BACKGROUND OF THE INVENTION

The present invention relates to a novel polydiorganosiloxane and a polymer modified by copolymerization with the novel polydiorganosiloxane, particularly a copolymer of the novel polydiorganosiloxane and a fiber-forming polymer.

There have been numerous disclosures of the use of specially tailored polysiloxanes in conjunction with other polymers. For example, U.S. Pat. No. 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.

U.S. Pat. No. 4,663,413 describes a linear polysiloxane-polylactone block copolymer which is miscible with base polymers, particularly nylon. Blending of the polysiloxane-polylactone block copolymer with the base polymer imparts desirable surface properties to the base polymer.

U.S. Pat. No. 4,987,203 describes a polyorganosiloxane which contains a fluorinated substituent at its α-terminal position and a substituent having an epoxy linkage at its δ>-terminal position. 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.

The use of polysiloxanes as fiber surface treating compositions is also known. For example, 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.

A related disclosure which concerns the incorporation of polysiloxanes into base polymers is copending, commonly assigned U.S. Application Ser. No. 502,216, filed March 30, 1990. This application describes a polymeric release film comprising a blend of a base polymer and a copolymer additive, the copolymer additive comprising a hard segment polymer component and a soft segment polymer component, one of the soft segment components being a polydiorganosiloxane.

A significant limitation in the prior art concerning the modification of base polymers via the reactive incorporation of polysiloxanes, however, is the limited flexibility in selecting the specific reactive sites and amounts of the siloxane functional group relative to the backbone chain of the base polymer. For example, 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 fo- terminal end. One result of this limited reactive site is a reduction in reactive probability and the consequential tendency towards increased amounts of

unreacted polydiorganosiloxane. A need therefore exists for a more flexible method of incorporating polydiorganosiloxanes into base polymers which provides a wider range and more selectivity in controlling bonding locations and amounts for the siloxane functionality.

It is also known to modify polymers by using additives such as antioxidants, antistatic agents, flame retardants, plasticizers and ultraviolet light stabilizers. Typically, these additives are incorporated by coating and crosslinking on a polymer substrate or by blending with the polymer. These methods, however, suffer from a few significant drawbacks such as a lack of durability for coated additives that are non-crosslinked, insufficient bulk protection, and manufacturing inefficiency due to the need for additional coating or blending steps. It would be advantageous if a method could be found for incorporating additives into polymers that avoids these problems.

SUMMARY OF THE ^' INVENTION

It is therefore an object of the present invention to provide an efficient and versatile method for incorporating an additive into a base polymer. In accomplishing this object there is provided according to the present invention a polydiorganosiloxane comprising a structure represented by the following formula A:

X

I

L

T- ( - S - ) _β - ( - SiO- ) _f - T

(A)

wherein R _t is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, 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, cycloalkylene, aralkylene, fluoroalkylene, 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 fluoroarylene, amino perfluoroarylene, amino fluoroaralkylene, amino perfluoroaralkylene, amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido fluoroalkylene, amido perfluoroalkylene, amido fluoroarylene, amido 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;

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 (RjJgSiO-; 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; and the

R ₂ X X X

R _t R _x L L L L (-SiO-) _s , (-SiO-) _b . (-SiO-) _e , (-SiO-) _d , (-SiO-)β» (SiO-) _f t i i i i i

R _x L L R _t L L

I I l ι

R ₂ R X R ₂ units of formula A are arranged in a random or a block structure. There is also provided according to the present invention a modified base polymer comprising a structure:

BASE - CARRIER - FUNCTIONAL

wherein 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 terminal groups and -Si(R ₁ ).(R ₃ ) _b -0- repeating units;

FUNCTIONAL is a moiety that imparts an end use characteristic to said BASE; a and b are each 0, 1 or 2, provided a + b = 2 and b = 1 for at least one of said repeating units; each of R _t is the same or different and is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, fluoroalkyl, perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl, perfluoroaralkyl, alkyl ether, aryl ether, perfluoroalkyl ether and perfluoroaryl ether; and

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 following formula B:

^• -1

T- (-sϊo-).- (-sio-) _b - (-s -) _f T

I I

L

I t I I i 4 R X X X

I.

(B)

wherein R is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, 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, cycloalkylene, aralkylene, fluoroalkylene, 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 fluoroarylene, amino perfluoroarylene, amino fluoroaralkylene, amino perfluoroaralkylene, amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido fluoroalkylene, amido perfluoroalkylene, amido fluoroarylene, amido 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 precursor which is capable of reacting with a terminal or pendant group of said base polymer chain;

X is a functional group capable of imparting an end use characteristic to said base polymer;

T is (R^sSiO-; 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; and the

z Z i

R X R ₄

I ₄ 1 I

^• - Ri L L L

( -S10- ) a' ( - SiO- ) _b , ( - S10- ) , ( -SiO- ) d / ( - SiO- ) _e , ( - SiO- ) _f i I i I I

Ri L L L L L

I I /

? ^• R ₄ X X X

I

Z Z

units of formula B are arranged in a random or a block structure. There also is provided 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.

