WO2005062891A2

WO2005062891A2 - Process for producing polymeric articles using an activator composition

Info

Publication number: WO2005062891A2
Application number: PCT/US2004/043135
Authority: WO
Inventors: Lars Guenter Beholz
Original assignee: Lars Guenter Beholz
Priority date: 2003-12-24
Filing date: 2004-12-23
Publication date: 2005-07-14
Also published as: WO2005062891A3

Abstract

A method for modifying the surface characteristics of a polymeric substrate and/or virgin or regrind polymeric material in which a portion of the surface of the polymeric substrate and/or virgin or regrind polymeric material is contacted with a composition containing at least one oxidizing agent and an activator composition. The oxidizing agent in the composition is present in a kinetically degrading state capable of producing at least one chemical intermediate that is reactive with the polymeric substrate/virgin polymeric material. The inventive activator agent includes at least one of inorganic acids and/or inorganic acid precursors in optional combination with at least one organic acid or derivatives thereof. The activator agent may be present in the composition upon initial contact with the polymeric substrate/virgin polymeric material, or may be added to the composition subsequent to initial contact with the polymeric substrate/virgin polymeric material.

Description

PROCESS FOR PRODUCING POLYMERIC ARTICLES USING AN ACTIVATOR COMPOSITION

BACKGROUND [0001] The present invention claims priority from United States Provisional Application Numbers 60/531,894 and 60/531,900.

[0002] The present invention relates to a process for improving the adhesion characteristics of a polymeric substrate surface and/or of a virgin or recycled polymeric material moldable into a substrate exhibiting improved adhesion characteristics including, but not limited to polarity, reactivity and adhesion.

[0003] Polymeric materials provide excellent and versatile mechanical qualities and find use in a wide variety of applications. In certain instances, it is necessary to coat or otherwise modify the surface of polymeric materials to meet adhesion, polarity or reactivity requirements or to provide a protective surface to help the polymeric substrate withstand degradation or abrasion. Providing a high quality durable painted surface on certain polymeric substrates has been problematic due to generally poor surface adhesion qualities exhibited by various polymeric substrate materials. Poor surface adhesion is also problematic in situations in which other laminates, films or metallic layers are to be imparted onto the polymer. Situations can also include bonding of one polymer substrate to another polymeric material or to non-polymeric substrates.

[0004] To this end, much activity has been devoted to providing polymers with improved surface adhesion characteristics and to improving the surface polarity or reactivity characteristics of known polymeric materials. Methods include roughening of polymeric surfaces by exposure to strong mineral acids with or without the presence of strong oxidizers such as chromates, permanganates and the like. [0005] Other adhesion promotion methods involve the use of strong mineral acids in combination with concentrated mineral oxidants and strong mineral acid salts in aqueous treatment solutions. This art is taught in U.S. Pat. No. 3,869,303 to Orlov et al. Problems associated with the use of such strong mineral acids and toxic oxidizers include handling and disposal risks as well as the potential that the polymeric surface and substrates may be excessively degraded or compromised. Additionally, it is possible that the resulting polymeric substrate surface may be susceptible to unwanted oxidation or the like, necessitating immediate coating with the desired coating material.

[0006] Treatment of polyolefin materials for adhesive bonding using a non- chromate solution containing sulfuric acid in the presence of either lead dioxide, potassium iodate or ammonium persulfate is taught in U.S. Pat. No. 4,835,016 to Rosty et al. The Rosty reference also discusses the use of a solution containing bleach and detergent. In order to be effective, the Rosty reference teaches that the polymeric samples must be submersed in the prescribed solution for several days. Such protracted exposure is simply not practical in many treatment operations.

[0007] Treatment methods are also known which teach the use of peroxydisulfuric acid solutions with the optional use of accelerants capable of activating peroxydisulfuric acid oxidation reactions. In U.S. Pat. No. 3,695,915 to Morris, metal salts such as copper, ferrous or silver salts of sulfuric acid or nitric acid are employed to increase the rate, of evolution of oxygen. Care must be taken in employing the process disclosed in Morris lest excess concentrations of deleterious sulfuric acid are produced.

[0008] In U.S. Pat. No. 5,05,256 to Haag, a method for improving adhesion of paints to polydicyclopentadiene is proposed. A solution containing sodium hypochlorite and, preferably, a detergent is applied to the polymer by wiping. The solution is allowed to remain on the polymer surface for a 40-minute interval and is then washed off. Polydicyclopentadiene presents a unique and exotic polymeric structure. Without being bound to any theory, it is believed that the large number of unsaturated carbon— carbon linkages in the cyclic functionalities provides a material uniquely susceptible to interaction with hypochlorite compounds. Unfortunately, the method described in Haag has not been readily adaptable to other more commonplace polymers.

[0009] In U.S. Pat. Nos. 6,100,343 and 6,077,913 and Canadian Pat. No. 2,325,732 to Beholz, a method for improving adhesion of paints, glues, laminates and the like to polymeric substrates is described. A solution containing an oxidizer, such as bleach, and an organic acid, such as acetic acid, is contacted with the surface to be treated. Although the adhesion is imparted to the objects surface quickly and with ease, the method described by Beholz is limited in that only organic acids were determined to be appropriate activating species. This greatly reduced the number and type of activating agents that may be inexpensively employed. Furthermore, depending on the organic acid used, there is a significant potential for release of hazardous organic byproducts into the environment or volatile organic compounds (NOCs) into the air.

