WO2007139810A2 - Photo-induced copolymer functionalized substrates - Google Patents

Abstract

Articles comprising polymer(s) comprising photoreactive and/or photoreacted pendent moieties on or coupled to a textile or paper substrate, and related methods of use.

Description

Photo-induced Copolymer Functiόnalized Substrates This application claims priority benefit from provisional application serial no. 60/802,851, filed May 23, 2006, the entirety of which is incorporated herein by reference. Background of the Invention.

Innovations in the textile industry, while often fostered by fashion trends, can also be driven by the more mundane. For instance, improved durability, wettability, stiffness and other such functional or structural characteristics have been realized through the development and use of a range of polymeric coatings and textile treatments. Quality and marketing have literally made Scotchgard^® material a household word. Various other perflouro chemicals (PFCs) have also found widespread application.

However in recent years, PFCs have been increasingly subject to regulatory scrutiny over environmental concerns. Manufacturing issues arise by way of stock materials and processing techniques, together with the generation of hazardous chemical wastes. Further, PFCs, other halogenated hydrocarbons and their degradation products have been shown environmentally deleterious. As a result, the manufacture and use of such materials has been discontinued or is on the market decline. Notwithstanding such concerns, PFCs and related hydrocarbon materials provided a very limited platform from which to develop other chemistries. The molecular structure responsible for the recognized benefits is the same structure precluding further function and textile improvement. Such limitations are evident in that solutions of such materials must be chemically modulated for textile application, and separate additives are often needed to immobilize or fix the material on the textile.

As a result, the development of new textile coating materials remains an ongoing concern in the art. Photoreactive polymers have drawn some interest, primarily due to the possibility of their application as photoresists. Commercially available photoresists, however, are typically composed of toxic monomers such as acrylates, coated by organic solvents such as l-methoxy-2-propyl acetate, and washed with organic solvents or bases^; — all of which pose both health and environmental issues. An organic-solvent-free photoresist which could be coated and washed with only pure water is the expected approach from a green chemical process. Similar goals are shared in the art relating to textile treatments. Summary of the Invention.

In light of the foregoing, it is an object of the present invention to provide textile composites, polymeric coatings and/or methods for their use and/or implementation, thereby overcoming various deficiencies and shortcomings of the prior art, including those outlined above. It will be understood by those skilled in the art that one or more aspects of this invention can meet certain objectives, while one or more other aspects can meet certain other objectives. Each objective may not apply equally, in all its respects, to every aspect of this invention. As such, the following objects can be viewed in the alternative with respect to any one aspect of this invention. It is an object of the present invention to provide an approach to textile coatings alleviating the environmental concerns of the prior art, providing polymeric materials, copolymers and/or their respective monomeric components without dependence on fluorination or other forms of halogenation to effect desired properties and functionalities. It can be another object of the present invention, alone or in conjunction with one or more of the preceding objectives, to provide a flexible coating technology and molecular platform for the introduction of a variety of chemical functions and performance properties.

It can be another object of the present invention to provide, in conjunction with such a coating technology, a polymeric component which can be controllably deposited on a textile and immobilized thereon without resort to separate compositional additives. , .

It can be another object of the present invention, in view of the foregoing, to provide such polymeric materials and coating technologies in the context of one or more non-textile applications, such as paper and paper products. Other objects, features, benefits and advantages of the present invention will be apparent from this summary and descriptions of certain embodiments, and will be readily apparent to those skilled in the art having knowledge of various textiles, papers, polymeric compounds and coating technologies. Such objects, features, benefits and advantages will be apparent from the above as taken into conjunction with the accompanying examples, data, figures and all reasonable inferences to be drawn therefrom, alone or with consideration of the references incorporated herein.

In part, the present invention can comprise an article or composite comprising a textile component; and a first polymer compound thereon or coupled thereto, the first compound comprising at least one monomeric component comprising a pendent photoreactive moiety, or photoreacted with another such moiety of a second polymer compound. Such polymer compounds, monomeric component(s) and photoreactive moiety or moieties thereof are limited only by capacity for intra- or intermolecular covalent bond formation upon irradiation. Without limitation, the monomeric component can comprise a pendent photoreactive moiety selected from a thymine, a cinnamic acid (e.g., cinnamic acid, a salt or derivative thereof) or a combination of such moieties or derivatives. In certain other embodiments, the monomeric component of the first polymer is reacted with a corresponding monomeric component of the second polymer, the resulting photoreaction product cross-linking the polymer compounds. Regardless, the first and second polymer compounds can have substantially the same monomeric components, by chemical identity or ratio one to another. In certain other embodiments, the first and second polymer compounds can differ by monomeric identity and/or ratio, providing at least one monomeric component of one polymer compound is photoreactive with a monomeric component of another polymer compound. In certain embodiments, cyclodimerization of such monomeric components can cross-link the monomeric components to provide a polymeric textile coating.