Further objects, features and advantages of the present invention will become apparent from the detailed description of preferred embodiments that follows.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "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 polydiorganosiloxane chain according to the general formula

.AAAAAAAAAA.... or . AAAAAAAAA. ι l i i i

B B BBB

I I I

B B BBB l i i » i

B B BBB

(random) (block)

The random structure is preferred since it permits the variation of structural parameters such as the effective molecular weight between the reactive Si sites depending upon the desired properties of the copolymer. The more regular spacing between the -L-R ₂ - bonding sites also allows for more uniform variation of the effective molecular weight. "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 seatbelts. 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 (C-NH)

0 structure along with the (CH ₂ ) _X chain as described in Cook, J., Handbook of Textile Fibres. Merrow Publishing Co., pp. 194-327 (1984). Nylon 6 and 66 are preferred. "Polyester" 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-)

II 0 repeating unit as described in Encyclopedia of Polymer Science and Engineering, Vol. 12., pub. by John Wiley & Sons, Inc., pp. 1-300 (2d ed. 1989).

It has been discovered that a 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. The term "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.

More specifically, the polydiorganosiloxane carrier preferrably includes those functional additives or moieties which are known to impart end use characteristics to polymeric fibrous structures. The typical classes of such functional additives include soil resistant agents, stain resistant agents, 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 fla mability

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 preventing biological degradation of a fiber by microorganisms. "Antistatic agent" as used herein means a moiety that reduces the accumulation or increases the rate of dissipation of electrical charge on the surface of a fiber. "Antioxidant" as used herein means a moiety that inhibits or reduces the rate of oxidative degradation of a fiber. "Plasticizer" as used herein means a moiety which increases the workability, flexibility or distensibility of a fiber. "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) . Such fluorochemicals typically include one or more fluoro aliphatic or fluoro aromatic radicals, preferably perfluoroalkyl or perfluoro aromatic radicals. Particularly preferred 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. Illustrative of other fluorochemicals are fluorocarbonylimino biurets (described, for example, in U.S. Pat. No. 4,958,039), fluorochemical amine compounds (described, for example, in U.S. Pat. No. 4,841,090), and fluoroaliphatic substituted guanidines (described, for example, in U.S.

Pat . No . 4 , 540 , 497 ) .

Numerous known classes of 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 carboxylated aromatics. A particularly preferred sulfonated aromatic has a structure of (S0 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. Especially preferred is a monosulfonated phenylene having a structure of

A particularly preferred carboxylated aromatic has a structure of (COOM)-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). 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.

Illustrative of other 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 condensation products (described, for example, in U.S. Pat. No. 4,501,591) .

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. The following are examples of such benzophenone and benzotriazole radicals:

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-dodecyl- oxybenzopheneone, 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. 4,226,763; 4,265,804; 4,278,589; 4,668,235; 5,106,891; and 5,095,062, all incorporated herein by reference. Illustrative of useful substituted benzotriazoles are 2(3' -t-butyl-2' -hydroxy-5' -methyl-phenyl) -5- chlorobenzotriazole, 2 (3' ,5' -di-t-butyl-2' -hydroxy- phenyl) -5-chlorobenzotriazole, 2 (2' -hydroxy-3' ,5-di-t- amyl-phenyl)benzotriazole, 2 (2' -hydroxy-3' ,5' -di-t- butyl)benzotriazole, 2 (2' -hydroxy-5' - emthylphenyl)benzotriazole, and 2 (2' -hydroxy-δ-t- octylphenyl)benzotriazole.

A list of some commercially available UV stabilizers is found in Chemical Additives for the

Plastics Industry. Table A-16, pp. 440-446 (Noyes Data Corp. 1987) . Other UV light stabilizers include heterocyclic benzoates (described, for example, in U.S. Pat. No. 4,308,194), benzazines (described, for example, in U.S. Pat. No. 4,260,809), benzoxazoles

(described, for example, in U.S. Pat. No. 4,162,254), condensed aromatics such as substituted and unsubstituted napthyl

substituted and unsubstituted anthracene, substituted and unsubstituted phenanthryl, 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.

Especially preferred are 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, incorporated herein by reference) , particularly substituted phenyls containing from 1 to 5 halogen, especially bromine, substituents.

Other examples of chlorinated radicals are chlorinated aliphatics or alkyls, preferably C ₁₀ to C ₃₀ paraffins with chlorine contents of 20 to 70 percent. Other examples of brominated radicals are brominated aliphatics, decabromobiphenyl oxide, and brominated alkyl cyclohexanes (described, for example, in U.S. Pat. No. 4,801,405) .