[0010] Additionally, polymeric materials provide excellent and versatile mechanical qualities and find use in a wide variety of applications. In certain instances, it would be highly advantageous to take advantage of the robust structural characteristics of various polymers while imparting surface characteristics not representative of the bulk polymer. For example, chromatographic and solid phase synthetic medias are primarily based on one of either of two solid supports, silica and polystyrene. Although these solid supports find utility in many applications, their use is limited due to their solubility properties. Silica based media are soluble in basic aqueous medias and polystyrene is soluble in a variety of common organic solvents. Furthermore, bonds of substrates to silica are inherently weak resulting in diminished media performance with time. For example, C-18 bound to silica is a very common media for reverse phase chromatography. The media makes available a very hydrophobic phase into which non- polar compounds may be retained allowing polar molecules to pass through the column without being significantly retained. . With time, the C-18 chains are lost as the bond to silica is relatively labile. Thus as time elapses the media becomes more and more polar in nature and thus less retentive to hydrophobic moieties. Polyethylene (PE) or polypropylene (PP) supported medias would have the advantage of the medias being virtually insoluble in any solvent. Furthermore, the bonding of species to carbon atoms results in bonds that are strong relative to bonds to silica.

[0011] Other applications in which species tethered to PE or PP as well as other polymeric substrates would find great utility include bonding biocompatible, reactive or otherwise functional polymers to the HPE or HPP substrates, greatly modifying the surface polarity, adhesiveness or hydrophilicity and/or reactivity such as, but not limited to, the incorporation of functionality to allow the formation of cross- linked structural components, drug release matrices and the like.

[0012] To this end, activity has been devoted to providing polymers with "permanent" chemically modified surface characteristics and to chemically modifying the surface characteristics of known polymeric materials.

[0013] Heretofore, no method has been proposed which promotes surface adhesion characteristics of a broad range of polymeric substrates in an efficient, economical and environmentally responsible manner that reduces reliance on chemical compounds which present handling and disposal difficulties; and, it is an object of the present invention to provide such a method. Since many of the compounds previously suggested for polymeric adhesion promotion are costly, difficult to obtain, or present handling or disposal problems, or may result in the formation of hazardous organic byproducts such as NOCs, it is a further object of the present invention to provide a method for improving surface adhesion characteristics of common polymeric substrates which employs relatively low-cost chemical commodities in an easily handled fluid medium such as an aqueous solution which does not require undue special handling considerations and will result in little or no emissions of organic compounds into the environment. It is desirable to provide a method and composition that can be incorporated onto the polymeric material at any point in its processing, using either an aqueous, vaporous or gaseous solution or an anhydrous mixture of reagents, thereby advantageously rendering a polymeric material which is paintable and/or exhibits improved surface adhesion, polarity or reactivity characteristics. It is also desirable that the method yield relatively consistent treatment results and be easy to implement and monitor in a plant or manufacturing setting. It is desirable that improvements in polymeric surface adhesion be accomplished in a rapid and uniform manner over the entire targeted polymeric surface area. Finally, it is desirable that the adhesion improvement method be one, which yields sufficiently permanent improvement in adhesion characteristics without unduly compromising other performance characteristics of the polymer.

[0014] Additionally, no method has been proposed which permits the replacement of halogen atoms on a broad range of halogenated polymeric substrates in an efficient, economical manner. Thus, it is desirable to provide methods that may be used to alter the surface characteristics of a halogenated polymeric material at any point in its processing, thereby advantageously rendering a polymeric material with a coating which permits its applicability to a broad range of uses. It is also desirable that the method yield a relatively consistent treatment results and be easy to implement and monitor in a plant or manufacturing setting. It is also desirable that alterations in polymeric surface adhesion be accomplished in a rapid and uniform manner over the entire targeted polymeric surface area. Finally, it is desirable that the adhesion modification method be one that yields sufficiently permanent alteration in adhesion characteristics without unduly compromising other performance characteristics of the bulk polymer.

SUMMARY [0015] The present invention is a method for improving surface adhesion, polarity and/or reactivity characteristics of a polymeric substrate or virgin or recycled polymeric material in which the portion of the surface of the polymeric substrate and/or entire virgin or recycled polymeric material to be treated is contacted with a composition containing at least one oxidizing agent and an activator. The oxidizing agent in the composition employed in the method of the present invention is present in a kinetically degrading state capable of producing at least one chemical intermediate that is reactive with the polymeric substrate and/or virgin polymeric material. Contact between the composition containing the oxidizing agent and activator compositions and the polymeric substrate/virgin polymeric material is maintained for an interval sufficient to modify functional groups present in the polymeric substrate/virgin polymeric material. The oxidizing agent of choice is a halogenated bivalent oxygen compound. The halogenated bivalent oxygen compound of choice is one that is capable of a controlled rate of oxidation and capable of activation to yield the desired kinetically degrading state. The reaction may be promoted by any suitable mechanical or chemical mechanism is greatly accelerated by an activator agent containing as a primary activator component an inorganic acid or acids or acid precursors optionally in combination with a compound or compounds having at least one carboxylic acid group, a carboxylic acid derivative, or synthetic equivalents thereof. The activator agent or agent combination may be present in the composition upon initial contact with the polymeric substrate/virgin polymeric material or may be added to the composition subsequent to initial contact with the polymeric substrate/virgin polymeric material.

[0016] Also, chemical methods for converting the halogen atoms or species on the surface of halogenated polyethylene (HPE), as well as other halogenated polymers, to other biocompatible, bioactive, chemical, organometallic, metal, polymeric or structural entities are disclosed herein. The method disclosed herein is predicated on the unexpected discovery that the halogen atoms on the surface of HPE are reactive despite their sterically hindered state. The methods described herein are executed in a variety of matrices in which the HPE is only very slightly soluble while the entities replacing the halogen atoms are at least slightly soluble. A variety of reagents for carrying out these conversions are also disclosed herein.

DETARJED DESCRIPTION [0017] The disclosure herein is predicated upon the unexpected discovery that the adhesion characteristics of a polymer substrate, particularly adhesion characteristics between the polymer substrate and an applied organic film can be significantly enhanced by processing the polymeric substrate with a solid, fluid and/or vaporous material containing at least one oxidizing agent that is subsequently activated using as a primary activating agent an inorganic acid.

