GB2445854A - Hydrophilic polymer substrates - Google Patents

Abstract

A method for the preparation of a polymer substrate e.g. polycarbonate, comprises; treating the substrate with SO3 to form a hydrophilic layer, and eliminating contact of the substrate with the sulphur trioxide once the hydrophilic layer has formed. Residual sulphonic acid groups may be neutralised by contacting the substrate with a base. The SO3 can be either liquid or gaseous and can be produced by the oxidation of SO2 in the presence of a catalyst and/or UV radiation. The SO3 may be added in a dry atmosphere in a concentration of 0.5-20 % by volume for a period of 5 seconds - 30 minutes if gaseous or 1 second to 10 minutes if liquid. The sulphonation process can be aided using heat or UV radiation. Prior to contact with the SO3 the polymer substrate may be exposed to organic solvents. A hydrophilic substrate layer is also disclosed, which comprises a polar functional group, especially a sulphonic group, bonded to the polymer.

Description

METHOD OF SULFONATION OF POLYMER SUBSTRATE TO IMPART A

HYDROPHIUC LAYER IN SAID SUBSTRATE WITH IMPROVEMENT IN AT

LEAST ONE OF ANTI-FOG, ANTI-STATIC, WETTABILITY, LUBRICITY AND ANTI-MICROBIAL PROPERTIES, AND ARTiCLES MADE THEREBY This Application claims the benefit of U.S. Provisional Application Serial No. 60/885,O9lfiled January 16, 2007, and U.S. Utility Patent Application Serial No. 11/748,252 filed May 142007, which are both incorporated herein in their entirety.

The present invention is directed to a method for sulfonating polymer substrates to impart a hydrophilic layer in said substrate to impart improvement in at least one of anti-fogging, anti-static, wettability, lubricity and/or anti-microbial properties.

The present invention is further directed to polymer substrates having a hydrophilic layer obtained by sulfonation to impart improvement in at least one of anti-fogging, anti-static, wettability, lubricity and/or anti-microbial properties of such polymer substrates.

The present invention yet further relates to a method of sulfonating clear polymer substrates to impart a hydrophilic layer in said substrate exhibiting improved at least one ofanti-lbgging, anti-static, wettability, lubricityand/or anti-microbial properties without substantially affecting the transparency of said treated polymer substrate.

The present invention further relates to articles made from clear polymer substrates treated with a sulfonation process to impart a hydrophilic layer in said substrate that imparts improvement in at least one of anti-fogging, anti-static, wettabiity, lubricity and/or anti-microbial properties without substantially affecting the transparency of said articles.

Polymer substrates and articles made therefrom commonly exhibit static and fogging properties that affect their usefulness in many applications to which they are used. In addition, under certain conditions, the lubricity and anti-microbial properties of polymers used for medical and packaging uses can be improved to increase their usefulness in medical and packaging fields. Moreover, wettability becomes an issue for many applications and has an effect on many of the properties of the polymer. For example, the phenomenon commonly called fogging is observed widely in various applications of transparent polymer films or sheets. The term fogging describes the condensation of water vapor from air, in the form of discrete water droplets, on a polymer surface. In such situations, light transmitted through polymers that suffer from "fogging" is scattered by the water droplets accumulated on the surface of the polymer, causing the view to be hindered. Polymers are generally non- polar compounds that repel water to a certain degree, according to their surface tension. When affinity of the condensate for the substrate is high, the contact angles between the droplets and the substrate surface are low and very little lbgging occurs. In addition, two other key factors influencing the fogging phenomenon are the level of moisture in the air and the difference in temperature between the air and the polymer part. One route that has been widely used to help minimize fogging is improving the wetting performances of the polymer. Wettable surfaces allow liquid films to form at their surfaces instead of droplets. In this case, the contact angles are very low and the transmittance of light and formation of images are not prevented, Typical anti-fogging additives contain molecules composed of both a hydrophilic part that is attracted by water, and a long hydrophobic part, such as a lipophilic part, adapted to the polymer substrate, such as esters of fatty esters. Another common method employed in combatting fogging is through temporary or permanent coatings. While it has been known that polymers can be sulfonated to have increased anti-static properties, there have been no studies of using sulfonation to obtain anti-fog, wettable transparent layers that have improved anti-static, anti-fogging, anti-microbial, improved wettability and improved lubricity. Moreover, when polymers, in the form of powders, are used in paints or other mixtures they must exhibit some degree of wettability in order to be useful. In some applications such as paints and retarding additives for cements, polymer powders are added and then a substantial amount of surfactant must be added to permit the polymers to be sufficiently wetted to form a useful composition. The improved wettability of the sulfonated powders in the present invention substantially reduces the amount of surfactant in such compositions to impart the same or improved properties.