Examples of 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 (described, for example, in U.S. Pat. No. 4,193,914), and brominated polyphenylphosphonates (described, for example, in U.S. Pat. No. 4,178,283). Examples of 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 (described, for example, in U.S. Pats. No. 4,180,495; 3,900,444; 3,786,114 and 4,049,612).

A list of some commercially available flame retardants is found in Chemical Additives for the

Plastics Industry. Table A-9, pp. 268-278 (Noyes Data Corp. 1987) . Other flame retardants include aromatic

sulfonamides (described, for example, in U.S. Pats. No. 4,243,418 and 3,730,418), and s-triazines (described, for example, in U.S. Pat. No. 4,234,341).

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, isothiazolinones and organotins. Antistatic agents useful in this invention include the known classes of nitrogen-containing compounds such as long chain amines, amides and quaternary ammonium salts, sulfonic acids and alkyl aryl sulfonates, polyoxyethylene derivatives, polyglycols and their derivatives, polyhydric alcohols and their derivatives and phosphoric acid derivatives. In the context of the present invention, these compounds, of course, exist as radicals bonded to the polydiorganosiloxane. A general description of such antistatic agents is found in Kirk-Othmer. Encyclopedia of Chemical Technology. Vol. 3, pp. 540-575 (John Wiley & Sons, 4th ed. 1992) . A list of some commercially

available antistatic agents is found in Chemical Additives for the Plastics Industry. Table A-2, pp. 164-174 (Noyes Data Corp. 1987) .

Particularly useful among conventional antistatic agents are quaternary ammonium salts.

Especially preferred is a chlorine, bromine or iodine salt of quaternary ammonium which is bonded to the linking group -L- via a phenylene radical as shown below:

Known classes of antioxidants useful in this invention are hindered phenols, hindered amines and aromatic amines. In the context of the present invention, these compounds, of course, exist as radicals bonded to the polydiorganosiloxane as shown by the way of example below:

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- ert-butyl-4-hydroxybenzyl)benzene, tetra:is [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-hydroxy- hydrocinnamate) . Illustrative of 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. Illustrative of 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.

Illustrative of other 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.

A general description of antioxidants, including a list of some commercially available 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-l, pp. 152-163 (Noyes Data Corp. 1987) . Conventional 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. Illustrative of useful hydrophilic moieties are those containing ethylene oxide (-CHjCHjO-),

ethylene imine (-CH ₂ CH ₂ NH-) , or acrylamide (-CH ₂ -).

CH ₂ -C(0) -NH ₂ Typically, 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) . For example, the hydrophilic moiety could have a structure of (-NHCH _J CH _J -^-NH-CH _J , 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 -0-. Each of the R _x substituents can be the same or different and generally can be any aliphatic, aromatic, alicyclic or heterocyclic radical. Among the more useful R _x substituents are alkyl, aryl, cycloalkyl, aralkyl, fluoroalkyl, perfluoroalkyl, fluoroaryl, perfluoroaryl, fluoroaralkyl, perfluoroaralkyl, alkyl ether, aryl ether, perfluoroalkyl ether and perfluoroaryl ether. The alkyl, fluoroalkyl, perfluoroalkyl, alkyl ^" ether and perfluoroalkyl ether groups can be straight-chained or branched and preferably contain 1 to 25, especially 1 to 10, carbon atoms. The aryl _* fluoroaryl, 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. The aralkyl, fluoroaralkyl and perfluoroaralkyl groups preferably contain 7 to 15 carbon atoms. Methyl and trifluoromethyl are particularly preferred for the R _x 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 _x

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. The production of linear 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 references cited therein. For utilization in the present invention, however, conventional linear 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. Preferably, a plurality of the silicon atoms are bonded to base polymer reactive sites and a plurality of the silicon atoms are bonded to a functional moiety. 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, however, 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 unsaturated bond in a reactive position so that a carbon-silicon bond is formed between the siloxane and the precursor compound. Preferably, the precursor

compound includes a vinyl group, more preferably an allyl or allyloxy group. Illustrative of 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 perfluoroalkylene, amino fluoroarylene, amino perfluoroarylene, amino fluoroaralkylene, amino perfluoroaralkylene, amido alkylene, amido arylene, amido cycloalkylene, amido aralkylene, amido fluoroalkylene, amido perfluoroalkylene, amido fluoroarylene, amido 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 radicals. By "divalent radical" is meant a radical that has at each terminal end a bond to another non-hydrogen atom. Accordingly, "alkylene" is used herein as indicating such terminal bonds rather than as indicating that the linking radical, -L-, includes a C=C bond. By "amino" is meant a divalent radical that includes -NH- as well as the linking carbon atoms. By "amido" is meant a divalent radical that includes -NHC(O)- as well as the linking carbon atoms. By "keto" is meant a divalent radical that includes -C(0)- as well as the linking carbon atoms. The 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. The arylene, fluoroarylene, perfluoroarylene and arylene ether groups and their amino, amido and keto equivalents preferably contain 1 to 3 C ₆ rings which may be substituted. The cycloalkylene group and its amino, amido and keto equivalents preferably contains 3 to 10 carbon atoms. The aralkylene, fluoroalkylene, 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 -0-CH ₂ - and (-CF ₂ -) _n , respectively, wherein n is 1 to 15, preferably 3.