[0018] The present disclosure is also predicated on the unexpected discovery that the halogen atoms on the surface of halogenated polymers are reactive despite their sterically hindered state. The chemical methods described herein are executed in a variety of matrices wherein the halogenated polymers are only very slightly soluble while the entities replacing the halogen atoms are at least slightly soluble. A variety of reagents for carrying out these conversions are also disclosed herein.

[0019] It is contemplated that surface processing/treatment of the polymer substrate may take place at any point in manufacture of the substrate, from treatment of the virgin or recycled polymeric material, and/or treatment of the material during molding/forming into a substrate, and/or treatment of the substrate after forming.

[0020] More particularly, the polymer of choice for treatment can be a halogenated polymer for which treatment converts at least a portion of the halogenated moiety present at or near the surface of the polymeric to a different chemical, organometallic, metallic, polymeric or structural entity or entities.

[0021] In surface treatment processing method as disclosed herein, it is contemplated that the oxidizing agent employed is a bivalent oxygen compound present in the fluid material in a kinetically degrading state. The oxidizing agent is capable of producing at least one chemical intermediate that is significantly reactive with atoms present in the polymeric substrate. The kinetic degradation of the oxidizing agent is enhanced or augmented by the presence of an activator agent.

[0022] The primary activator agent employed herein is one containing a chemical compound or formulation that includes an inorganic acid or acids or such functionality or their precursors that is optionally in combination with a chemical compound that has at least one carboxylic acid group, a carboxylic acid derivative, or synthetic equivalents thereof. It has been found, quite unexpectedly, that oxidation of the bivalent oxygen compound proceeds at a controlled rate, which is made useful by the creation of the kinetically degrading state. This process can be utilized to a process resulting in attachment to halogen atoms or other species on polymer surfaces and that the specific reagents employed to accomplish this are not limited.

[0023] As used herein, the term "activator" refers to chemical entity or entities that accelerate placement of the oxidizer or oxidizers into a kinetically degrading state. More specifically, disclosed herein are a class of activators that employ an inorganic acid(s) or inorganic acid precursor(s) as the primary activating species. An organic acid or acids or synthetic equivalents thereof may also be present in the activator.

[0024] As used herein, the term "primary activating species" refers to activator species that tend to ionize more quickly in solution than the organic activator species. The primary activating may also act synergistically with other activating agents to more efficiently place the oxidizing agent in a kinetically degrading state.

[0025] As used herein, the term "kinetically degrading state" is defined as a non-equilibrium state in which the oxidizing agent, specifically the halogenated bivalent oxygen compound experiences a change in oxidation state over time with the oxidizing agent having its highest oxidation number in its liighest concentration at a point closest to the initiation of the reaction process with a concomitant decrease in concentration of this species over time. The concentration of oxidizing agents having lower or lowest oxidation states is at its lowest at the outset of the method of the present invention with a concomitant increase in this species over time. The kinetically degrading state of the oxidizing agent produces at least one chemical intermediate or species that is reactive with the polymeric substrate. The chemical intermediate or species may be stable, unstable or transient. Stable intermediates can be defined herein as those that are readily isolatible for quantification and analysis. Unstable intermediates are defined herein as those that cannot be isolated for such quantification and analysis. Transient intermediates are considered those that react rapidly with the polymeric substrate or other components present in the system [0026] As used herein, the term "oxidizing agent" is a chemical compound which readily gives up oxygen, accomplishes the removal of hydrogen from another, preferably organic, compound or serves to attract negative electrons to accomplish the eventual hydrogen removal from the target compound.

[0027] The term "controlled rate of oxidation" as used herein is defined as a chemical reaction rate that proceeds with efficient evolution of quantities of reactive intermediate sufficient to interact with the polymeric substrate. The oxidation process proceeds without generation of excessive quantities of by-product such as devolved gaseous product or the like.

[0028] The method as disclosed herein can also include the step of introducing a suitable radical initiator into contact with the oxidizing agent to assist in placing the oxidizing agent into a chemically degrading state. Introduction can be by any means suitable for establishing contact between the oxidizing agent and the radical species.

[0029] As used herein the term "radical initiator" is taken to mean a compound or physical phenomenon that can contribute or possess electrons that can be utilized by the oxidizing agent. These can include, but need not be limited to, physical phenomena such as radiation as well as various molecules, and molecular fragments.

[0030] As used herein more specifically in the treatment of halogenated polymers, the term "chemical means" refers to the use of acids, bases, oxidizers, reducers, chemical catalysts, chemical radical initiators, heat, pressure and the like to promote, initiate, catalyze or otherwise make possible the conversion of the halogen atoms or species present in or associated with polymeric matrices to other species. It will be apparent to those skilled in the art that it is the ultimately the object of this invention to chemically convert halogen atoms or halogen species on polymer surfaces to other species and that the chemical means is not limited. [0031] As used herein, the term "halogenated polymer" refers to any polymer that has been or is halogenated. The polymeric material may be molded or present in any configuration or formation. Halogenation may be present throughout the polymeric object or matrix such as would be the case with polyvinylchloride (PNC). Alternately, the halogenation may be present or concentrated at or near the surface of the substrate such as in HPE. In the method disclosed herein the halogenated polymeric substrates or halogenated virgin polymeric materials for which conversion can be effected are, generally, those having halogen atoms attached to carbon atoms and are also characterized by the presence of large percentages of covalent carbon to carbon bonds such as alkane linkages present throughout the polymeric lattice. The halogenated polymeric materials of choice may be either thermosetting or thermoplastic materials. Nonlimiting examples of suitable halogenated polymers include addition polymers such as polyolefins, substituted polyolefins, and polyolefm blends. Halogenated polyolefins such as halogenated addition polymers including at least one of polyethylene, polypropylene polyisobutylene, polystyrene, polyisoprene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chlorides, polyvinylidine chlorides, polyacrylonitriles, and polyvinylacetates can be advantageously treated in the method disclosed herein.

