WO1994028053A1 - Polydiorganosiloxane et polymere modifie par ce dernier - Google Patents

Polydiorganosiloxane et polymere modifie par ce dernier Download PDF

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Publication number
WO1994028053A1
WO1994028053A1 PCT/US1994/005998 US9405998W WO9428053A1 WO 1994028053 A1 WO1994028053 A1 WO 1994028053A1 US 9405998 W US9405998 W US 9405998W WO 9428053 A1 WO9428053 A1 WO 9428053A1
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Prior art keywords
amino
keto
amido
ether
group
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PCT/US1994/005998
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English (en)
Inventor
Vinod Ram Sastri
Yousef Mohajer
John Armstrong Young
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Alliedsignal Inc.
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Publication of WO1994028053A1 publication Critical patent/WO1994028053A1/fr

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    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • 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
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • 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

Definitions

  • the present invention relates to a novel polydiorganosiloxane and a polymer modified by
  • 4,640,962 describes a polyester resin, and a polyester fiber made from that resin, that includes siloxane block polymer units in the polyester matrix.
  • the siloxane block polymer units migrate to the surface of the polyester fiber during its formation so as to provide a silicon-sheathed polyester fiber.
  • copolymer with the base polymer imparts desirable surface properties to the base polymer.
  • This modified polyorganosiloxane can be chemically grafted onto a synthetic resin such as polyamide via a bond between the epoxy linkage and a group in the synthetic resin reactive with the epoxy linkage.
  • U.S. Pat. No. 5,070,168 describes a silicone polymer which includes an ether amino pendant group. The polymers deposit on substrate surfaces via the pendant group to form surface-modifying features.
  • polysiloxanes as fiber surface treating compositions.
  • U.S. Pat. No. 4,459,382 describes treating a fiber substrate with a composition comprising a liquid carrier, a first polydiorganosiloxane containing at least two epoxy-containing organic radicals and a second
  • polydiorganosiloxane selected from the group consisting of polydiorganosiloxanes containing at least two amino-containing hydrocarbon radicals and at least one polyalkyleneoxide radical and polydiorganosiloxanes containing at least two carboxy-containing hydrocarbon radicals and at least one polyalkyleneoxide radical.
  • This composition is said to confer upon the fibers enhanced antistatic properties, water absorbency, stain resistance, softness, smoothness, crease resistance and compression recovery.
  • copolymer additive comprising a hard segment polymer component and a soft segment polymer component, one of the soft segment components being a
  • the polyorganosiloxane disclosed in U.S. Pat. No. 4,987,203 permits the attachment of only one base polymer chain per polydiorganosiloxane molecule since each polydiorganosiloxane molecule only includes one epoxy group which is positioned at its foterminal end.
  • One result of this limited reactive site is a reduction in reactive probability and the
  • additives such as antioxidants, antistatic agents, flame retardants, plasticizers and ultraviolet light stabilizers.
  • additives such as antioxidants, antistatic agents, flame retardants, plasticizers and ultraviolet light stabilizers.
  • fluoroalkyl perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl, perfluoroaralkyl, alkyl ether, aryl ether, perfluoroalkyl ether and perfluoroaryl ether;
  • L is a divalent linking radical selected from the group consisting of alkylene, arylene,
  • perfluoroalkylene fluoroarylene, perfluoroarylene, fluoroaralkylene, perfluoroaralkylene, alkylene ether, arylene ether, perfluoroalkylene ether,
  • perfluoroaralkylene ether amino alkylene, amino arylene, amino cycloalkylene, amino aralkylene, amino fluoroalkylene, amino perfluoroalkylene, amino
  • fluoroaralkylene amino perfluoroaralkylene, amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido fluoroalkylene, amido
  • perfluoroalkylene amido fluoroarylene, amido
  • keto alkylene keto arylene, keto cycloalkylene, keto aralkylene, keto fluoroalkylene, keto perfluoroalkylene, keto fluoroarylene, keto perfluoroarylene, keto fluoroaralkylene and keto perfluoroaralkylene;
  • R 2 is a radical capable of reacting with a terminal or pendant group of a base polymer
  • X is a moiety capable of imparting an end use chararacteristic to said base polymer
  • T is (R 1 ) 3 SiO-;
  • a is 0 to 2000
  • b, c, d, e, and f are each 0 to 1000, provided that b + c + f ⁇ 1 and d + e + f ⁇ 1;
  • units of formula A are arranged in a random or a block structure.
  • modified base polymer comprising a structure:
  • BASE is a base polymer that has at least one terminal or pendant group selected from the group consisting of amino, carboxyl and hydroxy;
  • CARRIER is a polydiorganosiloxane comprising (R 1 ) 3 SiO- terminal groups and -Si(R 1 ) a (R 3 ) b -O- repeating units;
  • FUNCTIONAL is a moiety that imparts an end use characteristic to said BASE
  • each of R 1 is the same or different and is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, fluoroalkyl, perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl,
  • R 3 is a connecting group that includes a carbon that is capable of bonding with Si and a radical that is selected from the group consisting of a radical capable of bonding with said terminal or pendant group of said BASE and a radical capable of bonding with said FUNCTIONAL moiety.