It has been found that if a 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 particular reactive group depends in part upon the base polymer which is to be modified. In addition, the reactive radical should be selected so that the by-products of the copolymerization are inert in the sense that they do not degrade the resulting copolymer. Suitable ^ reactive radicals include epoxy, CH ₂ - CH -;

" o'

isocyanate radicals, 0 = C = N - ;

blocked or substituted isocyanate, B - C - NH -

II

0 wherein B is caprolactam, phenol, ketoxime or a pyrazole;

carbodiimide, R ₅ - N = C = N - Rj - , wherein R ₅ is a C _x to C ₅ alkyl or an aryl group;

anhydride, R ₆

0 = C C = 0

"V _• ^** 0 wherein R^ is a polyalkylene or substituted polyalkylene radical, preferably dimethylene, CH - CH -

and caprolactim ether, N = C - 0 -

H _ __X i l

H ₂ __ __I_2

CH ₂

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. The following polydiorganosiloxane carriers

(without the bonded functional moiety) are especially preferred:

A, B and C are commercially available and D and E could be obtained via conventional organic synthesis techniques. As described above, 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 effective molecular weight of each repeating unit is controlled based upon the respective mole percents of the reactants used to produce the polydiorganosiloxane. In other words, 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. For example, 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 comprising hydrosilylation and hydrolysis/condensation. The hydrosilylation step serves to attach the functional moiety (X or FUNCTIONAL) or reactive radicals, R ₂ , to the silicon atom and the hydrolysis/condensation step serves to form the polydiorganosiloxane backbone chain. The hydrosilylation can be performed before or after the hydrolysis/condensation, but it is preferred to perform the hydrosilylation after hydrolysis/condensation. Conventional hydrosilylation techniques are described in Chojo et al., 186 Macro. Chem.. pp. 1203, 1211 (1985); Chojo et al., 19 Polymer Bulletin, p. 613 (1988); Crivello et al. , 28 Journal of Polymer Science. Part A: Polymer Chemistry, p. 479 (1990) ; Crivello et al., 30 Journal of Polymer Science. Part A: Polymer Chemistry, pp. 1-11 (1992); U.S. Pat. No. 4,467,082; Speier, 17 Advanced Organometal Chemistry, p. 407 (1979); and Ojima et al., Reviews on Silicon. Germanium. Tin, and Lead Compounds. Vol. 5, No. 1, pp. 7-66 (1981) . In general, a Ri-hydrogen siloxane unit,

Ri - Si - 0 - H or R,-hydrogen silane unit, R _x

- Si - H is dissolved in dry tetrahydrofuran (THF) and 10 ^"6 M of catalyst (based on siloxane or silane content) is also added. A C=C bond-containing reactant, preferably a vinyl-containing reactant, is dissolved in dry THF in molar proportions based on siloxane or silane content and added dropwise to the siloxane or silane solution, with constant stirring under an inert nitrogen atmosphere. Once addition is complete, stirring is continued at room temperature for two hours. The solution then is heated to a gentle reflux for an

additional 2-30 hours (depending upon the double bond- containing reactant) until disappearance of the Si-H bond as determined by infra-red spectroscopy. The solvent then is removed to obtain the product. It should be recognized that a dihydric siloxane or silane unit also could be used, thus permitting the addition of two C=C bond-containing reactants to one silicon atom.

It is apparent from the hydrosilylation reactive scheme that in order for the reaction with the siloxane or silane monomer to be effected the various functional additives described above should (1) be modified to include at least one unsaturated bond in a reactive position or (2) be able to react with a C=C bond- containing precursor that has undergone hydrosilylation so that the precursor has become a pendant group on the polydiorganosiloxane backbone chain.