[0032] While the process disclosed herein is particularly efficacious when employed with halogenated polyolefm addition polymers, it is to be understood that the process can also be employed to replace the halogen atoms of other halogenated polymers. Such halogenated polymers include, but are not limited to, halogenated polyalkyls and polyalkyl acrylates such as at least one of PNC, polystyrene (PS), polyurethane (PU), polymethyl methacrylate, and polymethyl acrylate.

[0033] Halogenated polyethylenes composed of substituted or unsubstituted alkalene monomers may also be treated by the process of the present invention. Examples of halogenated substituted alkylene polymers include polytetrafluoro ethylene, polytrichlorofluoroethylene and the like. Finally, other halogenated addition polymers can successfully be treated. This includes materials such as polyformaldehyde, polyacetaldehyde, polyisoprene and the like.

[0034] Additional halogenated condensation polymers that can be treated by the process disclosed herein include polyesters such as polyethylene terephth.alate and polybutylene terephthalate as well as polyamides, polyesters, polyurethanes, polysiloxanes, polyphenolformaldehydes, urea formaldehydes, melaminefornαaldehydes, cellulose, polysulfides, polyacetates, and polycarbonates.

[0035] The halogenated polymeric material employed in the halogenated substrate or halogenated virgin polymeric material can also be a thermoplastic elastomer such as at least one of styrene-isoprene-styrene, styrene-butadiene-styrene, copolyesters, copolyester ethers, silicone-polyamides, silicone-polyesters, silicone-polyolefins, silicone- styrenes, aromatic polyether-urethanes, alpha cellulose filled ureas, polyvinyl chloride- acetates, and vinylbutyrals.

[0036] The halogenated polymeric material employed in the halogenated substrate or halogenated virgin polymeric material may further be a co-polymer such as at least one of the group that includes polyester-polyethers, polyether-polysiloxanes, polysiloxane-polyamides, polyesteramides, copolyamides, and nylons.

[0037] It is also within the purview of this disclosure that the halogenated polymeric substrate or halogenated virgin polymeric material can be a blend or alloys containing any of the enumerated polymers as a major constituent. Various blends and alloys are known to the skilled artisan. It is contemplated that the process disclosed herein can be utilized with various polymeric blends and alloys without undue adverse consequences to the blend or alloy.

[0038] In the surface treatment method disclosed herein, polymeric substrates or virgin or recycled polymeric materials for which adhesion, polarity or reactivity improvement can be effected are, generally, those having hydrogens attached to carbon atoms characterized by large percentages of covalent carbon bonds; typically alkane linkages present throughout the polymeric lattice. Without being bound to any theory, it is believed that the presence of large numbers of covalent bonds in the polymeric lattice renders the polymeric material relatively unreactive and difficult to make adhesive, polar or reactive. The polymeric materials of choice may be either thermosetting or thermoplastic materials. Examples of suitable polymers include addition polymers selected from the group consisting of polyolefins, substituted polyolefins, and polyolefin blends. Preferred polyolefins are addition polymers selected from the group consisting of polyethylene, polypropylene polyisobutylene, polystyrene, polyisoprene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chlorides, polyvinylidine chlorides, polyacrylonitriles, polyvinylacetates, and mixtures thereof. It has been found that the process disclosed herein is particularly efficacious when performed on these addition polymers. Adhesive properties inherent in certain polyolefin addition polymers are particularly low. Modification of such properties to increase paintability of the polyolefin is highly desirable and, heretofore, limitedly successful.

[0039] While the surface treatment process disclosed herein is particularly directed to polyolefin addition polymers, it is to be understood that the process can also be employed to increase adhesive properties of other polymers which are generally recognized as more paintable. These latter polymers include halogenated polyalkyls and polyalkyl acrylates, selected from the group consisting of polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, and mixtures thereof.

[0040] Polyethylenes composed of substituted or unsubstituted alkalene monomers may also be treated by the process of the present invention. Examples of substituted alkylene polymers include polytetrafluoroethylene, polytrichlorofluoroethylene and the like. Finally, other addition polymers can successfully be treated. This includes materials such as polyformaldehyde, polyacetaldehyde, polyisoprene and the like.

[0041] Condensation polymers which exhibit marked increases in adhesive ability include polyesters selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and mixtures thereof. Other polymeric materials which can be treated by the process of the present invention can be condensation polymers such as those selected from the group consisting of polyamides, polyesters, polyurethanes, polysiloxanes, polyphenolformaldehydes, urea formaldehydes, melamineformaldehydes, cellulose, polysulfides, polyacetates, polycarbonates, and mixtures thereof.

[0042] The polymeric material employed in the substrate or virgin polymeric material can also be a thermoplastic elastomer selected from the group consisting of styrene-isoprene-styrene, styrene-butadiene-styrene, copolyesters, copolyester ethers, silicone-polyamides, silicone-polyesters, silicone-polyolefins, silicone-styrenes, aromatic polyether-urethanes, alpha cellulose filled ureas, polyvinyl chloride-acetates, vinylbutyrals, and mixtures thereof. Other polymeric material surfaces that can be modified by the following invention include but are not limited to polymers classified as amorphous, crystalline, isotactic, syndiotactic and the like. It is also contemplated that the material may be a suitable mixture, blend or alloy of such polymers..

[0043] The polymeric material employed in the substrate or virgin polymeric material may further be a co-polymer selected from the group consisting of polyester- polyethers, polyether-polysiloxanes, polysiloxane-polyamides, polyesteramides, copolyamides, ethylene-tetrafluoroethylene, nylons, and mixtures thereof. Most preferred co-polymers include those with ethylene, propylene, or other olefinic functionality within.

[0044] It is also within the purview of the disclosure contained herein that the polymeric substrate or virgin or recycled polymeric material can be a blend containing as a major constituent any of the enumerated polymers.