Patchen, U.S. Patent No. 6,923,997 discloses anti-fogging compositions and methods of using the same. Various compositions for food packaging uses are disclosed.

For example, one composition of the anti-fogging composition is (i) a nonionic surfactant blend comprising a fatty acid ester and an ethoxylated compound and (ii) acetone.

Another example is an anti-fogging nonionic surctant blend comprising a fatty acid ester and an ethoxylated compound and (ii) a solvent selected from methyl acetate, isopropyl alcohol, ethanol, and mixtures thereof. The method of defogging the food packaging surface entails selecting a surfactant, providing (I) an anti-fogging nonionic surfactant blend comprising a fatty ester and an ethoxylated compound and applying the anti-fogging composition to the surface. Another method disclosed comprises selecting a surface, providing an anti-fogging nonionic surfactant blend comprising a fatty acid ester and an ethoxylated compound and (ii) a solvent selected from methyl acetate, isopropyl alcohol, ethanol, and mixtures thereof to fomi an anti-fogging composition, and applying the anti-fogging composition to the surface.

Bates, U.S. Patent No. 6,706,389discloses a packaging film that includes a heat sealable layer coated with one or more anti-fogging agents disposed on a binder; an anti-blocking agent, and no more than about 800 ppm slip agent. The heat sealable layer includes a polymer that includes mer units derived from ethylene while the binder includes a polymer that includes mer units derived from an ester of(meth)acrylic acid and/or vinyl acetate mers. The anti-blocking agent can be in any layer of the film where it provides the desired anti-fogging effect. Such a film, as well as packaging made therefrom, can be used to package a variety of products, having particular utility with respect to most products.

Dixon, U.S. Patent No. 2,272,831 discloses a sulfonation of clearpolystyrene to impart anti-static properties to a surface of a treated substrate without substantially affecting the surface appearance and transparency of the polystyrene substrate. The sulfonation occurs by the exposure of the surface of a polystyrene substrate to concentrated sulfuric acid solutions.

Wailes, U.S. Patent No. 3,959,561 discloses a method for the rapid rendering of transparent polymer articles astatic by treating the articles with gaseous sulfur trioxide (SO3) followed by treatment with a base such as ammonia and water or dilute aqueous ammonia. The articles are rendered pennanently astatic without affecting their Iransparency.

It is thereibre desirable to provide an improved polymer substrate and method of producing such substrate which addresses problems and/or which more generally offers improvements or an alternative to existhig arrangements.

According to the present invention there is therefore provided a method for the preparation of a polymer substrate, and a polymer substrate prepared by the method, as described in the accompanying claims. There is also provided a polymer substrate as further described in the accompanying claims.

In an embodiment of one aspect of the invention there is provided a method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static, wettability, lubricity and/or anti-miciobial properties. The method comprises treating a polymer substrate in a diy atmosphere with a sufficient concentration ofSO3for a sufficient time to form a hydrophilic layer in said substrate, and substantially eliminating contact of said SO3with said substrate when a desired treatment of said polymer substrate has occurred to form a hydiophilic layer with at least one of said improved properties.

In another aspect of an embodiment of the present invention is a hydrophilic polymer substrate layer obtained by sulfonation with the formula: P-x wherein P is a polymer; and X is a polar functional group; wherein said layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettability and/or anti-microbial properties. For purposes of this application, sulfonic groups are included in the definition of polar fimctional groups as used herein.

The layer fbrmed in a polymer according to at least one embodiment of the present invention can be imparted to a wide variety of polymer substrates without affecting transparency of the substrate. Accordingly, the process and articles formed according to the present invention find applicability in any areas such as sunglasses, ski and other protection goggles, such as eye or safety goggles, tail light lenses, head lamp lenses, helmet visors, lenses, contact lenses, transparent polymer covers, lids and fihns.