This modification of the functional additives can be accomplished based on conventional organic synthesis as shown, for example, in Allen and Gates, Organic Synthesis. Vol. 3, pp. 418-421; U.S. Pat. No. 4,467,082; and U.S. Pat. No. 4,278,804, all incorporated herein by reference. This modified portion of the functional additive is the precursor of the linking group L. Preferably, the functional additive is modified by reacting a functional moiety- containing compound with a vinyl-containing compound, CH^CH-W-Y, where W is optional and is an alkyl, aryl or aralkyl and Y is any radical capable of reacting with the functional moiety-containing compound. If W is present it preferably is an alkyl containing 1 to 6 carbon atoms, preferably 1, or an alkyl phenylene containing 1 to 6 carbon atoms in addition to the 6 aromatic carbon atoms. Illustrative of possible radicals for Y include isocyanato, glycidyl ether, halogen, hydroxy, carboxyl, amino and mercapto. The modified functional additive, therefore, preferably

will have a structure of CH ₂ =CH- (CH ₂ ) _n -Y-X, where X is the functional moiety and n is 1 to 6.

Alternatively, the functional additive itself does not have to be modified but can be reacted with a pendant group already attached to the polydiorganosiloxane backbone. In this case, the siloxane unit is reacted with a precursor having a structure of CH ₂ =CH-W-Y, where W and Y are the same as identified previously, to produce a siloxane of the structure CH ₃

-(-Si-0-)-

CH ₂ -CH ₂ -W-Y. 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.

The synthesis of a modified UV light stabilizer, a modified hydrophilic group and a modified reactive group are described below.

Synthesis of 4-allyloxy-2-hydroxy-benzophenone UV light stabilizer:

In a dry 1000 ml round bottom flask the following materials were mixed: 107.0 g (0.05 mol) of 2,4- dihydroxybenzophenone (available f om Aldrich) , 60.5 g (0.05 mol) of allyl bromide (available from Aldrich), 68.1 g (0.05 mol) of anhydrous potassium carbonate (available from Aldrich), and 300 ml of dry acetone. The solution was refluxed 24 hours under dry nitrogen. The resulting solution was filtered and the filtrate poured into a 1000 ml separatory funnel. To the funnel 150 ml of water was added and the solution consecutively extracted with 150 ml CHjClj; 150 ml CHC1 ₂ ; and 90 ml CH ₂ C1. The organic layers were

combined and dried over anhydrous magnesium sulfate. The solution was filtered and the solvent from the filtrate was removed under reduced pressure. The product was recrystallized from hexane and dried. The final product, 4-allyloxy-2-hydroxybenzophenone

(hereinafter referred to as "RT2") consisted of yellow crystals having a melting point of (68-70 °C) and a yield of 70%.

Synthesis of a modified poly ethylene glycol methyl ether hydrophilic group:

In a dry 100 ml three-necked, round bottom, flask the following materials were mixed, 27.6 g (0.05 mol) of poly ethylene glycol methyl ether of molecular weight of 550 g/mol ("MPEG") (available from Aldrich) , 4.17g (0.05 mol) of allyl isocyanate (available from Aldrich) , and 4 drops of dibutyltin dilaurate catalyst (available from Atochem) . This reaction is exothermic and there is a corresponding increase (appr. 25 °C) in the temperature of the solution. The solution was stirred at room temperature for three hours. An infrared analysis did not show an isocyanate band at 2264 cm' ¹ , indicating that the reaction had gone to completion. The final product was a clear, slightly viscous liquid. It weighed 30.0 g and was produced in 94.8 % yield. This product is referred to hereinafter as ⁿ RT7".

Synthesis of reactant RT8:

In 1 dry, 100 ml 3 neck, round bottom flask the following materials were mixed, 5.66 g (0.05 mol) of caprolactam (available from AliiedSignal) , and 4.l7g (0.05 mol) of allyl isocyanate (available from

Aldrich) . The solid caprolactam readily dissolved into the allyl isocyanate to yield a clear slightly viscous

solution. The solution was refluxed for 1 hour. It became a transparent biege color and remained slightly viscous. After an hour of reflux the reaction had gone to completion, and was confirmed by infrared by the disappearance of the isocyanate band at 2200 cm" ¹ . The final product weighed 8.6g, giving a percentage yield of 87.50% and is designated hereinafter as "RT8".

If the hydrosilylation is carried out first, a silane unit is used as the starting reactant and has a preferred structure of:

. ^*

A - Si - A i H wherein A is a halogen such as chloride, a carboxy such as acetoxy, a hydroxy or an alkoxy. The silane unit could also be dihydric. When this silane unit undergoes hydrosilylation the hydrogen is replaced by the C=C bond-containing functional moiety or reactive group to form a structure of

- R,

A - Si - A

L

R ₂ or

A -

I

X

These silane units then undergo hydrolysis/condensation to form the functionalized polydiorganosiloxane as shown below for a typical functionalized polydiorganosiloxane:

R.

(R _j ) ₃ SiA + A- Si -A + A- Si -A + A- Si -A + ASKRj ) ;, i i i

R, LL L L ii li

R ₂ X

In general, the individual silane reactants are dissolved in toluene or THF so that all the reactants together constitute about 30% by weight of the solution. Water is added and the solution is stirred for 2-6 hours at room temperature and at 60-70°C for another 2-6 hours. The amount of water added can vary depending upon the functionalities present and the rates of condensation desired. The solution is then cooled, and the solvent removed under reduced pressure and the resulting siloxane is isolated. This hydrolysis/condensation synthesis is described in Noll, W. , Chemistry and Technology of Silicones, pub. by Academic Press (1968) .