In certain embodiments, at least one of the aforementioned polymer compounds can comprise at least one adjunct monomeric component comprising a moiety whereby the polymer compound is at least partially solvolytic with respect to any associated fluid medium, whether organic or aqueous. With regard to the latter, such an adjunct monomeric component can comprise an ionic moiety selected from, but not limited to, ammonium, pyridinium, sulfonium, sulfonate, acetate, benzoate, phosphate, phosphonate moieties and combinations thereof. Likewise, such a polymer compound can comprise other monomeric components comprising one or more pendent moieties and/or functional groups selected to provide one or more desired performance properties, when applied to or contacted with a textile component. Such monomeric components, moieties and/or pendent groups are limited only by synthetic technique and incorporation into a polymer compound. For instance, such moieties or functional groups can be pendent to one or more ethylene, vinyl, styrene, ethylene glycol and propylene glycol monomers and the corresponding polyalkylenes, polyvinyls, polystyrenes and poly(alkylene) oxides.

Notwithstanding any polymer compound or monomeric component thereof, the textile component of such a composite can comprise natural fibers or filaments, synthetic fibers or filaments, or a combination thereof. In certain embodiments, as illustrated more fully below, the textile component can be shaped, folded or otherwise configurationally-manipulated prior to and/or during polymer photoreaction. In part, the present invention can comprise an article or composite comprising a paper component; and a first polymer compound thereon or coupled thereto, the first compound comprising at least one monomeric component comprising a pendent photoreactive moiety or photoreacted with another such moiety of a second polymer compound. Such polymer compounds, monomeric component(s) and photoreactive moiety or moieties thereof are limited only by capacity for intra- or intermolecular covalent bond formation upon irradiation. Without limitation, the monomeric component can comprise a pendent photoreactive moiety selected from a thymine, a cinnamic acid (e.g., cinnamic acid, a salt or derivative thereof) or a combination of such moieties or derivatives. In certain other embodiments, the monomeric component of the first polymer is reacted with a corresponding monomeric component of the second polymer, the resulting photoreaction product cross-linking the polymer compounds. Regardless, the first and second polymer compounds pan have substantially the same monomeric components, by chemical identity or ratio one to another. In certain other embodiments, the first and second polymer compounds can differ by monomeric identity and/or ratio, providing at least one monomeric component of one polymer compound is photoreactive with a monomeric component of another polymer compound. In certain embodiments, cyclodimerization of such monomeric components can cross-link the monomeric components to provide a polymeric paper coating. In certain embodiments, at least one of the aforementioned polymer compounds can comprise at least one adjunct monomeric component comprising a moiety whereby the polymer compound is at least partially solvolytic with respect to any associated fluid medium, whether organic or aqueous. With regard to the latter, such an adjunct monomeric component can comprise an ionic moiety selected from, but not limited to, ammonium, pyridinium, sulfonium, sulfonate, acetate, benzoate, phosphate, phosphonate moieties and combinations thereof. Likewise, such a polymer compound can comprise other monomeric components comprising one or more pendent moieties and/or functional groups selected to provide one or more desired performance properties or strengthen or beneficially enhance one or more structural aspects, when applied to or contacted with a paper component. Such monomeric components, moieties and/or pendent groups are limited only by synthetic technique and incorporation into a polymer compound. For instance, such moieties or functional groups can be pendent to one or more ethylene, vinyl, styrene, ethylene glycol and propylene glycol monomers and the corresponding polyalkylenes, polyvinyls, polystyrenes and poly(alkylene) oxides.

Notwithstanding any polymer compound or monomeric component thereof, the paper component of such a composite can comprise one or more of a range of natural cellulosic fibers, optionally in conjunction with one or more synthetic fibers or filaments. In certain embodiments, as illustrated more fully below, the paper component can be shaped, folded or otherwise confϊgurationally-manipulated prior to and/or during polymer photoreaction. In part, the present^' invention can also be directed to a method of using a polymer component to affect textile or paper properties. Such a method can comprise providing either a textile or a paper substrate; contacting the substrate with at least one polymer compound comprising at least one monomeric component comprising a pendent photoreactive moiety and at least one solvolytic adjunct monomeric component; and irradiating the polymer(s) at a wavelength and for a time at least partially sufficient for monomer photoreaction and polymer cross-linking. Without limitation, such a polymer compound can be any one or a combination of the polymers described, illustrated, or otherwise inferred herein. Monomeric components and corresponding photoreactive moieties can, likewise, be selected from any or a combination of such components and/or moieties described, illustrated or inferred herein.

In certain embodiments, the textile substrate and polymer compound can be contacted one with the other using a medium comprising a solvent. Polymer solubility can be a function of at least one of the adjunct monomeric components. In certain embodiments, an adjunct monomeric component can comprise an ionic moiety of the sort described above, such that the polymer is at least partially soluble in an aqueous medium.

For purpose of the present methods and composites, the following terms or expressions, unless otherwise used, will be understood as having meanings ascribed thereto by those skilled in the art or as otherwise indicated with respect thereto:

"Textile" or "textile substrate" means a cloth, fabric and/or material structurally or texturally similar to a cloth or fabric, together with fiber, filament and/or thread components thereof, and/or an article or product manufactured or made from or using such a cloth, fabric or material, or fiber, filament or thread components thereof. Representative embodiments, without regard to manufacturing process or end-use application, include but are not limited to those of natural origin (e.g., silk, cotton, etc.) and the range of synthetics. Illustrating the former, natural cotton textiles such as Bleached Desized Cotton Print Cloth

(78x76) (ISO 105/F02) and American Eagle Outfitters 100% Macau Cotton Shirt RN# 54485 are typical of mercerized combed cotton broadcloths. Where the first of these embodiments demonstrates the applicability of the invention at the manufacturing stage typical of traditional durable press treatments, the latter embodiment demonstrates the applicability on finished cotton fabric. Such embodiments illustrate the range of compatibility with the cotton finishing operations of bleaching, desizing, mercerization, and combing. Other non-limiting embodiments also include textiles based on synthetic fibers such as polyesters, nylons, rayon and poly lactic acid. In such embodiments the stiffening and shape retention effects of the polymer-textile composite can be most pronounced for textile substrates with mass to area ratios of less than about 180gm/m².