In addition, the invention finds application in medical arts, because substrates treated according to further embodiments of the present invention can be formed into articles such as catheters, intravenous bags, tubing, contact lenses, and valves to be implanted in the body; the articles formed with a hydrophilic layer obtained by sulfonation according to the present invention exhibit at least one of improved lubricity, wettability and anti-microbial properties.

Embodiment s of the present invention may be utilized to fbrni polymer pellets and powders that can be used to create other polymer substrates that have the hydrophilic layer obtained by sulfonation infused throughout. In addition, a polymer powder such as an acrylic powder, with a hydrophilic layer obtained by sulfonation can be used in paints or concrete retarding compositions. The improved wettability exhibited by such treated polymer powders can substantially reduce the amount of surfactants in such paints or concrete retanier solutions.

These and other aspects of the invention will become apparent upon a reading

of the following specification and examples.

One aspect, the present invention is a method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static wettability, lubricity and anti-microbial properties. The invention includes treating a polymer substrate with a sufficient concentration of SO3 for a sufficient time to form a hydrophilic layer in said substrate and substantially eliminating contact of said SO3 with said substrate when a desired treatment of said polymer substmte has occurred to form a hydrophilic layer with at least one of said improved properties.

The sulfonation of the polymer substrate may be conducted in a batch or continuous process. In this regard, reference is made to pending US Patent Application No, 11/672,332 entitled "Method of Sulfonating an Article andRelated Apparatus" filed February 7,2007, assigned to the assignee of this application and incorporated herein by reference in its entirety. Specifically, in a batch process, a sulfonating chamber is provided wherein a polymer substrate is placed. Noble gasses such as argon or nitrogen, or dry air are used to purge the chamber and the polymer substrate in order to reduce moisture in the chamber. A sulfonating source, which may be gaseous or liquid, is introduced to the chamber and the substrate therein. The sulibnating source is preferably S03,and may be produced by the oxidation of SO2in the presence of at least one catalyst, such as, but not limited to V5O2and/or ultraviolet (UV) radiation. Sulfonation reagents also include: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, trimethylsilyl sulfonyl chloride, sodium bisulfute pymlysis, commercially available SO3 and mixtures thereof. If in gaseous form, the SO3is introduced to said substrate in an amount of from about 0.5% by volume to about 20% by volume fora time period of about 5 seconds to about 30 minutes to form said hydrophilic layer. If in a liquid form, the SO3 is introduced to the polymer substrate for a time period of from about Isecond to about 10 minutes to form said hydrophilic layer. The reaction may proceed at ambient temperature and pressure. If desired, sufficient heat or UV radiation can be introduced to aid the sulfonation process to form a hydrophilic layer in said substrate. In this regard, it is contemplated that the temperature could range up to the glass transition temperature of the polymer substrate.

In order to improve the treatment of the polymersubstrate, the polymer substrate maybe exposed to organic solvents prior to sulfonation to enable more facile contact and reaction between the substrate and the SO3 to permit the hydrophilic layer to be imparted further into said polymer substrate. Examples of solvents can include, but are not limited to, acetone, hexanes and dichioromethane, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.

The method may further include neutralizing the treated by sulfonation polymer substrate with a base to neutralize any residual sulfomc acid groups or other protic species. A suitable base may be selected from the group consisting of alanine, ammonia, dimethylamine, ethylarnine, glycine, hydrazine, methylamine, triethylamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates and diacid phosphates, metal citrates, metal acetates, metal ascorbates, derivates thereof, and mixtures thereof.

Although the advantages of the methods and articles of the present invention are not related to any particular theory, it is hypothesized that during sulfonation, hydrogen atoms and derivatives thereof which are bonded to carbon atoms in the hydrocarbons are replaced by sulfonic acid groups, where they become bonded and form a barrier layer. It may be that the hydrophilic polymer substrate layer obtained by sulfonation can be expressed by the formula: P-x wherein P is a polymer; and X is a polar functional group; wherein the layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettability and/or anti-microbial properties. For purposes of this application, sulfonic groups are included in the definition of polar functional groups as used herein.