  • Another embodiment of the present invention is a base polymer comprising a plurality of polymer chains, wherein at least one of the polymer chains forms a copolymer with a polydiorganosiloxane, the copolymer having a structure represented by the
  • R 1 is selected from the group
  • fluoroalkyl perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl, perfluoroaralkyl, alkyl ether, aryl ether, perfluoroalkyl ether and perfluoroaryl ether;
  • L is a divalent linking radical selected from the group consisting of alkylene, arylene,
  • perfluoroalkylene fluoroarylene, perfluoroarylene, flouroaralkylene, perfluoroaralkylene, alkylene ether, arylene ether, perfluoroalkylene ether,
  • perfluoroaralkylene ether amino alkylene, amino arylene, amino cycloalkylene, amino aralkylene, amino fluoroalkylene, amino perfluoroalkylene, amino
  • fluoroaralkylene amino perfluoroaralkylene, amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido fluoroalkylene, amido
  • perfluoroalkylene amido fluoroarylene, amido
  • keto perfluoroarylene amido fluoroaralkylene, amido perfluoroaralkylene, keto alkylene, keto arylene, keto cycloalkylene, keto aralkylene, keto fluoroalkylene, keto perfluoroalkylene, keto fluoroarylene, keto perfluoroarylene, keto fluoroaralkylene and keto perfluoroaralkylene;
  • Z is a base polymer chain
  • R 4 is a bonding group derived from a
  • X is a functional group capable of imparting an end use characteristic to said base polymer
  • T is (R 1 ) 3 SiO-;
  • a is 0 to 2000
  • b, c, d, e, and f are each 0 to 1000, provided that b + c + f ⁇ 1 and d + e + f ⁇ 1;
  • units of formula B are arranged in a random or a block structure.
  • a process for imparting an end use characteristic to a base polymer comprising the steps of (a) contacting a base polymer having a terminal or a pendant functional group with a polydiorganosiloxane having a structure represented by formula A above and (b) subjecting the resultant base polymer/polydiorganosiloxane combination to a reactive condition so that a chemical bond forms between the terminal or pendant functional group of the base polymer and R 2 of the polydiorganosiloxane.
  • base polymer denotes a polymer to which the polydiorganosiloxane is added resulting in the formation of a
  • polydiorganosiloxane/base polymer copolymer It is the properties of the base polymer which the addition of the polydiorganosiloxane is intended to modify.
  • Polymer chain denotes the linear chain of recurring monomer units which forms the backbone of the base polymer.
  • “Graft copolymer” denotes a copolymer wherein the base polymer chain segments are grafted onto the polydiorganosiloxane chain in random or block order. In other words, the -L-R 2 - bonding sites are distributed in random or block order along the
  • the random structure is preferred since it permits the variation of structural parameters such as the
  • Polymeric fibrous structure denotes a polymer or copolymer which has been formed into a continuous filament (single or multiple) of a running or extremely long length, or cut or otherwise short fiber known as staple, or a material which includes such a formed polymer or copolymer.
  • An example of a polymeric fibrous structure is a textile component such as a tape, fiber, yarn or other profile which typically has been tufted, woven, or otherwise constructed into fabric suitable for final use in home furnishings, particularly as floor covering or upholstery fabric.
  • Another example is a tape, fiber, yarn or other profile which has been woven into a fabric for use in
  • a further example is a tape, fiber, yarn or other profile which has been constructed into cord used for reinforcing tires.
  • Polyamide denotes nylon 6, nylon 66, nylon 4, nylon 12 and other polymers containing the
  • Nylon 6 and 66 are preferred.
  • Polyethylene terephthalate denotes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyalkylene adipate, polyesters of dihydric phenols, liquid crystal polymers and other polymers containing the (-C-0-)
  • polydiorganosiloxane can be used as a carrier for incorporating functional additives easily into a base polymer.
  • These functional additives designated herein as X or FUNCTIONAL, are capable of imparting end use characteristics to the base polymer.
  • end use characteristics is intended to mean a property which enhances or is advantageous to the use of a product made from the base polymer.
  • the polydiorganosiloxane carrier preferrably includes those functional additives or moieties which are known to impart end use
  • the typical classes of such functional additives include soil resistant agents, stain resistant agents, and
  • ultraviolet stabilizers ultraviolet stabilizers, flame retardants, lusterants, water repellants, preservatives, antistatic agents, antioxidants, plasticizers and hydrophilic agents.
  • Soil resistant agent as used herein means a moiety that prevents soil from entering a fiber or that allows soil to leave the fiber.
  • Stain resistant agent as used herein means a moiety that imparts to a fiber the ability to resist staining, particularly staining of polyamide fibers by acid dyes such as Food, Drug and Cosmetics Red Dye No. 40.
  • Ultra violet (UV) stabilizer as used herein means a moiety that inhibits or reduces fiber degradation caused by exposure to UV light.
  • "”Flame retardant” as used herein means a moiety that reduces the combustibility or flammability of a fiber.
  • Lusterant as used herein means a moiety that imparts increased luster or shininess to a fiber.
  • Water repellant as used herein means a moiety that imparts to a porous substrate such as a fiber an ability to repel water.
  • Preservative as used herein means a moiety, such as antibacterial, antimicrobial, antimold and antialgal agents, which assists in
  • Antistatic agent as used herein means a moiety that reduces the accumulation or
  • Antioxidant as used herein means a moiety that inhibits or reduces the rate of oxidative degradation of a fiber.
  • Polyizer as used herein means a moiety which increases the
  • Hydrophilic agent as used herein means a moiety which increases the aqueous solubility/dispersibility of the polydiorganosiloxane carrier.
  • Soil resistant agents which may be used with this invention include fluorochemicals in the form of fluorinated radicals which are well known in the art (see U.S. Pat. No. 5,135,046, incorporated herein by reference).