[0045] It is to be understood that various polymeric substrates or virgin polymeric material have varying degrees of adhesion ability. Thus, the method of the present invention is most efficaciously employed for improving polymeric materials with relatively poor initial adhesion/polarity/reactivity characteristics such as polyolefin polymeric substrates/virgin polymeric materials, polyester polymeric substrates/virgin polymeric materials, and mixtures thereof. The specific polymeric substrates/virgin polymeric materials for which the adhesion improvement method of the present invention shows the most dramatic results are polymers selected from the group consisting of polyethylene, polypropylene, polystyrene, polyisobutylene, polyethylene terephthalate, polybutylene terephthalate, ethylene-tetrafluoroethylene and mixtures thereof. It is anticipated that the polymeric substrates most advantageously improved by the process of the present invention are those that contain one or more of the enumerated polymers as a major constituent thereof. It is also within the purview of this invention that the polymeric substrate may include other compounds such as plasticizers, elastomers, plastomeis, fillers, oxidation stabilizers, thermal stabilizers, fire retardants, colorants, and the like compatible with the adhesion improvement method of the present invention.

[0046] In the surface treatment method disclosed herein, at least a portion of the surface area of the polymeric substrate is contacted with a fluid material containing at least one oxidizing agent. It is anticipated that the method disclosed herein can be successfully implemented on polymeric material which has been formed, extruded, or otherwise processed into a finished or intermediate part generally considered ready for painting or other processing for which increased adhesion characteristics are desired. Examples of such processes include, but are not limited to, joining, laminating and the like. It is within the purview of this invention that the entire polymeric substrate be contacted with the fluid material containing the oxidizing agent. However, it is also within the purview of this invention that the polymeric substrate be masked or otherwise prepared so that only the desired portion of the surface area of the polymeric substrate be so treated.

[0047] The fluid material containing the oxidizing agent may be any liquid, vaporous or gaseous composition or combination thereof that is capable of containing and conveying the oxidizing agent into contact with the polymeric substrate surface to be treated. Preferably, the fluid material is an aqueous solution containing sufficient quantities of the oxidizing agent to effect the appropriate chemical reaction in the desired manner at the desired rate. The polymeric surface may be exposed to this solution or separate solutions contaimng the activator and oxidizer by dip, spray or vaporous contacting of said reagents with or without reagent matrices.

[0048] The oxidizing agent of choice is one that is capable of kinetically degrading from its highest oxidized state into lower intermediates in a controlled or controllable reaction mechanism. The oxidizing agent may also be a material that can be rendered capable of such kinetic degradation in a controlled rate of reaction.

[0049] The oxidizing material employed can be is a compound that will generally evolve halogen or a halogen analog at a controlled rate, particularly when brought into contact with materials containing functionality of carboxylic acid, carboxylic acid derivative, or synthetic equivalents thereof. As used herein, the term "halogen or a halogen analog" is defined as one of the electronegative elements of Group NIIA of the Periodic table or a material that will perform the same or similar function in the process of the present invention. Halogens that can be employed include at least one of chlorine, bromine, and iodine. Halogen analogs can include at least one of boron, nitrogen and mixtures thereof.

[0050] In the surface treatment process disclosed herein, the oxidizing agent may be is a halogenated bivalent oxygen compound including at least one of oxycompounds of chlorine, and oxycompounds of bromine, oxycompounds of iodine, oxycompounds of nitrogen. Without being bound to any theory, it is believed that the selected oxidizing compounds kinetically degrade into an intermediate.

[0051] Oxycompounds of chlorine which can be utilized as the bivalent oxygen oxidizing agent include at least one of hypochlorous acid, alkali metal salts of hypochlorous acid and hydrates thereof, alkaline earth metal salts of hypochlorous acid and hydrates thereof, perchloric acid, alkali metal salts of perchloric acid and hydrates thereof, alkaline earth metal salts of perchloric acid and hydrates thereof, chloric acid, alkali metal salts of chloric acid and hydrates thereof, alkaline earth metal salts of chloric acid and hydrates thereof.

[0052] Oxycompounds of bromine which can be utilized as the bivalent oxygen oxidizing agent at least one hypobromous acid, alkali earth metal salts of hypobromous acid and hydrates thereof, alkaline earth metal salts of hypobromous acid and hydrates thereof, bromic acid, alkali metal salts of bromic acid and hydrates thereof, alkaline earth metal salts of bromic acid and hydrates thereof.

[0053] Oxycompounds of iodine which can be employed as the bivalent oxygen include at least one of iodic acid, alkali metal salts of iodic acid and hydrates thereof, alkaline earth metal salts of iodic acid and hydrates thereof, periodic acid, alkali metal salts of periodic acid and hydrates thereof, alkaline earth metal salts of periodic acid and hydrates thereof.

[0054] Oxycompounds of boron that can be employed as the bivalent oxygen compound include at least one ofboric acid, alkali metal salts of boric acid and hydrates thereof, alkaline earth metal salts ofboric acid and hydrates thereof, perboric acid, alkali metal perborates and hydrates thereof, alkaline earth metal perborates and hydrates thereof.

[0055] Oxycompounds of nitrogen which can be employed as the bivalent oxygen oxidizing agent include at least one of nitric acid, alkali metal salts of nitric acid and hydrates thereof, alkaline earth metal salts of nitric acid and hydrates thereof.

[0056] The oxycompound of choice can be a compound or mixture of compounds capable of kenetic degradation in a sufficiently controlled steady manner. Nonlimiting examples of suitable oxycompounds employed as the oxidizing agent include at least one of hypochlorous acid, alkali metal salts of hypochlorous acid, hydrates of hypochlorous acid, alkaline earth metal salts of hypochlorous acid and hydrates of alkaline earth metal salts. Specific oxidizing agents include, but are nto limited to, hypochlorous acid, calcium hypochlorite, sodium hypochlorite, calcium hypochlorite tetrahydrate, lithium perchlorate, lithium perchlorate trihydrate, magnesium perchlorate, magnesium perchlorate dihydrate, potassium chlorate, sodium perchlorate, lithium nitrate, magnesium iodate tetrahydrate, magnesium nitrate hexahydrate, nitro salicylic acid, sodium perborate tetrahydrate. In at least one embodiment of the method disclosed herein, the oxidizing agent is selected from the group consisting of hypochlorous acid, calcium hypochlorite, sodium hypochlorite, lithium perchlorate, magnesium perchlorate, sodium perchlorate, potassium chlorate, and mixtures thereof with materials such as sodium hypochlorite, calcium hypochlorite, calcium hypochlorite tetrahydrate, and mixtures thereof being of particular utility.