The bonds of the new layer material are nre polar, and therefore, are less likely to allow penneation of hydrocarbons. In one variation, this advantage is realized byusing polymeric materials which are sulfonatable by the methods of the present invention.

Suitable polymers for sulfonation may be selected from the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylmethaciylates, derivatives of alkyl methaciylates, polyamides, polyimides, polyamido ethers, amido copolymers, polyimidoethers, imido copolymers, derivatives of imido copolymers, cellulosics, derivatives of cellulosics, polysulfones, derivatives of polysulfones, polyesters, copolymers of polyesters, allyl diglycol caibamates, polystyrenes, It is contemplated that the above described method can be used to impart a hydrophilic layer obtained by sulfonation to articles such as catheters, intravenous bags, tubing, contact lenses, and valves to impart improvement in at least one of lubricity and anti-microbial pmperties to said treated articles.

This method can also be used to impart a hydrephilic layer obtained by sulfonation to articles such as CDs, DVDs, High Definition DVDs, safety goggles, eyeglasses, sunglasses, ski glasses, and other optical media, packaging, contact lenses, automotive head lamp lenses, instrument panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart improvement in at least one of anti-static and anti-fogging properties to said articles.

Moreover, the method can be used to impart a hydrophilic layer obtained by sulfonation to polymer pellets and powders to impart at least improved wettability. When the powders are acrylic powders used in paints, the use of treated powders substantially reduces the use of surfactants in said paint. In addition the use of treated acrylic powders as concrete retarders substantially reduces the amount of surfactants used in concrete applications, such as oil well applications. When the polymer pellets are treated by sulfonation and subsequently fonned into articles, the hydrophilic layer is disbursed throughout the formed polymer substrate.

Objects and advantages of this invention are further illustrated by the following examples. The particular materials and amounts thereof, as well as other conditions and details, recited in these examples should not be used to limit this invention.

EXAMPLES

Polycarbonate substrates were treated utilizing SO3 created from a 20% by volume SO2 feedstock for 30 seconds in dry air up to about 10 minutes at 2% by volume SO2feedstock in dry air. The sulfonation chamber was purged with dry air before, between and after the sulfonation steps. The samples were neutralized by rinsing in water, in situ neutralization or with neutralization agents consisting of diluted solutions of weak basic reagents (salts of weak inorganic and organic acids, such as sodium bicarbonate, sodium citrate, sodium acetate) stronger bases such as group I metal hydroxides, ammonia, ammonia water. The samples were tested to determine the anti-ibg, wettabiity, anti-static and visual properties of the polymer substrate with ahydrophilic layerobtained by sulfonation. In order to determine anti-fogging properties, the hydrophilic layer obtained by sulfonation was subjected to fogging by a "hot fog or breath test" and the contact angle of the individual drops of condensed water were measured. The wettability was measured by the formation of water sheets rather than beading when water was applied to the samples. Anti-static was determined by visual inspection to determine whether treated samples attracted dust. Visual properties were determined by visual inspection of the samples after different periods of time or different treatments. All percents are by volume. The results are set forth in the following table.