If the hydrosilylation is performed second, a mixture of

R.

is hydrolyzed/condensed following the above-described procedure to form a polydiorganosiloxane having a structure of

Ri (Rι) ₃ SiO -(-Si0-) _n - SKR^ H The polymethyl hydrogen siloxane species of this structure is referred to hereinafter as "RTl". This polydiorganosiloxane then undergoes hydrosilylation to attach the -L-X and -L-Rj groups to the silicon atoms. The preparation of specific functionalized polydiorganosiloxanes is described below. These functionalized polydiorganosiloxanes are examples only

and other functionalized polydiorganosiloxanes can be prepared by similar methods.

Example 1 - Reactive polydiorganosiloxane with UV Stabilizer

In a 1000 ml, 3-necked, dry, round bottomed flask was weighed 34.826 g of a polymethyl hydrogen methyl octyl siloxane (hydride equivalent = 232 molecular weight) (designated as "RTl") to which was added 650 ml dry THF. 0.03 g H ₂ PtCl ₆ x HjO was added to the siloxane/THF mixture. The solution was stirred and the flask was fitted with a nitrogen inlet, a condenser and an addition funnel. The addition funnel contained 19.071 g allyloxybenzophenone (designated as "RT2") , 8.058 g allylphenyl ether (designated "RT4") , 1.717 g allylglycidyl ether (designated "RT3") and 50 ml dry THF. In this instance, RT4 serves as a diluent. The solution in the addition funnel was added dropwise at room temperature. Once addition was complete, the reaction was heated slowly until a gentle reflux was obtained. The reaction was allowed to proceed for 16 hours. Completion of the reaction was indicated by infra-red analysis of the disappearance of the Si-H band at 2250 cm ^"1 . The THF was removed using a rotary evaporator leaving a yellow, viscous liquid (designated "Example 1" above) . The reaction scheme is set forth below:

( RT2 )

₂ P 1 C I ₆ / T HF

( 0- ).

( )'5

( EXAMPLE 1 )

Example 2 - Reactive Polydiorganosiloxane with Antistatic Agent Moiety

In a 500 ml, 3-necked, dry, round bottomed flask was weighed 6.0 g polymethylhydrosiloxane (hydride equivalent = 60, n is 35) (available from Petrarch Systems) (designated "RTl") to which was added 100 ml dry THF. The flask was fitted with a nitrogen inlet, a condenser and an addition funnel. The addition funnel contained 27.6 g chloromethyl styrene (designated "RT5"), 2.4 g allylglycidyl ether (designated "RT3"), 100 ml dry THF and 0.03 g H ₂ PtCl ₆ .

The solution in the addition funnel was added dropwise at room temperature with constant stirring. Once addition was complete, the reaction mixture was warmed to a gentle reflux. Refluxing was continued for 16 hours and the mixture was cooled. Completion of the reaction was indicated by infra-red analysis of the disappearance of the Si-H band at 2250 cm ^"1 .

A solution of 50 g of N,N-dimethylbenzylamine (designated "RT6") in 50 ml dry THF was added dropwise to the cooled solution with constant stirring at room temperature via an addition funnel. Once addition was complete, the mixture was stirred at room temperature for 2 hours and subsequently heated to a gentle reflux for an additional 16 hours. The solution was cooled and filtered. The residue was washed with THF and dried to give 49.0 g of a pale yellow solid (designated "Example 2" above) . The reaction scheme is set forth below:

(RT1

(RT3)

H ₂ PtC I _β /THF /70 ^β C

( EXAMPL E 2 )

E 26

This reactive scheme is an example of where the functional additive (RT6) is not modified prior to hydrosilylation, but instead reacts with the repeating units derived from the chloromethyl styrene (RT5) . In this instance, the linking radical is an aralkylene, specifically, - (CH ₂ ) ₂ -C ₆ H ₄ -CH ₂ - .