[0057] The oxidizing agent can be present in aqueous solution in a concentration sufficient to provide material that can kinetically degrade to an intermediate that will interact with the polymeric substrate with which it is brought into contact.

[0058] In the surface treatment process of the present invention, the oxidizing agent is maintained in an aqueous solution at a concentration between about 0.25% and 25% by volume, with an oxidizing agent concentration between about 0.5% and about 6.00% by volume being preferred and an oxidizing agent concentration between about 2.6% and about 6.00% by volume being most preferred. It should be noted that an oxidizer concentration of 6.00% is the concentration of various consumer-grade bleach compositions. The oxidizing agent of the present invention may be used in solid form, and/oi as a solid(s) suspension.

[0059] It is within the purview this disclosure that other liquid or gaseous materials can be employed as an activating agent for the oxidizing agent, provided that the liquid or gaseous material does not adversely interact with the oxidizing agent or polymeric substrate. Aqueous solutions can be advantageously employed for purposes of economy and handling ease. However, it is also to be understood that the activating agent may be used in solid form, and/or as a solid(s) suspension. [0060] The oxidizing agent may be employed in combination with a suitable activating agent capable of preferably reacting with the oxidizing agent to produce the intermediate species which is, in turn, reactive with the polymeric substrate. The activating agent is an organic material or derivative thereof having at least one carboxylic acid functionality or derivative thereof.

[0061] The primary activating agent employed in the process disclosed herein can include an inorganic acid or acids or inorganic acid precursors or various mixtures and may be comprised of any inorganic acid type including but not limited to binary acids, Bronsted acids, hydrohalic acids, oxyacids such as hypohalous acids (HXO), Halous Acids (HXO₂), Halic Acids (HXO₃), Perhalic Acids (HXO₄), Paraperhalic Acids (H₅XO₆), Lewis acids, mineral acids, polyprotic acids, ternary acids, or weak or strong inorganic acids or acid salts and acids formed from the class of pseudohalides and pseudohalogens. Examples of inorganic acids and their precursor identities include but are not limited to the following: Arsenic, Arsenious, -Boric, Carbonic, Chromic, Germanic, Hydrocyanic, Hydrogen Sulfide, Hydrogen Peroide, Hypobromous, Hypochlorous, Hypoiodous, Iodic, Nitrous, Periodic, o-Phosphoric, Phosphorous, Pyrophosphoric, Selenic, Selenious, m-Seliάc, o-Selicic, Sulfuric, Sulfurous, Telluric, Tellurous, Tetraboric, and the like. Examples of inorganic acids and their precursor formulas include but are not limited to the following: HF, HC1, HBr, HI, H₂SO₃, H SO , HNO₂, HNO₃, HFO, HFO₂, HFO₃, HFO₄, H₅FO₆, HClO₂, HClO₃, HC10₄, H₅ClO₆, HBrO₂, HBrO₃, HBrO₄, H₅BrO, HIO₂, HIO3, HIO4, H5IO₆, H₂SeO₃, H₂SeO₄, H₃PO₃, H₃PO₄, SO₂, HSO₃ H₂SO₃, HSO₄ H₂SO₄, H₂S₂O₃, HNO₃, NO₂, N₂O₅, HMnO₄, H₂Cr₂O₇, PCI3, PCI5, POCl₃, P₄Oιo, H₃PO₃, H₃PO₄, HCN, HCNO, HNCO, HSCN, HSeCN, HTeCN, HN₃, HSCSN₃, H₂S, H₂Se, H₂Te, A1C1₃, FeCl₃, HSiO₃, H4SiO₄, H_fiSi₂O , BF₃-etherate, BC1₃, SnCl₄, H CO₃, CO₂, and the like. The optional carboxylic acid or acids has the general formula:

wherein x and y are integers between 0 and 20 inclusive, with the sum of x and y being an integer of 20 or less, wherein R is a functionality selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups, branched or unbranched alkyl groups, the alkyl group having between 1 and 27 carbon atoms, and mixtures thereof, and wherein each variable R', R", R'" and R"" is a functionality selected from the group consisting of hydrogen, amines, hydroxyl, phenyl, phenol radicals, and mixtures thereof, each of the above-mentioned R variable functionalities being chosen independently of the other R variable functionalities, and wherein R" may also be selected from the group consisting of anhydrides, halide salts, selenic acid salts, perchloric acid salts, boric acid salts, and mixtures thereof; and wherein the dicarboxylic acid has the general formula:

wherein x is an integer between 1 and 20 inclusive and R and R' are functionalities selected from the group consisting of hydrogen, hydroxyl radicals, amines, phenyl radicals and mixtures thereof. It is also contemplated that mixtures of various carboxylic acids and dicarboxylic acid compounds can be employed either alone or in combination with one another.

[0062] Heretofore the use of activator compositions incorporating as a primary component an inorganic acid, acids, and/or inorganic acid precursors was not thought to be of utility considered impractical due to the high reactivity of these activating reagents. The activator compositions disclosed herein were prompted by the discovery that controlled additions, decreased activator concentrations, and combinations of various inorganic acids alone or in combination with organic acids provide comparable if not improved adhesiveness while eliminating risks associated with the use of organic based activators.