  • fluorochemicals typically include one or more fluoro aliphatic or fluoro aromatic radicals, preferably perfluoroalkyl or perfluoro aromatic
  • fluorochemicals are straight chain perfluoroalkyls having a structure of CF 3 - (-CF 2 -) n - and perfluoro substituted perfluoro aromatics having the structure of (CH 3 - (-CF 2 ) n -) m Ar (F) 5-m - where n is 1 to 100, m is 1 to 5 and Ar is an aryl group, preferably phenyl.
  • fluorochemicals are straight chain perfluoroalkyls having a structure of CF 3 - (-CF 2 -) n - and perfluoro substituted perfluoro aromatics having the structure of (CH 3 - (-CF 2 ) n -) m Ar (F) 5-m - where n is 1 to 100, m is 1 to 5 and Ar is an aryl group, preferably phenyl.
  • fluorochemicals are fluorocarbonylimino biurets
  • stain resistant agents typically those which conventionally are coated on a fiber, may be used in this invention including, but not limited to, sulfonated aromatics and
  • a particularly preferred sulfonated aromatic has a structure of (SO 3 M) n Ar-, where M is sodium, potassium, lithium or hydrogen, n is 1 to 5 and Ar is an aryl group, preferably phenylene.
  • a monosulfonated phenylene having a structure of
  • a particularly preferred carboxylated aromatic has a structure of (COOM) n Ar-, where M is sodium, potassium, lithium or hydrogen, n is 1 to 5 and Ar is an aryl group, preferably phenylene. Especially preferred is monocarboxylated phenylene having a structure of
  • Another useful stain resistant moiety is a sulfonated carboxylated phenylene such as sulfonated isophthalic (SPOSA), terephthalic or benzoic acid (described, for example, in U.S. Pat. Nos. 4,579,762).
  • SPOSA sulfonated isophthalic
  • terephthalic terephthalic
  • benzoic acid described, for example, in U.S. Pat. Nos. 4,579,762
  • a carboxyl group also be could be directly attached to the linking group, L, resulting in the structure of -L-COOH or -L- COOM, wherein M is Na, K or Li.
  • sulfonated aromatics are sulfonated phenol-aldehyde condensation products, especially sulfonated phenol-formaldehyde condensation products (described, for example, in U.S. Pats. No. 4,501,591; 4,592,940; 4,680,212; 4,839,212; 4,877,538), sulfonated naphthol-aldehyde condensation products, especially sulfonated naphthol- formaldehyde
  • UV light stabilizers that may be used in this invention include the known classes of UV light stabilizers. Most prevalent among the known classes of UV light stablizers are benzophenones and
  • benzotriazoles which, it will be recognized, are used in their corresponding radical form in this invention.
  • Substituted hydroxybenzophenones are the most common benzophenones.
  • Illustrative of useful substituted hydroxybenzophenones are 2,6- dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4- dihydroxybenzophenone, 2-hydroxy-4,4'- dimethoxybenzophenone, 3-benzoyl-2,4- dihydroxybenzophenone, 2-hydroxy-4-dodecyloxybenzopheneone, 2,2'-dihydroxy-4-n- octyloxybenzopheneone, 4-alkoxy-2-hydroxybenzophenone, and 4-butoxy-2,2'-dihydroxybenzophenone.
  • Benzotriazole UV light stabilizers particularly substituted
  • benzotriazoles such as 2-hydroxyphenylbenzotriazoles, are described, for example, in U.S. Pats. No.
  • UV light stabilizers include heterocyclic benzoates (described, for example, in U.S. Pat. No. 4,308,194), benzazines (described, for
  • napthalenetetracarboxylic acid (described, for example, in U.S. Pat. No. 4,814,366), and triazines such as substituted 2-hydroxyphenyltriazines (described, for example, in U.S. Pat. Nos. 5,106,891 and 4,831,068).
  • the preferred types of flame retardants are organic compounds containing halogen and/or phosphorus (described, for example, in U.S. Pat. No. 4,222,926, incorporated herein by reference) which are used in this invention in their radical form.
  • the organic radicals may be aliphatic, aromatic or alicyclic.
  • halogenated aryls described, for example, in U.S. Pat. No. 4,222,926 and U.S. Pat. No. 4,171,330, beginning at column 7, line 40,
  • substituted phenyls containing from 1 to 5 halogen, especially bromine, substituents.
  • chlorinated radicals are chlorinated aliphatics or alkyls, preferably C 10 to C 30 paraffins with chlorine contents of 20 to 70 percent.
  • brominated radicals are brominated aliphatics, decabromobiphenyl oxide, and brominated alkyl cyclohexanes (described, for example, in U.S.
  • halogenated phosphorus radicals include brominated copolyphosphonates (described, for example, in U.S. Pat. No. 4,229,552), aryl diphosphates (described, for example, in U.S. Pat. No. 4,203,888), 2-chloralkyl (2-chloroalkyloxy)hydrocarbylphosphinylproprionates
  • phosphonated radicals include those listed in U.S. Pat. No. 4,102,853, incorporated herein by reference, phosphonated triazines (described, for example, in U.S. Pat. No. 4,191,715), and poly(metal phosphinate)s
  • Preferred lusterants that can be used in this invention include cholestryl and its acids and salts.
  • Other lusterants that can be used are other cholesteric and liquid crystal moieties as described, for example, in Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 14, pp 395-427 (John Wiley & Sons, 3rd ed. 1981).
  • Preferred water repellants that can be used with this invention include moieties that have a perfluoroalkyl radical (described, for example, in U.S. Pats. No. 4,833,188, 3,916,053, 3,356,628, 3,329,661, 3,752,783, 4,617,057 and 4,296,224, all incorporated herein by reference).