Example 3 - Polydiorganosiloxane with UV Stabilizer Moiety

In a dry 1000 ml round bottom flask the following materials were mixed; 21.0 g (0.35 mol) of the polymethylhydrosiloxane of Example 2 (RTl), 0.01 g of Wilkinson's catalyst (available from Aldrich) , 2 drops of platinum-divinyltetramethyldisiloxane catalyst

(available from Huls) , and 200 ml of anhydrous THF. In a dry 250 ml addition funnel the following materials were mixed; 89.9 g (0.35 mol) of 4-allyloxy-2-hydroxy¬ benzophenone (RT2) , and 220 ml of anhydrous THF. The solution from the addition funnel was added dropwise with constant stirring. The solution was yellow and opaque after the addition was complete. The mixture was then refluxed for 20 hours after which an infrared spectrum was taken. The infrared spectrum did not show a band for Si-H at 2160 cm ^"1 . Norit carbon (available from Aldrich) was added to remove impurities. The solution was filtered through a thin bed of Celite ^® (a diatomaceous earth product available from Aldrich) . The solvent in the filtrate was removed under reduced pressure. The resulting product was a yellow, viscous liquid that weighed 44.0 g. This product is designated "Example 3" and is an example of polydiorganosiloxane of formula C, described hereinafter. The reaction scheme is set forth below:

C RT2 _ι

C EXA MPLE 3)

Example 4 - Reactive Polydiorganosiloxane with UV Stabilizer Moiety

In a dry, 1000 ml, three-necked, round bottom flask, the following materials were mixed; 6.0g of the polymethylhydrosiloxane of Example 2 (RTl) , 30 ml of anhydrous THF, and 0.06g of Wilkinson's catalyst

(available from Aldrich) . In a dry 250 ml addition funnel the following compounds were added; 18g (0.26 mol) 4-allyloxy-2-hydroxy-benzophenone (RT2) , 3.5g (0.016 mol) allyl glycidyl ether (RT3) , and 60 ml of anhydrous THF. The solution from the addition funnel was added dropwise to the flask over 30 minutes with

constant stirring. This yielded a bright yellow and clear solution. The solution was stirred and refluxed under a dry nitrogen atmosphere. The progress of the reaction was monitored using Fourier Transform infrared spectroscopy ("FTIR"). The Si-H bond has a strong absorption at 2164 cm ^"1 . The solution was refluxed for 48 hours. 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 - Reactive Polydiorganosiloxane which includes two functional moieties

Synthesis of Polydiorganosiloxane:

In a dry 1000 ml, 3 neck, round bottom flask the following materials were mixed: 21.9g (0.37 mol) of the polymethylhydrosiloxane of Example 2 (RTl) , 5 drops of

platinum-divinyltetramethyldisiloxane catalyst (available from Huls) , and 150 ml of anhydrous THF. In a 500 ml addition funnel the following materials were mixed: 12.6 g (0.02 mol) of RT7, 9.0 g (0.05 mol) of RT8, 76.2 g (0.35 mol) of RT2, and 200 ml of anhydrous THF. The solution from the addition funnel was added dropwise to the round bottom flask mixture over 1 hour at room temperature with constant stirring. This solution was golden yellow, and non-viscous. The solution then was heated to gentle reflux for 24 hours. Infrared analysis did not have the Si-H band at 2164cm" ¹ indicating that the reaction has gone to completion. Norit carbon was added and the solution warmed slightly. The solution was filtered through a bed of Celite ^® and the solvent was removed under reduced pressure. The final product weighed 101.3 g. It was a viscous, dark yellow/brown liquid. This product is designated "Example 5". The reaction scheme is set forth below:

H

0 CH _j

( EXAMPLE 5)

In 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.

The incorporation of the functionalized 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 characteristics. 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. Particularly suitable terminal or pendant groups include carboxyl, amino and hydroxy groups. Types of 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 _j , 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. In other words, 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. According to formula B, R represents the bonding structure which forms as a result of the copolymerization. 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. Illustrative of 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:

o

HOOC-Ny-NH- (-CHj-CH-L-) ₂ \ OH

H ₂ N-Ny-COOH + HjC-CH-L- -» HzN-Ny-C-O-CH _j -CH-L-

\ / \\ \

0 0 OH

R ₂ is an isocyanate group:

H _j N-Ny-COOH + 0=C=N-L- -» HOOC-Ny-NH-C-NH-L-

II O

H _j N-Ny-COOH + 0=C=N-L- -» H^-Ny-C-O-C-NH-L-

II ii 0 0

H _j N-Ny-C-NH- - ll

0

R ₂ is a blocked isocyanate: H _j N-Ny-COOH + B-C-NH-L- -» HOOC-Ny-NH-C-NH-L- + BH

II (heat) I.

O O

HjN-Ny-COOH + B-C-NH-L- -» HjN- Ny-C-O-C-NH-L- + BH il (heat) n u

O O O heat * (-C0 ₂ )

0

R ₂ is an oxazoline group:

H _j N-Ny-COOH + 0-C-L- - H^-Ny-C-0-CH ₂ --_H ₂ -NH-C-L-

' »- ii w H_C N O 0

CHj

R, is a carbodiimide group:

H ₂ N-Ny-CO0H + R ₄ -N=C=N-L- -> HOOC-Ny-NH-C-NH-L- W

N-R ₄

H-N-Ny-COOH + R ₄ -N=C=N-L- -» HjN-Ny-C-O-C-NH-L- O N-R ₄ heat l

0 R ₄ 0

R ₂ is a succinic anhydride group:

HjN-Ny-COOH + HzC-CH-L- -» HOOC-Ny-NH-C-CH _j -CH-L-

/ \ II I

0=C C=0 O COOH / O

R ₂ is a caprolactim ether group

H _j N-Ny-COOH + N-C-O-CH _j -L- -» H^-Ny-C-O-CH _j -L- + NH-CH^O

/ \ U / \ H _j C .____- H _j C-CH _j

\ / CH _j

As can be seen from above, 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.

