatus or method of any one or any combination of Embodiments 1 -34 optionally configured such that all elements or options recited are available to use or select from.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne des copolymères séquencés polysiloxane-polyamide. Selon divers modes de réalisation, la présente invention concerne un copolymère séquencé polysiloxane-polyamide comprenant le motif récurrent -[M1-M2]DP1-, où M1 représente un polydiorganosiloxane divalent, et M2 représente un polyamide divalent. La présente invention concerne également des procédés de fabrication dudit copolymère, des compositions et des articles manufacturés comprenant ledit copolymère, et des procédés d'utilisation dudit copolymère.
PCT/US2014/014082 2013-02-05 2014-01-31 Copolymère polysiloxane-polyamide, et ses procédés de fabrication et d'utilisation WO2014123775A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361760783P 2013-02-05 2013-02-05
US61/760,783 2013-02-05

Publications (1)

Publication Number Publication Date
WO2014123775A1 true WO2014123775A1 (fr) 2014-08-14

Family

ID=50239925

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/014082 WO2014123775A1 (fr) 2013-02-05 2014-01-31 Copolymère polysiloxane-polyamide, et ses procédés de fabrication et d'utilisation

Country Status (1)

Country Link
WO (1) WO2014123775A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180297937A1 (en) * 2017-03-22 2018-10-18 Iowa State University Research Foundation, Inc. Novel vegetable oil-based material as a substitute for carnauba wax
CN109384930A (zh) * 2018-09-30 2019-02-26 郑州大学 脂肪族直链聚酰胺与聚硅氧烷嵌段共聚物及其制备方法
WO2021101651A1 (fr) 2019-11-19 2021-05-27 Dow Silicones Corporation Composition aqueuse de revêtement de cuir

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US4766176A (en) 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
US5017654A (en) 1988-06-30 1991-05-21 Toray Silicone Company, Limited Thermosetting organosiloxane composition
US6051216A (en) 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents
US20040156807A1 (en) * 2003-02-12 2004-08-12 Zuchen Lin Method of making siloxane-based polyamide elastomers
US20080045687A1 (en) * 2004-12-01 2008-02-21 Nguyen Kimmai T Silicone Polyether-Amide Block Copolymers
US7799842B2 (en) 2005-06-14 2010-09-21 Dow Corning Corporation Reinforced silicone resin film and method of preparing same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US4766176A (en) 1987-07-20 1988-08-23 Dow Corning Corporation Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts
US5017654A (en) 1988-06-30 1991-05-21 Toray Silicone Company, Limited Thermosetting organosiloxane composition
US6051216A (en) 1997-08-01 2000-04-18 Colgate-Palmolive Company Cosmetic composition containing siloxane based polyamides as thickening agents
US6353076B1 (en) 1997-08-01 2002-03-05 Colgate-Palmolive Cosmetic composition containing siloxane-based polyamides as thickening agents
US20040156807A1 (en) * 2003-02-12 2004-08-12 Zuchen Lin Method of making siloxane-based polyamide elastomers
US20080045687A1 (en) * 2004-12-01 2008-02-21 Nguyen Kimmai T Silicone Polyether-Amide Block Copolymers
US7799842B2 (en) 2005-06-14 2010-09-21 Dow Corning Corporation Reinforced silicone resin film and method of preparing same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180297937A1 (en) * 2017-03-22 2018-10-18 Iowa State University Research Foundation, Inc. Novel vegetable oil-based material as a substitute for carnauba wax
US11319281B2 (en) 2017-03-22 2022-05-03 Iowa State University Research Foundation, Inc. Vegetable oil-based material as a substitute for carnauba wax
US11827583B2 (en) 2017-03-22 2023-11-28 Iowa State University Research Foundation, Inc. Vegetable oil-based material as a substitute for carnauba wax
CN109384930A (zh) * 2018-09-30 2019-02-26 郑州大学 脂肪族直链聚酰胺与聚硅氧烷嵌段共聚物及其制备方法
WO2021101651A1 (fr) 2019-11-19 2021-05-27 Dow Silicones Corporation Composition aqueuse de revêtement de cuir
US11518905B2 (en) 2019-11-19 2022-12-06 Dow Silicones Corporation Aqueous leather coating composition

Similar Documents

Publication Publication Date Title
KR101495215B1 (ko) 경화성 실리콘 조성물 및 이의 경화물
JP5345908B2 (ja) オルガノポリシルメチレン及びオルガノポリシルメチレン組成物
CN102050950B (zh) 含异三聚氰酸环的末端乙烯基聚硅氧烷
EP3318593B1 (fr) Matériau à dissipation de chaleur
CN107075221B (zh) 含氟聚合物-含氟有机聚硅氧烷复合材料、其制备方法、其用途以及用于该制备方法的前体组合物
KR100733052B1 (ko) 우수한 방오성 및 접착성을 갖는 실리콘 톱코트
WO2014123775A1 (fr) Copolymère polysiloxane-polyamide, et ses procédés de fabrication et d'utilisation
KR20220009409A (ko) 코팅 조성물 및 이의 용도
CN112739787B (zh) 官能聚硅氧烷
CN107429115A (zh) 底漆组合物、粘附方法和电/电子部件
KR20190119117A (ko) 플루오르화된 측기를 갖는 실리콘 엘라스토머
KR102470706B1 (ko) 축합 가교결합 입자의 제조 방법
EP3617273A1 (fr) Composition de gomme de silicone durcissable par addition
CA2040038A1 (fr) Produits d'etancheite a base de silicone
EP2831149B1 (fr) Copolymères séquencés de résine organosiloxane amphiphile linéaire
KR19980064563A (ko) 접착성이 개선된 경화성 유기 규소 조성물
CN117106307A (zh) 具有良好阻燃性的可固化的有机硅组合物
EP0455385A2 (fr) Procédé de durcissement de méthylhydrosiloxanes
CN116685650A (zh) 有机硅弹性体组合物
JP5105303B2 (ja) 液状シリコーンゴムコーティング剤組成物、エアーバッグ及びその製造方法
CN116438243A (zh) 混炼型硅橡胶组合物及硅橡胶固化物
KR102610344B1 (ko) 실리콘 고무 조성물
KR102216289B1 (ko) 경화성 실리콘 조성물
JP5605925B2 (ja) オルガノポリシルメチレン及びオルガノポリシルメチレン組成物
JP2024011536A (ja) ポリプロピレン樹脂とシリコーンゴムの接合物及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14708975

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14708975

Country of ref document: EP

Kind code of ref document: A1