Applications on denser fabric styles, such as terricloths, flannels, or carpets, can draw on the other effects or functionalities proffered by the present polymer treatment such as dye-attachment, bacteriostatic properties, tunable hydrophobicity, and tunable porosity. "Paper" or "paper substrate" means a cellulosic sheet or piece and/or a material structurally or compositionally. similar thereto, together with fibers or components thereof, and/or an article or ^"product manufactured or made from or using such a sheet, piece or material, or fibers thereof. Representative embodiments, without regard to manufacturing process, cellulosic origin or end- use application, include but are not. limited: tissue, newsprint, bible, bond, parchment, offset, uncoated book, and lower weight book paper and/or paper grade. Such embodiments can, without limitation, derive from cotton, denim, hemp, linen, flax, or wood pulps and mixtures thereof. Use or employment of this invention may be prior to or after a paper finished state, whether the paper is coated or uncoated (e.g., glossy, dull, rough, or smooth). A non-limiting example of a finished paper embodiment is 20 Ib. premium copy paper (WBM-21200). Illustrating another aspect of this invention enhanced, mechanical properties can be realized, especially so at lower weight grades in the 30-75 gm/m² range.

Without limitation as to substrate, photoreactive monomer component identity or relative amount, the polymer compound(s) can be irradiated at a wavelength ranging from about 200 nm to about 600 nm. The irradiation can be of an intensity and time to cross-link the polymer(s). In certain embodiments of such a methodology, polymer cross-linking can be at least in part a function of the ratio of the photoreactive monomeric component(s) to an adjunct monomeric component. Where, initially at least, partially soluble in a particular medium, sufficient cross-linking can insolublize and deposit the polymer(s) on either a textile or a paper substrate. For purpose of illustration only, where the textile or paper is configurationally-manipulated prior to or during irradiation, such deposition can be used to affect stiffness or shape of the substrate.

Various other mechanical properties of the resulting composite are a function of crosslink density, such properties including but not limited to elasticity, porosity and stiffness. While crosslink density can be effected by irradiation time, as mentioned above, other controllable factors include polymer molecular weight, irradiation wavelength and intensity. Other functional properties can be imparted to a textile or paper substrate, depending upon polymer design and composition, such functional properties including but not limited to tunable hydrophobicity, tunable porosity, anti-bacterial, toning (i.e., dyeing), reversible toning, conductivity and color.

Detailed Description of the Drawings.

Figure 1. ¹H NMR spectra of tripolymers in D₂O (a) PVBT 0 - 8.0 ppm (b) PVBTl , (c) PVBT2, (d) PVBT3, (e) PVBT4, and (f) PVBT5.

Figure 2. Photoresists are immobilized onto substrates by exposure to UV light. Unexposed regions are removed with a simple aqueous wash.

Figure 3. PVBTl (left) and PVBT5 (right) after irradiation and dying, illustrating improved coating with increased ratio of BDMQ. Figure 4. TGA curves of the five triblock copolymer/tripolymer systems under nitrogen atmosphere.

Figures 5 A-C. Graphic representations of the data of Tables 3 and 4. Detailed Description of Certain Embodiments.

As discussed above, polymers useful herewith are limited only by intra- or intermolecular covalent bonding upon irradiation. However, illustrating certain non-limiting embodiments of this invention, the composites and methods can be considered in conjunction with any polymers that comprise portions derived from a photoreactive monomer and an adjunct water-soluble monomer. Water-soluble monomers include, for example, cationic or anionic monomers, or they can contain an appropriate ratio of oxygen and nitrogen to carbon so as to promote hydration through hydrogen bonding. Examples of useful water-soluble monomers are vinylbenzylammonium cations, vinylbenzylsulfonium cations, N- alkylvinylpyridinium ions, vinylphenylsufonate anions, vinylbenzoate anions, vinyphenylphosphate anions, vinylbenzamide ions, and vinylphenylsufonamide ions. Suitable non-ionic monomers include, for example, ethylene oxide, propylene oxide and oxazoliηes, for example, 2-ethyl-2-oxazoline.