  • Preferred preservatives that can be used with this invention include organosilicon quaternary ammonium salt (described, for example, in U.S. Pat. No. 4,835,019) and those preservatives listed in U.S. Pat. No. 4,624,679, incorporated herein by reference, such as phenoxarsines, phenarsazines, maleimides, isoindole docarboximides, halogenated aryl alkanols,
  • Antistatic agents useful in this invention include the known classes of nitrogen-containing compounds such as long chain amines, amides and
  • Particularly useful among conventional antistatic agents are quaternary ammonium salts.
  • a chlorine, bromine or iodine salt of quaternary ammonium which is bonded to the linking group -L- via a phenylene radical as shown below:
  • antioxidants useful in this invention are hindered phenols, hindered amines and aromatic amines.
  • hindered phenols hindered phenols
  • hindered amines hindered amines
  • aromatic amines aromatic amines
  • the hindered phenols typically can be monophenols, bisphenols, thiophenols or polyphenols.
  • Illustrative of hindered phenols are, 2,2'-methylenebis(6-tert-butyl-p-cresol), 1,3,5-trimethyl- 2,4,6-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy hydrocinnamate)]methane, 2,6-di-tert-butyl-4-methylphenol (i.e., butylated hydroxytoluene), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4-thiobis(6-tert-butyl-3-methylphenol), and N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
  • hindered amines also known in the art as hindered amine light stabilizers "HALS" are nitrogen-containing cyclic compounds including piperidines such as 2,2,6,6-tetramethylpiperidines and piperazines.
  • aromatic amines are p-phenylenediamines such as N,N' -disubstituted-p-phenylenediamines; diphenylamines such as alkylated diphenylamines; dihydroquinolines; and hydroquinones such as 2,5-di-tert-amylhydroquinone and tert-butylhydroquinone.
  • antioxidants are 2-mercaptobenzothiazole (described, for example, in U.S. Pat. No. 4,803,236), those described in U.S. Pat. No. 4,829,113 such as phenyl phosphates, phenyl phosphites, polyphenylene oxide, 2-mercaptobenzimidazole, and fluorocarbon wax.
  • antioxidants is found in Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 3, pp. 424-447 (John Wiley & Sons, 4th ed. 1992), incorporated herein by reference. Another list of commercially available antioxidants is found in Chemical Additives for the Plastics Industry. Table A-1, pp. 152-163 (Noyes Data Corp. 1987).
  • plasticizers also may be used in this invention and are described in Encyclopedia of Polymer Science and Engineering. Supplement Vol., pp. 568-647 (John Wiley & Sons, 2nd ed. 1989), incorporated herein by reference.
  • useful hydrophilic moieties are those containing ethylene oxide (-CH 2 CH 2 O-), ethylene imine (-CH 2 CH 2 NH-) , or acrylamide
  • the hydrophilic moiety contains at least one of these units and, more preferably, is a straight chain polymeric structure having a repeating plurality of these units (preferably 1 to 10 repeating units) .
  • the hydrophilic moiety could have a structure of (-NHCH 2 CH 2 -) x -NH-CH 3 , where x is 1 to 10.
  • the present invention is based upon a linear polydiorganosiloxane structure comprised of repeating units of -Si(R 1 ) 2 -O-.
  • R 1 substituents can be the same or different and generally can be any aliphatic, aromatic, alicyclic or heterocyclic radical.
  • R 1 substituents are alkyl, aryl, cycloalkyl, aralkyl, fluoroalkyl, perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl,
  • perfluoroalkyl ether and perfluoroaryl ether are straight-chained or branched and preferably contain 1 to 25, especially 1 to 10, carbon atoms.
  • perfluoroaryl, aryl ether and perfluoroaryl groups preferably contain 1 to 3 C 6 aromatic rings which may be substituted.
  • the cycloalkyl group preferably contains 3 to 15 carbon atoms.
  • fluoroaralkyl and perfluoroaralkyl groups preferably contain 7 to 15 carbon atoms.
  • trifluoromethyl are particularly preferred for the R 1 groups attached to the repeating silicon atoms.
  • Attachment of a methyl group to the repeating silicon atoms is advantageous due to its lower surface energy which contributes to the lubricity of the copolymer during processing and the propensity of the copolymer to migrate to the surface of the fiber.
  • An alkyl, especially methyl, is particularly preferred for the R 1 groups attached to the terminal silicon atoms.
  • the fluoro radicals are advantageous due to their ability to enhance soil removal from fibrous structure which include the copolymer.
  • polydiorganosiloxanes is well known in the art and is described, for example, in Encyclopedia of Polymer Science and Engineering. Vol. 15, pub. by John Wiley & Sons, Inc., pp. 234-258 (2d ed. 1989) and the
  • polydiorganosiloxanes must be modified so that at least one of the silicon atoms is bonded to a functional moiety (-L-X- or -R 3 -FUNCTIONAL) and at least one of the silicon atoms is bonded to a reactive site (-L-R 2 or R 3 ) for the base polymer.
  • a plurality of the silicon atoms are bonded to base polymer
  • a silicon atom can have bonded to it one or two base polymer reactive sites, one or two functional moieties, or a base polymer reactive site and a functional moiety.
  • Each modified polydiorganosiloxane molecule can include more than one type of reactive site groups and more than one type of functional moieties.
  • the reactive site group and the functional moiety must be compatible in the sense that they do react with each other. For example, if the functional moiety includes an amine, the
  • reactive site group cannot be an epoxy because the epoxy and the amine would react to form a cyclic group.
  • the linking group, -L- can be any divalent radical that is derived, as detailed below, from a hydrosilylation reaction between a siloxane monomer and a precursor compound that includes at least one
  • the precursor compound includes a vinyl group, more preferably an allyl or allyloxy group.