[0063] Some other additional suitable primary activators may include hydroxylamine hydrochloride, phosphorous pentachloride, phosphorous pentoxide, phosphoryl chloride, sulfurous acid, sulfuryl chloride, thionyl chloride, and, less preferably, phenols and catechols (these are both weakly acidic). It is to be understood that the numbers mentioned above in both formulae for the number of carbons represented by "x" and "y" represent most "simple" molecules. However, it is to be understood that these formulas are illustrative, and the present invention is not to be limited thereto. Within the purview of the present invention, there is no real limit on the number of carbons represented by "x" and "y." In the extreme case of polymers, x and y would simply be between 2000 and 500,000. Also, in the instance of polymers, the number and distribution of x and y could vary greatly from ordered to random and from alternating to block.

[0064] A nonlimiting example of a polymer that may degrade in water to yield an acid suitable for use as the activating agent includes, but is not limited to polyp osphoric acid. Examples of suitable acidic polymers include, but are not limited to poly(melamine-co-formaldehyde)s, polyacrylic acids, and salts thereof.

[0065] Further, regarding each of the R variables mentioned hereinabove, ie. R, R¹, R", etc., it is to be understood that the R groups are not intended to be limited to the above-identified species. For example, in a random branched polymer, the R groups may include a nearly infinite array; eg. the R groups may contain repeating ether linkages (such as in PEG), repeating amide linkages (such as in the polyamides), etc. The R groups may also contain combinations of any variety of functional groups. Another possibility is that one R group may be attached to another R group forming a ring. These rings may also contain functionality and branching. Furthermore, any of the branches in any of the aforementioned systems may be terminated with an additional functional group. A partial listing of functional groups that are commonly found in or at the end of molecules include: ethers, esters, amides, ketones, aldehydes, alcohols, nitrites, alkenes, alkynes, cyano groups, sulfur, sulfates, phosphor, phosphates, nitrogen, amines, nitro groups, as well as diazonium species etc.

[0066] Suitable carboxylic acids include at least one of butyric acid, lactic acid, propionic acid, heptanoic acid and formic acid. Derivatives of these mild carboxylic acids are also contemplated, as well as synthetic equivalents thereof. Specifically contemplated are acid anhydrides, acid chlorides, acid bromides and polyacids, such as heptanoic acid, butyric anhydride, heptanoic anhydride and the like. Examples of acid chlorides that can be effectively employed include, but are not limited to, palmitic chloride, fumeryl chloride, and the like.

[0067] Suitable dicarboxylic acids, acid derivatives, and synthetic equivalents thereof include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, and fumaric acid. It is within the purview of this disclosure that the activating agent be a mixture of these compounds. It is also within the purview of this disclosure that the activating agent be a derivative of dicarboxylic acid including, but not limited to, acid anhydrides, acid chlorides, acid bromides and polyacids. Particular examples of these include, but are not limited to materials such as acetic anhydride, oxalic acid dihydrate, acetile bromide, acetile chloride, 2 acetile benzoic acid, 4 acetile benzoic acid, bromoacetic acid, acetic acid, glacial acetic acid, vinegar, calcium oxylate, chlorobenzoyl chloride, 3 chlorobenzoyl chloride, citric acid, citric acid monohydrate, bibenzilazodicarboxylate, diglycolic acid, fumaric acid, furmeryl chloride, galic acid, galic acid monohydrate, oxalic acid, subasic acid, pyruvic acid, succinic acid, succinic anhydride, succinyl chloride, 5 sulfo salicylic acid, tannic acid, tartaric acid, and mixtures thereof.

[0068] An additional class of dicarboxylic acids includes the bridged carboxylic acids of the phthalate and succinimide types, such as terephthalic acid and succinimide. [0069] It is to be understood that the amino acids and poly-amino acids form another class of acids contemplated as being effective activating agents. Suitable examples thereof include, but are not limited to aspartic acid and polyaspartic acid.

[0070] In a preferred embodiment of the surface treatment method, the activating agent of choice is one which, when added to the solution containing the oxidizing agent will result in the dissolution of the activating agent and dispersal throughout the solution. The addition of activating agent may also lead to an increase in solution temperature depending upon the particular activating agent employed and the amount added. Preferably, the amount and particular activating agent employed produces a rate of kinetic degradation of oxidizing agent which is manageable and yields a treatment solution which will provide for prolonged successful polymeric surface adhesion promotion. Ideally, the rate of kinetic degradation is one that will permit use of the treatment solution for intervals upwards of a day before replacement or recharging is required, with use intervals of seven to ten days being preferred. The interval during which the treatment solution is active will vary depending upon parameters such as temperature, the amount of polymeric substrate treated and the like.

[0071] In the surface treatment process disclosed herein the primary activating agent is maintained in an aqueous solution at a concentration between about 0.02% and 10% by volume, with a primary activating agent concentration between about 0.2% and about 2% by volume being preferred. The preferred amount of said organic acid in said inorganic activator solution is at a concentration between about 0.02 % and 10 % by volume with the organic acid concentration between about 0.2% and about 2% by volume being preferred.

[0072] In the surface treatment process disclosed herein, the activating agent material is preferably one that will promote dissolution of the activating material without liberation of undesirable gasses such as halogen gas or other unsuitable byproducts or VOCs. In a preferred embodiment, the amount of activating agent employed is that sufficient to produce reactive intermediate capable of adhering to and/or interacting with the polymeric substrate. In the preferred embodiment, it is anticipated that the reactive intermediates react with the plastic substrate to add functionality that improves the adhesive properties of the polymeric material without unduly compromising polymeric performance.

[0073] Other compounds may be used as the activating agent, including but not limited to potassium acetate, and hydrogen peroxide.