Suitable photoreactive monomers are capable of polymerization with a solubilizing monomer(s) of the sort described above. They can also induce a solubility or polarity change within the molecule upon irradiation so as to impart a macroscopic change in the bulk polymer. Useful examples include vinylbenzylthymine, vinylbenzyluracil, vinylphenylcinnamate, vinylcoumarins, vinylchalcones, N-acryloylamidopyridinium halides and combinations thereof. From an alternative respective, certain monomers used with this invention can be represented by structures which impart such functionality, and include free radical addition polymerizable monomers, (e.g. vinyls), which include one or more ethylenically unsaturated bonds per molecule in which the ethylene bond is part of a pi conjugated set of bonds capable of absorbing actinic radiation. In order to direct site of polymerization, such embodiments can include constituents which provide a resonance structure that stabilizes the formation of radical on the vinyl group and provide greater steric hindrance for ethylene feature such that the vinyl site is the preferred radical formation site. For example, thymine and uracil derivatives useful for preparing copolymeric mordants of this invention include 1- (vinylbenzyl) uracil (VBU), l-(vinylbenzyl)-3-methylthymine (VBMT), 1- (vinylphenyl) thymine (VPT), and l-(vinylbenzyl) thymine (VBT). Vinylbenzylstyrylpyridinium also meets such parameters. Arylthylenes and ((aryl)vinyl)benzenes such as the vinylstilbenes, 4-bromo-2,5-dioctyl-(E)-4'- vinylstilbene and 4-nitro-4'-vinylstilbene are also useful. To modulate photosensitivity some embodiments provide an ethylene moiety alpha-beta unsaturated with respect to a carbonyl. Such is also the case with vinyl-3-phenyl- acrylic acid, vinylitaconic acid, vinylcrotonic acid, vinylisocrotonic acid, and vinylmaleic acid. Upon irradiation with an appropriate radiation, e.g., light such as ultraviolet (UV) light, these photoreactive polymers are activated, e.g., crosslinked or otherwise stiffened, to become water-insoluble.

Useful polymeric compounds include polystyrene-based polymers, with hydrating moieties and pendant photoreactive moieties that upon irradiation undergo a crosslinking reactions, for example, [2 + 2] photodimerization (cyclization) reactions. Examples of the photoreactive moieties include thymine (e.g., benzyl thymine), uracil, and other organic moieties capable of participating in [2 + 2] photocyclization reactions. Such polymers can include multi-functional vinylbenzyl and vinylphenyl pendant thymine (and/or uracil) groups, and are described, for example, in U.S. Patent Nos. 5,708,106 and 5,455,349. Other examples include, but are not limited to, polymers containing cinnamates

(Nakayama et al., Polymer Sci., Part A: Polymer Chemistry (1992), 30(11):2451- 7), coumarins (Delzenne et al., Ind. Chim. Beige (1967), 32(Spec. No.), 373-8), and chalcones (Mihara et al., Polymer Journal (Tokyo, Japan) (2002), 34(5), 347- 355). Other useful polymers include those described in "New Thymine and Uracil Photopolymers" Cheng et al., Proceedings of the IS&T's 47th Annual Conference. The Physics and Chemistry of Imaging Systems, 810, 1994; "Copolymeric Mordants and Photographic Products and Processes Containing Same," Grasshoff et al., U.S. Patent No. 5,395,731 (March 7, 1995); "Vinylbenzyl Thymine Monomers and Their Use in Photoresists," Grasshoff et al., U.S. Patent No. 5,455,349 (October 3, 1995); "The Synthesis of l-[Vinylbenzyl]thymine, A Very Versatile Monomer," Cheng et al. J. Polymer Sci., Part A: Polymer Chem. 1995, 33, 2515; "Method of Imaging Using a Polymeric Photoresist Having Pendant Vinylbenzyl Thymine Groups," Grasshoff et al., U.S. Patent No. 5,616,451 (April 1, 1997), and "Copolymers Having Pendant Functional Thymine Groups," Grasshoff et al., U.S. Patent No. 5,708,106 (January 13, 1998). Each of the foregoing patents and publications are incorporated herein by reference in its entirety. Many such monomers, and polymers made from such monomers, are also commercially available.

Another photoreaction mechanism to render a polymer insoluble is a photo ring expansion process that involves pyridinium ylides (See, e.g., Streith, Chimia (1991) 45(3):65-76 also incorporated herein by reference in its entirety.) In general, any photoreaction that generates covalent bonds, or dramatically alters molecular polarity and renders the polymer insoluble in the medium employed can be employed in conjunction with this invention.

Regardless, without limitation, the monomeric component(s) comprising photoreactive moieties of the polymer can be about 3% to about 50% or more by weight of the polymer, e.g., about 4, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, or about 45% by weight. Monomeric percentage can be chosen for a particular polymeric design, depending on desired cross-linking and corresponding function and mechanical properties. Once applied to a textile or a paper substance, and where applicable in a desired configuration, the soluble (e.g., water-soluble) polymers are irradiated for a time sufficient to crosslink or otherwise activate the polymer and render it insoluble. Broad UV light (e.g., from about 200 ran to about 600 nm, or from about 250 nm to about 400 nm) or actinic radiation, e.g., UV light at specific wavelengths, such as 285 nm,^'can be used to cross-link the polymer. Irradiation of the polymer initiates, for example,' [2 + 2] cyclization reactions between the photoreactive moieties, which causes the polymer to become water-insoluble and deposited on the substrate, as well as to become stable to other environmental conditions (e.g., air and light). Polymers with thymine photoreactive moieties are activated or crosslinked by light at a wavelength of about 285 nm. Other polymer systems are responsive to light irradiation at a wavelength of up to about 360 nm. In addition, the effective wavelength of light can be adjusted by adding a photosensitizing comonomer, e.g., by incorporating a sensitizer into the polymer backbone, or by adding a sensitizer to the application solution. Both techniques allow a molecule of one wavelength to, by energy transfer, sensitize the photoreaction to a desired wavelength. Suitable photosensitizers that can be added to the solution include benzoporphyrin, benzophenones, cinnamates, Methylene Blue, and fluorescein.