  • divalent radicals that can serve as linking groups, -L- are alkylene (such as methylene (-CH 2 -), ethylene (-CH 2 -CH 2 -), propylene (-CH 2 -CH 2 -CH 2 -), and C 4 to C 15 methylene), arylene (such as phenylene), cycloalkylene, aralkylene, fluoroalkylene, perfluoroalkylene, fluoroarylene, perfluoroarylene, fluoroaralkylene,
  • perfluoroaralkylene alkylene ether, arylene ether, perfluoroalkylene ether and perfluoroaralkylene ether, amino alkylene, amino arylene, amino cycloalkylene, amino aralkylene, amino fluoroalkylene, amino
  • perfluoroaralkylene amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido
  • fluoroalkylene amido perfluoroalkylene, amido
  • fluoroaralkylene amido perfluoroaralkylene, keto alkylene, keto arylene, keto cycloalkylene, keto aralkylene, keto fluoroalkylene, keto
  • amino is meant a divalent radical that includes -NH- as well as the linking carbon atoms.
  • amino is meant a divalent radical that includes -NHC(O)- as well as the linking carbon atoms.
  • keto is meant a divalent radical that includes -C(O)- as well as the linking carbon atoms.
  • alkylene fluoroalkylene
  • perfluoroalkylene, alkylene ether, perfluoroalkylene ether groups and their amino, amido and keto equivalents preferably contain 1 to 15 carbon atoms and can be branched or unbranched.
  • fluoroarylene, perfluoroarylene and arylene ether groups and their amino, amido and keto equivalents preferably contain 1 to 3 C 6 rings which may be
  • the cycloalkylene group and its amino, amido and keto equivalents preferably contains 3 to 10 carbon atoms.
  • perfluoroaralkylene and perfluoroaralkylene ether groups and their amino, amido and keto equivalents preferably contain 7 to 15 carbon atoms.
  • Particularly preferred are alkylene, alkylene ether and
  • fluoroalkylene groups such as (-CH 2 -) n , (-CH 2 -) n -O-CH 2 - and (-CF 2 -) n , respectively, wherein n is 1 to 15, preferably 3.
  • polydiorganosiloxane is modified to include certain reactive radicals, R 2 , the polydiorganosiloxane can be chemically attached to the terminal or pendant groups of a large variety of base polymer chains.
  • the reactive radical should be selected so that the base polymer which is to be modified.
  • the reactive radical should be selected so that the base polymer which is to be modified.
  • Suitable R 2 reactive radicals include epoxy, ;
  • B is caprolactam, phenol, ketoxime or a
  • R 6 is a polyalkylene or substituted
  • polyalkylene radical preferably dimethylene
  • R 7 is a C 1 to C 5 alkyl group
  • epoxy particularly preferred are epoxy, blocked isocyanate and anhydride because of the efficiency of their reaction with the terminal or pendant groups of the base polymer.
  • A, B and C are commercially available and D and E could be obtained via conventional organic synthesis
  • the polydiorganosiloxane of formula A and the base polymer of formula B can include up to six different repeating units represented by the subscripts a, b, c, d, e and f.
  • the subscript a can range from 0 to 2000, preferably 25 to 1500, and more preferably 100 to 1000.
  • the subscripts b, c, d, e and f can each, individually, range from 0 to 1000, preferably 1 to 250, and more preferably 5 to 100, provided b + c+ f ⁇ 1 and d + e + f ⁇ 1.
  • the specific amounts for the subscripts a, b, c, d, e and f are dependent upon the relative molar amounts of the reactants used to produce the polydiorganosiloxane.
  • Each repeating unit can occupy any position along the backbone chain of the polydiorganosiloxane.
  • the backbone chain could consist of 3 units represented by the subscript a, followed by 1 unit represented by the subscript b, followed by 5 units represented by the subscript a, followed by 2 units represented by the subscript d.
  • the functionalized polydiorganosiloxanes of the invention may be produced by a two step method
  • hydrosilylation step serves to attach
  • hydrolysis/condensation step serves to form the
  • hydrosilylation can be performed before or after the hydrolysis/condensation, but it is preferred to perform the hydrosilylation after hydrolysis/condensation.
  • This modified portion of the functional additive is the precursor of the linking group L.
  • Illustrative of possible radicals for Y include isocyanato, glycidyl ether, halogen, hydroxy, carboxyl, amino and mercapto.
  • the functional additive itself does not have to be modified but can be reacted with a pendant group already attached to the
  • a functional moiety-containing compound then is reacted with this polydiorganosiloxane so that the functional moiety bonds to Y.
  • the same mechanism can also be applied to a silane unit.
  • RT2 a modified poly ethylene glycol methyl ether hydrophilic group
  • a silane unit is used as the starting reactant and has a preferred structure of:
  • A is a halogen such as chloride, a carboxy such as acetoxy, a hydroxy or an alkoxy.
  • the silane unit could also be dihydric.
  • silane units then undergo hydrolysis/condensation to form the functionalized polydiorganosiloxane as shown below for a typical functionalized
  • RT1 polymethyl hydrogen siloxane species of this structure. This polydiorganosiloxane then undergoes hydrosilylation to attach the -L-X and -L-R 2 groups to the silicon atoms.
  • polydiorganosiloxanes is described below. These functionalized polydiorganosiloxanes are examples only and other functionalized polydiorganosiloxanes can be prepared by similar methods.
  • RT2 allyloxybenzophenone
  • RT4 1.717 g allylglycidyl ether
  • 50 ml dry THF 19.071 g allyloxybenzophenone
  • RT4 serves as a diluent.