TABLE 1

Contact Angle Measurements on Pure Polycarbonate (PC) Samples (All pH values measured at surface of sample) Sample Sul1nation Neutrahzation TreatiTest visual Ant-1bg Contt Properties Angles ________ _________ _______ _____ _______ (Avg) Pure PC N/A N/A pH 7.0 Clear None/fog 73.5 in <1 mm 01 3 mm 5% N/A; 1 wk @ Clear Initially 45.6 SO2 water rinse 95 C in w/tiny good poor feedstock in only oven; pH pits after oven dry air 7.0 before oven; loss of Iranspa rency after oven Sample Sulfonation Neutralization Treat/Test visual Anti-fbg Contact ?tope*ties Angles _____ ________ _________ _______ _____ _______ (Avg.) 02 3 mm, 5% N/A; N/A Clear Good> 30.6 vol, SO2 water rinse w/tiny 60s hot feedstock in only pits fog test ___ dryair _____ ____ ___ ____ ___ 03 6 miii, 5% 0.IM sodium N/A Clear Excellent 5*40 SO2, acetate 10 wltuny > 60s hot feedstock in mm, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 04 6 mm, 5% 0.1 M sodium N/A Clear Excellent 8.0 SO2 acetate 60 w/tiny > 60s hot feedstock in mm, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 6 mm, 5% 0.1 M sodium N/A Clear Excellent 5.0 SO2 acetate 10 w/tiny > 60s hot feedstock in mm, Ambient pits fog test ______ diy air Temp ________ ______ ________ ______ 06 6 mm, 5% 0.IM sodium N/A Clear Excellent 7.0 SO2 acetate 60 w/tiny > 60s hot feedstock in miii, Ambient pits lbg test ______ dry air Temp ________ ______ _________ ______ 07 5.5 miii, 2% 0.1M sodium N/A Clear Good> 30.9 SO2 acetate 10 w/tiny 60s hot feedstock in miii, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 08 5.5 miii, 2% 0.1M sodium N/A Clear Good> 3 1.8 SO2 acetate 10 w/tuny 60s hot feedstock in mm, Ambient pits lbg test _____ dry air Temp _______ _____ _______ _____ 09 5 mm, 2% 0. IM sodium N/A Clear, Good> 11.1 SO2 acetate 10 no pits, 60s hot feedstock in mm, Ambient haze or fog test _____ thy air Temp _______ spots _______ _____ 10 mm, 2% 0.1 M sodium N/A haze Good> 7.9 SO2 acetate 10 60s hot feedstock in miii, Ambient fog test _____ dry air Temp _______ _____ _______ _____ Sample Sulfonation Neutralization Treat/Test visual Anti-tbg Contact Pmpethes An ______ ________ _________ _______ _____ _______ (Avg) 11 30s, 20% 0. 1M sodium 1 wk @ Clear, Good> 24.7 SO2 acetate 10 95 C in no pits 60s hot feedstock in mm, Ambient closed haze or fog test dry air Temp cont. pH spots 7.0 _________ ______ 12 3x20s, 13% 0.1M sodiwn 1 wk @ Clear, Very 8.0 SO2 acetate 10 95 C in no pits Good> feedstock in mm, Ambient closed haze or 60s hot dry air Temp cont. pH spots lbg test 7.0 ______ 13 3xlOs, 13% 0.IM sodium I wk @ Clear, Good 29.5 SO2 acetate 10 95 C in no pits feedstock in mm, Ambient closed haze or dry air Temp cont. pH spots 7.0 ______ 14 3x20s, 13% 0.1M 1 wk@ Clear, Good 18.8 SO2 bicarbonate 95 C in no pits feedstock in sol. I mm, closed haze or dry air Ambient cont. pH spots ______ __________ Temp 7.0 15 3mm, 5% 0.1M 1 wk @ Clear, Good 16.5 SO2 bicarbonate 95 C in no pits feedstock in sol. 6 mm, closed haze or dry air Ambient cont. pH spots ______ __________ Temp 7.0 16 2mm, 5% 0.1M N/A Clear, Increased, 34.1 SO2 bicarbonate no pits but not feedstock in sol. 10 mm, haze or excellent dry air Ambient spots _____ ________ Temp _______ _____ _______ _____ 17 imili, 13% 0.1M N/A Clear, Good 3 1.0 SO2 bicarbonate no pits feedstock in sol. 10 mm haze or dry air Ambient spots ______ _________ Temp _______ ______ _______ _____ Sample Sulfonation Neutralization Treat/Test viaual Anti-fbg Contact Properties Angles * .. . ________ ______... .. (Avg.) 18 4 miii, 2% 0.1M N/A Clear, Increased, 34.6 SO2 bicarbonate no pits but not feedstock in sol. 10 mm, haze or excellent dry air Ambient spots ______ ________ Temp _______ _____ _______ _____ 19 5 miii, 2% 0.1M N/A Clear, excellent 2-4 SO2 bicarbonate wlsligh feedstock in sol. 10 mm t dry air Ambient hazing Temp in some _____ ________ _________ _______ spots _______ _____ 4 mm, 2% 0.1M Water Clear Increased, N/A SO2 bicarbonate soak for 1 no pits, but not feedstock in sol. 10 mm, week @ haze or excellent dry air Ambient Ambient spots Temp temp. before! after Uv 21 4 mm, 2% 0.1M UV Clear Increased, N/A SO2 bicarbonate exposure no pits. but not feedstock in sol. 10 miii, outdoors A little excellent dry air Ambient (no rain, haze in Temp sunny spots weather, before/ I range after between water ________ ___________ _____________ 40-75 F) test As can be seen by reference to Table 1, surface hydrophilicity increased dramatically for polyvarbonate samples upon sulfonation. Polycarbonate samples treated by sulfonation can have contact angles that approach 0 while untreated samples have contact angles over 70 .