Water-soluble additives, for example, water soluble azo initiators, can also be used to aid in the cross-linking of the photoreactive polymers. Azo initiators can be selected with the appropriate temperature half-life, typically the 10 hour half-life decomposition temperature, T. Examples of water-soluble azo initiators include 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride (T = 41 ⁰C), 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate (T = 57 ⁰C)', and 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (T = 86 ⁰C). Water-soluble azo initiators are available from Wako Chemicals USA, Richmond, VA.

The length of time that the polymers maintain textile/paper shape or configuration can be controlled by the identity of the polymer (specifically the monomer composition from which the polymer is derived); e.g., depending on monomeric composition, by adjusting one or more of the following: (1) the ratio of photo-reactive monomer to solubilizing monomer incorporated into the polymer can be increased (while these results will vary depending on many parameters, a 1 :1 polymer ratio should provide the most or longest control, a 1 :2 ratio will be shorter, a 1 :4 ratio will be shorter lasting, a 1:8 ratio shorter still, and a 1:16 will be very short lived); (2) the length of time that the polymer is irradiated can be varied (in general, the longer the irradiation time, the greater the crosslink density, and the longer "hold" of the polymer); and (3) the identity of the photoreactive monomer can be changed. This will provide many gradations of "photoactivity." For example, photoreactive polymers based on thymine are more sensitive than those based on cinnamates, thus given the same amount of irradiation, the thymine-based polymers will provide a longer control or influence than the cinnamate-based polymers.

Representative of certain aspects of this invention, block tripolymers of vinylbenzylthymine (VBT), N,N_JN-triethyl-(4-vinylbenzyl)ammonium chloride (TEQ) and 7V-butyl-N,N-dimethyl-(4-vinylbenzyl)ammonium chloride (BDMQ) with differing monomer ratios were prepared and their properties are controllable by manipulating monomer ratio(s). These polymers are water soluble textile or paper and when irradiated with low levels of UV light undergo a 2π + 2π photodimerization reaction of thymine. The reaction significantly decreases water solubility, immobilizing the polymer on the substrate, and demonstrating application as a water soluble textile treatment. The tripolymers were characterized by NMR data and elemental analysis. Thermogravimetric analysis revealed that the tripolymers have two degradation stages corresponding to quaternary ammonium pendant groups and thymine. Evaluation of contact angle measurements showed that surface properties and hydrophobicity could be controlled by varying monomer ratios. While tripolymers, regardless of composition or component identity, are used in some manufacturing contexts to afford process and performance control, copolymers can be used with comparable effect in other contexts.

More specifically, as relates to one or more of the preceding objectives, minimization of exposure to toxic monomers, crosslinking agents and high energy radiation have been achieved with environmentally benign, thymine-containing, water-soluble photopolymers. Thymine based polymers are highly stable (pH, temperature), nontoxic, and when exposed to shortwave UV light undergo an enzymatically and UV light reversible 2π+2π photodimerization. Immobilization of the polymers can be achieved on a variety of substrates. Thymine based polymers are immobilized via crosslinking of benign polymers rather than via polymerization of toxic monomers, addressing the problem of toxic monomer leaching, and a simple aqueous wash is used to collect and reuse any non- crosslinked polymers. The thymine moiety of the corresponding monomer can be derived from renewable feed stocks, such as waste biomass.

Accordingly, TEQ and BDMQ, which have been known to possess high antimicrobical activities, along with VBT were used to prepare thymine based tripolymers with varying monomer ratios (scheme 1, where n is an integer >1, and m and 1 are selected from 0 and integers >1, providing with this non-limiting embodiment at least one of m and 1 is at least 1). The increased hydrophobic properties of BDMQ over TEQ allows control of the hydrophobicity of the polymers by increasing the amount of BDMQ monomer ratio within the tripolymer system. Tripolymers were characterized by NMR data and elemental analysis. Thermal and surface properties were determined by thermogravimetric analysis and evaluating contact angle measurements, respectively.

Scheme 1.

YBT Tripolymers. PVBTl (poly(VBT(l)-co-TEQ(8)), PVBT2 (poly(VBT(l)-co-TEQ(6)-co-BDMQ(2)), PVBT3 (poly(VBT(l )-co-TEQ(4)-co- BDMQ(4)), PVBT4 (poly(VBT(l)-co-TEQ(2)-co-BDMQ(6)) , and PVBT5 (poly(VBT(l)-co-BDMQ(8)) were prepared by the tripolymerization of VBT, TEQ, and BDMQ (Table 1). The polymer structures were characterized by ¹H NMR spectra, gel permeation chromatography (GPC), and elemental analysis.

Table 1. Synthesis of VBT:TEQ:BDMQ tripolymers, molecular weights, and elemental analysis³

Polymerization was carried out in water/isopropanol — 1/1 (250 ml) with AIBN (1 wt % mmol) under nitrogen. * Estimated by gel permeation chromatography with poly(ethylene oxide) standards in water/methanol = 70/30 buffer (acetic acid = 0.5 M, sodium acetate = 0.5 M).