  • Example 2 Reactive Polydiorganosiloxane with
  • RT5 2.4 g allylglycidyl ether (designated "RT3"), 100 ml dry THF and 0.03 g H 2 PtCl 6 .
  • Example 3 is an example of polydiorganosiloxane of formula C, described hereinafter.
  • the reaction scheme is set forth below:
  • Example 4 Infrared analysis showed that the Si-H band at 2164 cm -1 disappeared indicating that the reaction had gone to completion.
  • the solution was treated with decolorizing carbon and filtered through Celite ® .
  • the resulting solution was clear and bright yellow.
  • the solvent was removed by a rotary evaporator leaving a viscous liquid that weighed 57.7g.
  • the final product was dull orange. This product is designated "Example 4".
  • the reaction scheme is set forth below:
  • Example 5 The reaction scheme is set forth below:
  • Example 5 the reactive group R 2 is a blocked
  • isocyanate derived from RT8 and the linking radical, - L-, is propylene, (-CH 2 -) 3 .
  • the allyl isocyanate provides the reactive double bond necessary to effect hydrosilylation.
  • polydiorganosiloxane that includes a reactive radical, R 2 occurs via a copolymerization reaction between the functionalized polydiorganosiloxane and the base polymer. Due to the versatility of this invention, the amount of the polydiorganosiloxane carrier, and thus the functional additive, incorporated into the base polymer can be carefully controlled.
  • the functionalized polydiorganosiloxane carrier can be reacted with a wide variety of base polymers to form a copolymer.
  • a mixture of different functionalized polydiorganosiloxane carriers can be added to a base polymer depending upon the desired end use
  • Any base polymer that has a terminal or pendant group that can react with the reactive radical R 2 of the functionalized polydiorganosiloxane to form a copolymer can be used in this invention.
  • terminal or pendant groups include carboxyl, amino and hydroxy groups.
  • terminal groups include carboxyl, amino and hydroxy groups.
  • polymers, X or BASE, that include such terminal groups are polyamide, polyester, polyurea, polyimide,
  • polycarbonate, polyether, polyarylate, polyester ethers, telechelic functionalized polystyrene and telechelic functionalized polyolefin Since the polyolefins and polystyrenes do not include terminal groups that could react with the reactive radicals R 2 , they must first be modified by known methods such as graft polymerization to include a side chain attached onto the polyolefin backbone chain before they can react with the polydiorganosiloxane. The side chain must include a pendant group such as carboxyl, amino or hydroxy which reacts with R 2 .
  • a significant advantage of the invention is that it does not require the simultaneous formation of the base polymer and the base polymer/polydiorganosiloxane copolymer.
  • the repeating monomeric structure of the base polymer chain remains intact during formation of the copolymer of the invention.
  • This unique feature permits the initial production of the base polymer and then, at a later time and/or location, the base polymer can by modified by reacting the functionalized polydiorganosiloxane carrier with the base polymer to form the copolymer.
  • the copolymer structure resulting, from the reaction of the polydiorganosiloxane and the base polymer is represented by previously depicted formula B.
  • Another approach for representing the base polymer modified with the functionalized polydiorganosiloxane carrier is depicted previously as BASE - CARRIER - FUNCTIONAL.
  • R 4 represents the bonding structure which forms as a result of the
  • the R 4 structure depends upon the particular base polymer and the reactive radical or precursor R 2 which modifies the functionalized
  • polydiorganosiloxane that reacts with the base polymer.
  • the bonding structure between the base polymer and the polydiorganosiloxane are the following copolymers that will form with nylon as the base polymer (wherein Ny represents the repeating monomeric units of nylon):
  • R 2 is an epoxy group:
  • R 2 is an isocyanate group:
  • R 2 is a blocked isocyanate:
  • R 2 is an oxazoline group:
  • R 2 is a carbodiimide group:
  • R 2 is a succinic anhydride group:
  • R 2 is a caprolactim ether group
  • both the amino and carboxyl terminal groups of nylon react with the illustrated reactive radicals, but in some instances, such as where R 2 is an oxazoline, succinic anhydride or caprolactim ether, the reaction with one of the terminal groups is faster than with the other terminal groups.
  • polyethylene terephthalate will react with the reactive groups to form copolymers.
  • R 2 is an epoxy group the following copolymer is formed (wherein PE represents the repeating monomeric units of polyester):
  • hydroxy terminal group of a polyarylate will react with the reactive groups to form copolymers.
  • the backbone chain must include a side chain which has pendant groups that can react with the reactive radicals R 2 or a telechelic polyolefin with terminal groups that can react with the reactive radicals must be used.
  • polypropylene could be copolymerized with acrylic acid to form a side chain which includes carboxylic acid pendant groups or polypropylene could be copolymerized with maleic anhydride to form a side chain which includes anhydride pendant groups.
  • the base polymer are the fiber-forming polymers such as polyamide, especially nylon 6 and nylon 66, and polyester, especially PET, PEN and PBT.
  • the fiber-forming polymers such as polyamide, especially nylon 6 and nylon 66, and polyester, especially PET, PEN and PBT.
  • polydiorganosiloxane carrier reacted with the base polymer is such that the number of reactive sites (-L- R 2 ) are lower than the number of base polymer terminal groups. Accordingly, not all of the base polymer chains react with a polydiorganosiloxane to form a copolymer. On the other hand, substantially all of the polydiorganosiloxane reacts with the base polymer. In general, about 0.05 to 95, preferably about 0.2 to 25, more preferably about 0.2 to 5, weight%
  • polydiorganosiloxane is added to the base polymer, based upon the weight of the combined
  • copolymerization or bonding occurs between a terminal functional group of the base polymer and the reactive radical or site of the polydiorganosiloxane. Any reaction system can be used to effect the
  • copolymerization such as solution polymerization with catalysts or grafting polymerization by coating a polymer substrate with a solution of the
  • polydiorganosiloxane but the preferred system is melt extrusion.