In a similar fashion, the carboxyl and hydroxyl terminal group of a polyester, particularly polyethylene terephthalate, will react with the reactive groups to form copolymers. For example, when R ₂ is an epoxy group the following copolymer is formed

(wherein PE represents the repeating monomeric units of polyester) :

H-PE-C-O-CH CH-L- II i 0 OH

Likewise, the hydroxy terminal group of a polyarylate will react with the reactive groups to form copolymers.

For example, when R ₂ is an epoxy group the following copolymer will form (wherein PA represents the repeating monomeric units of polyarylate) :

PA-C ₆ H ₄ -0-CH ₂ -CH-L- OH In the case of polyolefins, 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. For example, 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.

Particularly preferred as the base polymer are the fiber-forming polymers such as polyamide, especially nylon 6 and nylon 66, and polyester, especially PET, PEN and PBT. By enabling the polydiorganosiloxane to be chemically anchored in the base polymer via the bonding occurring at the R--. reactive sites, the advantageous properties conferred by the functional moieties attached to the polydiorganosiloxane carrier are not lost during processing or use of the base polymer.

Typically, the amount of modified 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 polydiorganosiloxane and base polymer.

The functionalized polydiorganosiloxane carrier and the base polymer are reacted together so that 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. It is important to recognize that the linking group, -L-, must be inert during copolymerization of the polydiorganosiloxane and the base polymer. Accordingly, 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. For example, 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.

In the case of melt extrusion, the extrusion temperature 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. The 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. Alternatively, 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. In general, 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. The following examples illustrate the process used to produce the copolymers of the present invention.

Incorporation via Solution

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 polydiorganosiloxane solution. The PET fabrics were analyzed for xenon lightfastness by American Association of Textile Chemists and Colorists ("AATCC") Method 16E (225 kJ light source) graded by Gray Scale. AATCC Method 16E provides an indication of the propensity of a fabric to fade under specified conditions of exposure to UV light. The results are listed in Table 1.

TABLE 1

A comparison between the Gray Scale values for samples A and B and the control sample clearly demonstrates that the functionalized polydiorganosiloxane acts as a carrier for the UV light

stabilizer moiety. In view of the fact that 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.

Copolymerization via Reactive Extrusion- Polyamide Example

Nylon 6 chips can be dry blended with a predetermined amount of at least one liquid functionalized polydiorganosiloxane of the present invention. 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 terminal groups of the nylon 6 chains. To obtain a fiber, 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.

Copolymerization via Reactive Extrusion- Polyester Example

PET chips can be dry blended with a predetermined amount of at least one liquid functionalized polydiorganosiloxane of the present invention. The resultant blend would be dried at 160°C until a moisture content until a moisture content of 0.02% or below is reached and then extruded on a twin screw extruder at 290°C. The extrudate would be pulled into strands, quenched in a water bath, pelletized, and dried at 160°C in a vacuum oven. After this extrusion procedure, the epoxy groups of the functionalized polydiorganosiloxane would have bonded with the carboxylic acid terminal groups of the PET chains. To obtain a fiber, 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.

In addition to the functionalized 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

R, L L

I i I

T- ( - SiO- ) .- ( - SiO- ) _b - ( - SiO- ) _β -T

I I I

R _x R _x L

X ( C)

wherein R _x is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, 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, cycloalkylene, aralkylene, fluoroalkylene, perfluoroalkylene, fluoroarylene, perfluoroarylene, flouroaralkylene, perfluoroaralkylene, alkylene ether, arylene ether, perfluoroalkylene ether and perfluoroaralkyl ether; X is a functional group capable of imparting an end use characteristic to the base polymer; T is (R jSiO-; a is 0 to 1000; b and c are each 0 to 20, provided that b and c are not both 0; and the

units of formula C are arranged in a random or a block structure. A polydiorganosiloxane of formula C can be blended, preferably melt blended, with a

reactive functionalized polydiorganosiloxane and a base polymer. The functional moieties bonded to the polydiorganosiloxane of formula C will impart their end use characteristics to the base polymer. For instance, Example 3 can be melt blended with a reactive functionalized polydiorganosiloxane and a polyester or nylon to provide improved fade resistance and breaking strength.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.