The ¹H NMR spectra of the five tripolymer series are presented in Figure 1. Absence of peaks between 6.0 — 5.0 ppm (vinyl protons) verified that unreacted monomers were not present (Figure Ia). The ratio of TEQrBDMQ was determined by peak intensities from 2.0-0.9 ppm (alkyl substituent protons from BDMQ and TEQ) for the tripolymer series. PVBTl (Figure Ib) contains a broad peak at 1.2 ppm (ethyl proton). The addition of BDMQ in PVBT2 (Figure Ic) displays a developing broad peak at 0.9 ppm for the butyl proton within the alkyl substituent, with a decrease at 1.2 ppm (Figure 1 c and d) corresponding to a smaller ratio of TEQ. Complete disappearance at 1.2 ppm (br) is not expected as BDMQ contains a single propyl proton environment (1.27 ppm (br)). Verification of ethyl protons in the butyl substituent on BDMQ, in Figure Ie (PVB T4), is seen as a developing broad peak at 1.7 ppm. The amount of AIBN initiator added for each tripolymer synthesis was the same (1 wt %) and because TEQ and BDMQ are constitutional isomers, it is not surprising to find close molecular weights and elemental analysis data for all five tripolymers. Various features and benefits (e.g., hydrophobicity, processing and recyclization of unused polymer) of this invention can be illustrated through use of such monomers and their corresponding polymers in an unrelated context, such as their use as photoresists. The tripolymer films were prepared using a polymer solution of 0.1 g of a polymer from Table 1 in 1 :3 aqueous solution of ethanol then spin coated onto a glass slide and allowed to dry at ambient temperature. Immobilization of the polymer onto the slide is achieved with short wave UV light (Figure 2). Irradiation of exposed regions on the slide causes neighboring thymine molecules to undergo a 2π+2π photodimerization reaction (Scheme 2). Any remaining uncrossl inked polymers are removed with a simple aqueous wash. An anionic dye is used to label all crosslinked polymers for coating verification.

The patterns on the film (numbers and solid bars) are clearly visible on the slide coated with PVBT5 (Figure 3, right slide). The absence of the numbers and lighter color due to significantly less dye absorption using PVBTl (Figure 3, left slide) demonstrates the improved coating capabilities with increased amounts of BDMQ. FD&C green No. 3 has been used to mark otherwise clear and colorless regions that have been successfully crosslinked and demonstrate color density associated with dye absorption.

Scheme 2. The thermal properties were investigated with TGA in a nitrogen stream. The thermogravimetric curves of the tripolymers are compared in Figure 4. The initial 10.0% weight loss at 100⁰C occurs as a result of water evaporation. It must be noted the PVBT polymers have two degradation stages that correspond to TEQ and BDMQ at 175° C and VBT at 375° C. It can be seen that decomposition of the tripolymer systems does not change as a result of an increase or decrease in either TEQ nor BDMQ.

The measurement of water contact angle is an important characterization parameter for predicting and controlling the hydrophobic properties of benign conductive films. PVBTl, which contains zero BDMQ₃ has demonstrated the lowest contact angle at 63.5° (Table 2). Each polymer following in the series has expressed increased hydrophobic properties in accordance with increased amounts of BDMQ, reaching a maximum of 94.2° with PVBT5. This phenomena is believed due at least in part to increased non-covalent forces such as dipole-dipole and Van der Waals interactions caused by the two methyl and longer butyl substituents on BDMQ₃ rather than the three ethyl substituents on TEQ. A tripolymer system in which the hydrophibic properties of such films can easily be adjusted according to the specific surface properties required per application.

Table 2. Calculated Water Contact Angle

Tripolymers of VBT, TEQ and BDMQ with differing monomer ratios were prepared and their property control imparted by manipulating the monomer ratio has been investigated. ¹H NMR spectra has been used to verify monomer ratios within the tripolymer systems. TGA studies indicate that the thermal stability of the tripolymers is unchanged as a result of varying monomer ratios within the systems. Water contact angle data range from 63.6 ± 12.2° for PVBTl to 94.2 ± 5.6° for PVBT5. From such results, it is evident that water contact angles clearly reflect the increasing hydrophobicity of the films with increasing BDMQ composition, and the adjustable hydrophobic properties of such polymers as can be demonstrated using VBT with TEQ and BDMQ.

Examples of the Invention.

The following non-limiting examples and data illustrate various aspects and features relating to the polymers, composites and/or methods of the present invention, including the preparation and assembly of textile and paper composites having various polymeric coatings thereon, as are available through the methodologies described herein. In comparison with the prior art, the present composites and methods provide results and data that are surprising, unexpected and contrary thereto. While the utility of this invention is illustrated through the use of several composites, textile or paper substrates, polymers and monomeric components thereof, it will be understood by those skilled in the art that comparable results are obtainable with various other composites, textile substrates, paper substrates monomeric components and polymers, as are commensurate with the scope of this invention. Materials. All reagents and materials, unless specifically noted, were purchased from Sigma-Aldrich in its purest available form and used as received. VBT was synthesized from thymine and vinylbenzyl chloride as described in one or more of the aforementioned incorporated references. N-triethyl-(4- vinylbenzyl)ammonium chloride (TEQ) and N-butyl-N,N^r-dimethyl-(4- vinylbenzyl)ammonium chloride (BDQ) were synthesized from vinylbenzylchloride (VBCl). triethyl amine (TEA), and N, N-dimethybutylamine respectively. See, Ikeda, T.; Tazuke, S. Makromol Chem 1984, 185, 869-876.