  • the particular reaction conditions at which this copolymerization occurs vary depending upon the specific reactive groups and base polymers selected.
  • linking group, -L- must be inert during copolymerization of the polydiorganosiloxane and the base polymer.
  • the linking group, -L- cannot include any functionality which would react with the terminal group of the base polymer because such a reaction would result in the cleavage of the functional group X from the polydiorganosiloxane.
  • the linking group cannot include an ester linkage because an ester would react with the amine terminal group of a
  • polyamide base polymer or with the carboxyl terminal group of a polyester base polymer.
  • the extrusion should be about 10 to 50°C, preferably 10 to 30°C, higher than the melting point of the base polymer.
  • the extrusion can be carried out in either a single or twin screw extruder.
  • polydiorganosiloxane and the base polymer can be pre-blended in that chips or pellets of the
  • polydiorganosiloxane and the base polymer can be mixed prior to melting.
  • an on-line addition can be used in that the polydiorganosiloxane is added to the already molten base polymer.
  • Another method for incorporating the functionalized polydiorganosiloxane into the base polymer involves dissolving the functionalized polydiorganosiloxane in an organic solvent or, if the functionalized
  • polydiorganosiloxane includes a hydrophilic agent, in water and then applying this solution to the base polymer.
  • a solution containing about 0.05 to 10, preferably about 0.1 to 7, and more preferably about 0.2 to 5 wt.% of the polydiorganosiloxane is prepared and applied to a base polymer substrate such as a fiber.
  • Various methods for applying the solution include transporting the base polymer substrate through a bath of the solution, spraying the solution onto the base polymer substrate and transporting the base polymer substrate over a surface coated with the solution. The coated substrate then is cured so that the reactive radicals R 2 react with the base polymer thereby locking the functionalized polydiorganosiloxane into the base polymer.
  • the curing can be effected by drying the coated base polymer substrate to remove the organic solvent or water. More specifically, the coated base polymer substrate can be exposed to ambient atmosphere, subjected to temperatures ranging from 40 to 180, preferably 60 to 150, more preferably 80 to 150°C, and/or subjected to a stream of pressurized gas, typically air.
  • a stream of pressurized gas typically air.
  • the polydiorganosiloxane of Example 4 was dissolved in THF at wt. % levels indicated in Table 1.
  • PET fibers woven into a fabric for a seatbelt were passed through a bath of the dissolved polydiorganosiloxane at ambient atmospheric pressure and temperature.
  • the coated PET fabric was dried in air at ambient pressure and temperature for one hour then at 60 °C for an additional one hour.
  • the control sample was a PET fabric that was not coated with the
  • the PET fabrics were analyzed for xenon lightfastness by American
  • AATCC Method 16E (225 kJ light source) graded by Gray Scale. AATCC Method 16E provides an indication of the
  • polydiorganosiloxane acts as a carrier for the UV light stabilizer moiety.
  • a Gray Scale value of 5 signifies no visible fading and a Gray Scale value of 1 signifies a complete loss of color
  • the difference between a Gray Scale value of 2 and 2.5 is significant, indicating substantially improved UV protection.
  • Nylon 6 chips can be dry blended with a
  • the resultant blend would be dried at 80-120°C in a vacuum oven for 16 hours.
  • the blend would be cooled, tumbled again for 5 minutes and fed into a hopper of a twin screw extruder. Melt extrusion would be carried out at 250-270°C and the extrudate pulled into strands, quenched in a water trough and
  • pelletized The pellets would be dried in a vacuum oven at 80-120°C for 16 hours. After this extrusion procedure, the reactive groups of the functionalized polydiorganosiloxane would have bonded with the
  • the pellets produced by the extrusion procedure would be fed into a hopper of a single or twin screw extruder which has a continuous nitrogen flow and re-melted. During this re-melting any unreacted polydiorganosiloxane may react with the nylon 6.
  • the molten polymer leaving the extruder would be fed into a metering pump, a filter pack and then through a spinneret. The extruding and spinning steps would take place at 250-270°C.
  • the fiber produced from the spinneret would be drawn and jet textured according to conventional procedures. The draw ratio would be 2.8:1.
  • PET chips can be dry blended with a predetermined amount of at least one liquid functionalized
  • the resultant blend would be dried at 160°C until a
  • the pellets produced by the extrusion procedure would be fed into a hopper of a twin screw extruder and re-melted at 290°C.
  • the molten polymer leaving the extruder would be fed into a metering pump, a filter pack and then through a 32 hole, round cross-section, spinneret.
  • the spinning temperature would be 290 °C and a heated sleeve would be placed around the spinneret.
  • the fiber produced from the spinneret would be drawn at a 6:1 draw ratio.
  • polydiorganosiloxane that includes reactive groups
  • a polydiorganosiloxane which includes functional moieties but not reactive groups also can be included in the blend with the base polymer.
  • Such a functional moiety-only polydiorganosiloxane would have a structure represented by formula C wherein R 1 is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, fluoroalkyl,
  • fluoroaralkyl perfluoroaralkyl, alkyl ether, aryl ether, perfluoroalkyl ether and perfluoroaryl ether;
  • L is a divalent linking radical selected from the group consisting of alkylene, arylene, cycloalkylene, aralkylene, fluoroalkylene, perfluoroalkylene,
  • X is a functional group capable of imparting an end use characteristic to the base polymer
  • T is (R 1 ) 3 SiO-;
  • a is 0 to 1000
  • b and c are each 0 to 20, provided that b and c are not both 0;
  • a polydiorganosiloxane of formula C can be blended, preferably melt blended, with a reactive functionalized polydiorganosiloxane and a base polymer.