The breath test, hot ibg test, and wettability test show the formation of water sheets instead of beading and constitute additional evidence for increased h1rophilicity and anti-fog properties of polycarbonates treated by sulfonation. Moreover, it was observed that dust and other electrostatically charged particles did not accumulate on polycarbonate surfaces treated by sulfonation as they do on untreated polycarbonate surtces. Durability of the hydrophilic layer obtained by sulfonation was also demonstrated. Exposure ofpolycarbonate samples treated bysulfonation to heat in closed or open containers for up to a week did not deteriorate the visual aspect or decrease the anti-fog properties of samples treated by sulfonation if rinsed with a neutralizing solution after sulfonation. Exposure to outdoor UV light for 6 days did not lead to a decrease in anti-fog properties as assessed by wettability, hot fog and breath test. Finally, soaking in water at ambient temperature for 6 da did not lead to a decrease in anti-fog properties, as assessed by wettability, hot fog and breath tests.

While embodiments of the invention have been described and illustrated, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description, not words of limitation. It is understood that various changes and modification may be made without departing from the scope of the invention as set forth in the appended claims.

Claims (35)

1. A method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static wettability, lubricity and/or anti-microbial properties, the method comprising: treating a polymer substrate witha sufficient concentration of SO3for a sufficient time to form a hydrophilic layer in said substrate; substantially eliminating contact of said SO3 with said substrate when a desired treatment of said polymer substrate has occurred to form a hydrophilic layer with at least one of said improved properties.

2. The method of claim 1, further including neutralizing saidpolymer substrate with a base to neutralize any residual sulfonic acid groups and other protic species.

3. The method of claim 2, wherein said base is selected from the group consisting of alanine, ammonia, dimethylamine, ethylamine, glycine, hydrazine, methylamine, triethylainine, lithium hydroxide, sodium hydroxide, potassium hydroxide, mbidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates and diacid phosphates, metal citrates, metal acetates, metal ascorbates, derivates thereof, and mixtures thereof.

4. The method of any preceding claim, wherein said polymer substrate is substantially clear, said polymer selected fim the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylinethacrylates, derivatives of alkyl methaciylates, polyamides, polyimides, polyarrndo ethers, amido copolymers, polyimidoethers, imido copolymers, derivatives of imido copolymers, cellulosics, derivatives of cellulosics, polysulfones, derivatives of polysulfones, polyesters, copolymers of polyesters, allyl diglycol carbamates, polystyienes, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.

5. The method of any preceding claim, wherein said SO3is gaseous or liquid,

6. The method of any preceding claim, wherein the sulfonation occurs in a dry atmosphere with suflicient SO3 to form a hydrophilic layer in the substrate,

7. The method of any preceding claim, wherein said SO3is produced by oxidation of SO2in the presence of at least one catalyst and/or UV radiation.

8. The method of any of claims 1 to 6, wherein said SO3is produced from a sulfonation reagent comprising: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, Irimethylsilyl sulfonyl chloride, sodium bisulMepyrolysis, commercially available SO3, and/or mixtures thereof.

9. The method of any preceding claim, wherein said SO3is introduced to said substrate in an amount of from about 0.5% by volume to about 20 % by volume.

10. The method of any preceding claim, wherein said substrate is exposed to gaseous SO3for a time period of about 5 seconds to about 30 minutes to form said hydrophilic layer.

11 The method of any preceding claim, wherein said substrate is exposed to liquid SO3for a time period of from about 1 second to about 10 minutes to form said hydrophilic layer.

12. The method of any preceding claim, further including using sufficient heat or UV radiation to aid said sulfonation process to form a hydrophilic layer in said substrate.