ΝMR spectra were taken on Bruker 200 MHz ΝMR spectrometer. IRs were performed using Thermo electron corp. class 1 laser product. Elemental analysis was performed using the classical modified Pregl/Dumas technique on an Exeter Analytical 240 analyzer at UMass Amherst. Molecular weights were measured using Agilent 1 100 series gel permeation chromatography (GPC).

Example 1 Tripolymer Synthesis. PVBTl (poly(VBT(l)-co-TEQ(8)), PVBT2 (poly(VBT(l)-co-TEQ(6)-co-BDMQ(2))_s PVBT3 (poly(VBT(l)-co-TEQ(4)-co- BDMQ(4)), PVBT4 (poly(VBT(l)-co-TEQ(2)-co-BDMQ(6)) , and PVBT5 (poly(VBT(l)-co-BDMQ(8)) (where the number in the parentheses is the molar ratio for the respective monomers) were prepared by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBΝ) (1 wt % of AIBΝ per synthesis) as an initiator in 250 mL of a 50% (v/v) aqueous solution of isopropanol under nitrogen. The solution was held at 65°C for 16 hours while stirring, then cooled to room temperature and concentrated to 125 mL in vacuo. Polymerized product was purified by adding the aqueous solution to 1 L of acetone, then filtered and dried under vacuum for 2 days. ¹H ΝMR spectroscopy confirmed the absence of unreacted monomer and elemental analysis was used to confirm tripolymer ratios. PVBTl IR (ATR): v_c=0 = 1673 cm^"1, PVBT2 IR (ATR): v_c=o= 1671 cm^"1, PVBT3 IR (ATR): V₀=_O = 1658 cm^'1, PVBT4 IR (ATR): v_c=0 = 1673 cm^"1, PVBT5 IR (ATR): Vc=_O= 1673 cm^"1

Example 2 Thermal Analysis. The thermal stability of the five polymers series was studied using Q50 TGA and QlOO DSC instruments from TA Instruments. To perform the TGA experiment, the polymer samples were carefully weighed, put into the furnace of the instrument and heated, under nitrogen, over a range of 35 - 600⁰C at 10⁰C /min. Samples for the DSC experiment were carefully weighed, put into the furnace of the instrument and heated, under nitrogen, over a range of 23 - 300⁰C at 10⁰C /min. Example 3

Coating Procedures. Coatings were done on glass slides (VWR scientific 25X75mm microslides) using a Headway Research Inc. EC 10 ID spin coater. A solution of 0.1 g polymer in 1 :3 aqueous solution of ethanol was added to the spinning glass slide and held at 2000 RPM for sixty seconds. The samples were then dried at ambient conditions for one hour.

Example 4

Irradiation. The samples were irradiated with short-wave UV light (254 nm) using Spectrol inker XL-1000 UV Crosslinker manufactured by Spectronics Corp. (Westbury NY). The exposure levels varied between 0 and 360 mJ/cm². The samples were then submerged in water for two minutes while stirring using the Lab-Rotator and rinsed with water to remove any non-crossl inked polymer. The samples were dried at 8O⁰C for one hour. Two of three slides made for each sample were submitted for contact angle measurements. The third slide was toned with anionic dye FD&C green No. 3 powder (Warner Jenkinson Co., Inc.) for visual verification that a uniform coating had been achieved.

Example 5

Contact Angle Measurements. Contact angle measurements were taken on a Krϋss DSA 100 Dynamic Contact Angle Goniometer using drop shape analysis software at ambient temperature. The probe solvent in each case was water. Drop volume was fixed at 2.0 μL and set to drop at a rate of 10.0 μL/min. A lO second video file was created for each drop, measuring 5 frames per second. The data presented represents initial contact angle only, taken at the first frame in which the whole drop was fixed to the substrate without interference or contact with probe needle. Theta is reported as an average of angles measured on the left and right sides of drop images. Standard deviation reflects average theta over 10 readings taken randomly over the entire surface of each sample slide totaling 2 slides per polymer.

Example 6 Illustrating shape and configurational control of the sort available through this invention, paper and textile substrates were coated on one side with a VBT/TEQ polymer (e.g., PVBTl, in Table I). Representative substrates used were 20 Ib. premium copy paper (WBM-21200) and a textile available under Parisian Nosegay trade designation from the old Deerfϊeld Decorative Fabrics Collection, with Scotchguard® treatment, from old Deerfield Fabrics of Cedar Grove, New Jersey (demonstrating an extension of this invention to finish manufactured, post- treated textiles). With reference to Tables 3 and 4, the corresponding substrate was configured to provide either an inner or outer fold, with respect to the polymer coating. (That is, "inner" refers to a V-shaped fold or pleat, with the polymer coating therein; and "outer" refers to a V-shaped fold or pleat with the polymer coating on the outside or both sides thereof.)