  • Example 3 can be melt blended with a reactive

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

Polydiorganosiloxane comprenant une fraction susceptible de conférer une caractéristique d'utilisation finale à un polymère de base, ainsi que, de préférence, un radical susceptible de réagir avec un groupe terminal, ou rattaché par une extrémité, du polymère de base. L'invention se rapporte également à un polymère de base modifié par la formation d'un copolymère avec le polydiorganosiloxane, un groupe fonctionnel terminal du polymère de base étant lié au radical réactif du polydiorganosiloxane. Un procédé de production du copolymère est également décrit. Le polymère de base est de préférence composé d'un polymère à formation de fibres tel que le polyamide et le polyester. Le polydiorganosiloxane agit comme porteur par rapport à la fraction conférant la caractéristique d'utilisation finale.
PCT/US1994/005998 1993-05-28 1994-05-27 Polydiorganosiloxane et polymere modifie par ce dernier WO1994028053A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042267A1 (fr) * 1996-05-03 1997-11-13 Alliedsignal Inc. Nouvelles compositions de nylon
FR2781491A1 (fr) * 1998-07-21 2000-01-28 Rhodia Chimie Sa Utilisation d'une composition silicone fonctionnalisee pour la realisation de revetement et/ou d'impregnation hydrophobe et/ou oleophobe, a faible energie de surface
NL1020029C2 (nl) * 2002-02-21 2003-08-25 Dsm Nv Werkwijze voor de bereiding van ethylenisch onverzadigde verbindingen met lactam-geblokte isocyanaatgroepen, alsmede de bereiding en toepassing daarvan.
US20150283784A1 (en) * 2010-08-02 2015-10-08 Warrick James David Allen Composite articles and methods of producing same
US9797088B2 (en) 2010-08-02 2017-10-24 Syntor Fine Chemicals Limited Methods of treating textile fibres
CN111183178A (zh) * 2018-05-31 2020-05-19 美国陶氏有机硅公司 使用可移除酸催化剂制备氨基官能聚二有机硅氧烷的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659777A (en) * 1985-11-27 1987-04-21 Thoratec Laboratories Corp. Polysiloxane/poly(oxazoline) copolymers
EP0295561A2 (fr) * 1987-06-18 1988-12-21 General Electric Company Silicone-polyimides et méthode de préparation
US4937277A (en) * 1988-05-16 1990-06-26 Rhone-Poulenc Specialty Chemicals, L.P. Alkoxylated silicon polymers
US4987203A (en) * 1988-10-25 1991-01-22 Chisso Corporation Polyorganosiloxane compounds with epoxy group
EP0472912A2 (fr) * 1990-08-27 1992-03-04 General Electric Company Copolymères greffés ignifuges d'organopolysiloxane-polycarbonate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4659777A (en) * 1985-11-27 1987-04-21 Thoratec Laboratories Corp. Polysiloxane/poly(oxazoline) copolymers
EP0295561A2 (fr) * 1987-06-18 1988-12-21 General Electric Company Silicone-polyimides et méthode de préparation
US4937277A (en) * 1988-05-16 1990-06-26 Rhone-Poulenc Specialty Chemicals, L.P. Alkoxylated silicon polymers
US4987203A (en) * 1988-10-25 1991-01-22 Chisso Corporation Polyorganosiloxane compounds with epoxy group
EP0472912A2 (fr) * 1990-08-27 1992-03-04 General Electric Company Copolymères greffés ignifuges d'organopolysiloxane-polycarbonate

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997042267A1 (fr) * 1996-05-03 1997-11-13 Alliedsignal Inc. Nouvelles compositions de nylon
US5945469A (en) * 1996-05-03 1999-08-31 Alliedsignal Inc. Nylon compositions for UV stability
FR2781491A1 (fr) * 1998-07-21 2000-01-28 Rhodia Chimie Sa Utilisation d'une composition silicone fonctionnalisee pour la realisation de revetement et/ou d'impregnation hydrophobe et/ou oleophobe, a faible energie de surface
WO2000005315A1 (fr) * 1998-07-21 2000-02-03 Rhodia Chimie Utilisation d'une composition silicone fonctionnalisee pour la realisation de revetement et/ou d'impregnation hydrophobe et/ou oleophobe, a faible energie de surface
US6491981B1 (en) 1998-07-21 2002-12-10 Rhodia Chimie Use of functionalized silicone composition for producing a hydrophobic and/or oil-repellent coating and/or impregnation with low surface energy
NL1020029C2 (nl) * 2002-02-21 2003-08-25 Dsm Nv Werkwijze voor de bereiding van ethylenisch onverzadigde verbindingen met lactam-geblokte isocyanaatgroepen, alsmede de bereiding en toepassing daarvan.
US20150283784A1 (en) * 2010-08-02 2015-10-08 Warrick James David Allen Composite articles and methods of producing same
US9764529B2 (en) * 2010-08-02 2017-09-19 Syntor Fine Chemicals Limited Composite articles and methods of producing same
US9797088B2 (en) 2010-08-02 2017-10-24 Syntor Fine Chemicals Limited Methods of treating textile fibres
CN111183178A (zh) * 2018-05-31 2020-05-19 美国陶氏有机硅公司 使用可移除酸催化剂制备氨基官能聚二有机硅氧烷的方法

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