13. The method of any preceding claim, further including the step of exposing the polymer substrate to organic solvents prior to sulfonation to enable more facile contact and reaction between the substrate and the SO3 to permit the hydrophilic layer to be imparted further into said polymer substrate.

14. The method of any preceding claim, wherein said hydrophilic layer obtained by sulfonation is imparted to articles such as any one of catheters, intravenous bags, tubing, contact lenses, and valves to impart improvement in at least one of lubricity and antimicrobial properties to said treated articles.

15. The method of any preceding claim, wherein said hydrophilic sulfonated layer is imparted to articles such as any one of CDs, DVDs, High Definition DVDs, safety goggles, eyeglasses, sunglasses, ski glasses, and other optical media, packaging, contact lenses automotive head lamp lenses, instrument panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart improvnent in at least one of anti-static and anti-fogging properties to said articles.

16. The method of any preceding claim, wherein said hydrophilic layer obtained by sulfonation is imparted to polymer pellets and powders to impart at least improved wettability.

17. The method of claim 16, wherein said powders are acrylic powders used in paints; said treated powders substantially reducing use of surfactants in paint.

18. The method of claim 16, wherein said powder is acrylic powder used as a retarder in concrete to substantially reduce the use of surfactants in said concrete.

19. The method of any preceding claim, wherein said preparation may be batch or continuous.

20. A hydrophilic polymer substrate layer with the formula: P-x wherein P is a polymer; and X is any polar functional group wherein said layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettabiity and/or anti-microbial properties.

21. The hydrophilic polymer substrate layer of claim 20, wherein X is a sulfonic group.

22. The hydrophilic polymer substrate layer of claim 2Oor 21, wherein sulfonation of said substrate layer occurs in the presence of heat or (iv radiation.

23. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 22, wherein said polymer substrate is selected from the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylniethaciylates, derivatives of alkyl methactylates, polyarnides, polyimides, polyamidoethers, amido copolymers, potyimidoethers, imido copolymers, derivatives ofimido copolymers, cellulosics, derivatives ofcellulosics, polysulfones, derivative ofpolysulfones, polyesters, copolymers of polyesters, ally! diglycolcarbamates, polystyrenes, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.

24. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 23, wherein said treated polymer substrate layer is further treated with a base to neutralize any residual sulfonic acid groups and/or other protic species.

25. The.hydrophil Ic polymer substrate layer obtained by sulfonation of claim 24, said base selected from the group consisting of alanine, ammonia, dimethyl amine, ethylamine, glycine, hydrazine, methylamine, triethylamine; lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates, and diacid phosphates, metal citrates, metal acetates, metal ascorbates, and mixtures thereof.

26. The hydrophilic polymer substmte layer obtained bysulfonation of anyof claims to 25, wherein said SO3 is produced by oxidation of SO2 in the presence of at least one catalyst and/or UV radiation.

27. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 25, wherein said SO3 is produced from a sulfonation reagent comprising: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, trimethylsilyl sulfonyl chlOride, sodium bisulfate pyrolysis, commercially available SO3, and/or mixtures thereof.

28. The hydrophilic polymer subslmte layer obtained bysulfonation of anyof claims to 27, wherein said layer is imparted to articles such as catheters, intravenous bags, contact lenses and valves to impart improved at least one of lubricity, anti-fogging, and anti-microbial properties to said articles.

29. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 28, wherein said layer is imparted to articles such as CDs, DVDs, High Definition DVDs, and optical media to impart at least improved anti-static properties to said articles.

30. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 29, wherein said layer is imparted to an article such as safety goggles, eyeglasses, sunglasses, packaging, automotive headlamp lenses, instrumt panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart at least improved anti-fogging properties to said articles.

31. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 30, wherein said layer is imparted to polymer pellets and powders to impart at least improved wettability to said pellets and powders.

32. The hydrophilic substrate layer obtained bysulfonation of claim 31, wherein said powders are acrylic powders used in paints to substantially reduce the use of surfactants in said paint.

33. The hydrophilic substrate layerobtained by sulfonation ofclaim 31, wherein said powders are acrylic powders used in concrete as retarders to reduce the use ofsurfactants in said concrete.

34. A method substantially as hereinbefore described.

35. A polymer layer substantially as hereinbefore described.