Referring to Table 3, fabric coated with VBT without irradiation performed substantially no different than fabric coated with TEQ. Fabric coated with irradiated VBT showed improved configurational control, as measured by distance between folded edges. Incremental improvement was shown by coating on both sides. Similar results were evidenced with polymer-coated paper substrates, with folded edge distances reflecting stiffer fiber content and improved matrix strength. The results of Tables 3 and 4 are graphically displayed in Figures 5A-B with Figure 5 C showing the detail of Figure 5 A on an enlarged scale.

Table 4: Observations of Paper and paper-Polymer Composites.

As demonstrated by the preceding, this invention represents a departure from classic substrate coatings, to provide technically-designed textiles and papers offering a broad array of performance properties. Such innovations are achievable through use of polymeric platforms which can be compositionally varied as needed for specific chemical or mechanical function. Choice of monomeric components and/or functional groups thereon affords a modular approach heretofore unrecognized in the textile and paper arts.

Claims

We claim:

1. An article comprising a substrate component selected from a textile and a paper; and at least one of a first polymer compound and a second polymer compound, said polymer compound coupled to said substrate component, and comprising at least one monomeric component comprising a pendent moiety ' capable of photoreaction with another monomeric component comprising a pendent photoreactive moiety of at least one of said first and second polymer compounds.

2. The article of claim 1 wherein each said monomeric component comprises a pendent moiety selected from a thymine moiety, a cinnamate moiety and a combination of said moieties.

3. The article of claim 1 comprising a photoreaction product of said pendent moieties cross-linking said monomeric components.

4. The article of claim 3 comprising first and second polymer compounds.

5. The article of claim 4 wherein each said polymer compound comprises substantially the same monomeric components, and each said monomeric component comprises a pendent moiety selected from a thymine moiety, a cinnamic acid moiety and a combination thereof.

6. The article of claim 1 wherein at least one of said first and second polymer compounds comprises at least one adjunct monomeric component comprising a moiety at least partially solvolytic to a fluid medium.

7. The article of claim 6 wherein said adjunct monomeric component comprises an ionic moiety selected from ammonium, pyridinium, sulfonium, sulfonate, acetate, benzoate, phosphate and phosphonate ions and combinations thereof, said polymer compound at least partially soluble in an aqueous medium.

8. The article of claim 7 wherein at least one of said first and second polymer compounds is selected from a polyalkylene and a poly(alkylene)oxide.

9. The article of claim 7 wherein each of said first and second polymer compounds independently comprise a monomeric block of VBT, and a monomeric block of at least one of TEQ and BDMQ.

10. The article of claim 9 wherein said polymer compounds are irradiated.

11. The article of claim 10 wherein said substrate component is configurationally-manipulated prior to irradiation.

12. The article of claim 10 in one of a manufactured textile product and a manufactured paper product.

13. A method of using a polymer compound to affect a substrate property, said method comprising: providing a substrate component selected from a textile and a paper; contacting said substrate with at least one of a first and second polymer compound, each said polymer compound comprising at least one monomeric component comprising a pendent moiety capable of photoreaction with another monomeric component comprising another photoreactive pendent moiety and at least one adjunct monomeric component comprising at least one moiety at least partially solvolytic to a fluid medium; and irradiating said polymer compound at a wavelength and for a time at least partially sufficient for photoreaction of said photoreactive monomeric components, said polymer compound coupled to said substrate.

14. The method of claim 13 comprising first and second polymer compounds, each said polymer compound comprising substantially the same monomeric components.

15. The method of claim 14 cross-linking said polymer compounds, wherein said cross-linking is at least in part a function of the ratio of a

^•photoreactive monomeric component to an adjunct monomeric component.

16. The method of claim 13 wherein said substrate component is contacted with a polymer component in a fluid medium.

17. The method of claim 16 where the solubility of said polymer compound in said fluid medium is a function of one said adjunct monomeric component.

18. The method of claim 17. wherein at least one of said first and second polymer compounds is at least partially soluble in an aqueous medium.

19. The method of claim 13 comprising first and second polymer compounds, wherein each said photoreactive monomeric component comprises a pendent moiety selected from a thymine moiety, a cinnamic acid moiety and combinations thereof.

20. The method of claim 19 wherein at least one of said first and second polymer compounds is at least partially soluble in an aqueous medium.

21. The method of claim 20 wherein said polymer compounds are irradiated at a wavelength ranging from about 200nm to about 600nm.

22. The method of claim 13 wherein said substrate is configurationally manipulated prior to irradiation.

23. The method of claim 13 wherein said substrate component is manufactured to provide one of a textile product and a paper product.

24. An article comprising a substrate component selected from a textile and a paper; and the [2+2] photocyclization product of a block copolymer compound comprising a monomeric component comprising a pendent photoreactive moiety selected from a thymine moiety, a uracil moiety and an cinnamic acid moiety, and at least one monomeric component comprising a pendent quaternary ammonium salt moiety, said copolymer compound covalently cross-linked and coupled to said substrate component.

25. The article of claim 24 wherein said copolymer compound comprises about 3 wt. % to about 50 wt. % said photoreactive monomeric component.

26. The article of claim 25 wherein said photoreactive monomeric component is selected from VBU, VBMT₅ VPT, VBT and combinations thereof; and said other monomeric component is selected from TEQ, BDMQ and combinations thereof.

27. The article of claim 26 comprising a triblock copolymer of VBT, TEQ and BDMQ. .

28. The article of claim 24 selected from a manufactured textile product and a manufactured paper product.