[0074] In an embodiment of the surface treatment process, the primary activating agent is selected from the group consisting of inorganic acid or acids or inorganic acid precursors may be comprised of any inorganic acid type including but not limited to binary acids, Bronsted acids, hydrohalic acids, oxyacids such as hypohalous acids (HXO), Halous Acids (HXO₂), Halic Acids (HXO₃), Perhalic Acids (HXO₄), Paraperhalic Acids (HsXOβ), Lewis acids, mineral acids, polyprotic acids, ternary acids, or weak or strong inorganic acids or acid salts and acids formed from the class of pseudohalides and pseudohalogens. Examples of inorganic acids and their precursor identities include but are not limited to the following: Arsenic, Arsenious, o-Boric, Carbonic, Chromic, Germanic, Hydrocyanic, Hydrogen Sulfide, Hydrogen Peroide, Hypobromous, Hypochlorous, Hypoiodous, Iodic, Nitrous, Periodic, o-Phosphoric, Phosphorous, Pyrophosphoric, Selenic, Selenious, m-Selicic, o-Selicic, Sulfuric, Sulfiirous, Telluric, Tellurous, Tetraboric, and the like. Examples of inorganic acids and their precursor formulas include but are not limited to the following: HF, HC1, HBr, HI, H₂SO₃, H₂SO₄, HNO₂, HNO₃, HFO, HFO₂, HFO₃, HFO₄, H₅FO₆, HClO₂, HClO₃, HClO₄, H₅ClO₆, HBrO₂, HBrO₃, HBrO₄, H₅BrO, HIO₂, HIO₃, HIO₄, H5IO₆, H₂SeO₃, H₂SeO₄, H₃PO₃, H₃PO₄, SO₂, HSO₃ ^", H₂SO₃, HSO₄; H₂SO₄, H₂S₂O₃, HNO₃, NO₂, N₂O₅, HMnO₄, H₂Cr₂O₇, PC1₃, PC1₅, POCl₃, P₄Oιo, H₃PO₃, H₃PO₄, HCN, HCNO, HNCO, HSCN, HSeCN, HTeCN, HN₃, HSCSN3, H₂S, H₂Se, H₂Te, A1C1₃, FeCl₃, HSiO₃, HιSiO₄, H₆Si₂O₇, BFs-etherate, BC1₃, SnCl₄, H₂CO₃, CO₂, and the like. The optional carboxylic acid or acids has the general formula:

wherein x and y are integers between 0 and 20 inclusive, with the sum of x and y being an integer of 20 or less, wherein R is a functionality selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups, branched or unbranched alkyl groups, the alkyl group having between 1 and 27 carbon atoms, and mixtures thereof, and wherein each variable R', R", R¹" and R"" is a functionality selected from the group consisting of hydrogen, amines, hydroxyl, phenyl, phenol radicals, and mixtures thereof, each of the above-mentioned R variable functionalities being chosen independently of the other R variable functionalities, and wherein R" may also be selected from the group consisting of anhydrides, halide salts, selenic acid salts, perchloric acid salts, boric acid salts, and mixtures thereof; and wherein the dicarboxylic acid has the general formula:

wherein x is an integer between 1 and 20 inclusive and R and R' are functionalities selected from the group consisting of hydrogen, hydroxyl radicals, amines, phenyl radicals and mixtures thereof.

[0075] Nonlimiting examples of polymeric objects that may be treated by the herein disclosed method include but are not limited to very small objects such as particulates or powders or polymer coated powders, grains and the like, such as those that might be used as chromatographic media. Conversely, the polymeric objects may be very large such as truck components, jet skis, and boat hulls. Additional exemplary objects that may be modified with respect to their adhesive, polarity or reactivity characteristics include but are not limited to, particulate beds for bacterial growth, solid support media for solid supported chemistry; motorcycle components such as fuel tanks, fenders, and the like; automotive components such as A-, B- and C-pillars, fascias and the like; truck and RV components such as cabs, fenders, fascias and the like; passenger train, bus and aircraft components such as overhead baggage compartments, wall, ceiling and floor components and the like; farm equipment components such as roofs, tailgates, shoots, cabs and the like; watercraft components such as hulls, decks, roofs and the like; lawn and garden products such as furniture, fencing, blow molded sheds and the like, children's toys such as motorized vehicles, bikes, small scale automotive replicas and the like; tote boxes and containers such as tool boxes, cell phone housings, tool boxes and the like; building components such as window trim, siding, doors, garage doors, shingles, siding and the like; military components such as external panels on vehicles and helicopters, gun magazines and the like; home interior products such as cabinets, bathroom appliances, appliances such as cloths washing machines, dishwasher fronts and the like; out-of-doors products such as camper and cooler components and the like; sign and display components such as billboards, road signs and the like; micro-electronic components such as boards and medical device components and implants such as the inner surfaces of extracorporeal surfaces, catheters, stents, joint replacement components and drug delivery devices, and preparation of macroscopically enhanced surfaces such as visual, audio, or reactivity enhancement.

[0076] The efficiency of the activator in placing the oxidizing reagent in a kinetically degrading state may further be enhanced through the use of radical initiators. The addition of small amounts of iodine, for example, to the oxidizer solution prior to the addition of the activating agent has shone to greatly increase the rate of surface modification.

[0077] Radical initiators contemplated to assist in placing the oxidizing agent in a kinetically degrading state can include, but are not limited to, physical phenomena in various visible and nonvisible spectra such as ultraviolet as well as other forms of radiation including heat. Chemical radical initiators include but are not limited to iodine (12), Group IA metals such as Li, Na and K, Group IIA metals such as Be, Mg and Ca, Group B metals such as Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt, Au and the like. Also contemplated are combinations of known radical initiators such as metals in ammonia, iron in combination with peroxides and the like, as well as salts of metals such as TiC13 and NaNO2 and miscellaneous radical initiators such as diphenylpicrylhydrazyl radical (DPPH), Azo-type radical initiators, nitroxides and the like.

[0078] Types of peroxide radical initiators contemplated include, but are not limited to, hydroperoxides, ketone peroxides, peroxyacids, dialkylperoxyacids, peroxyesters, peroxycarbonates, diacylperoxides, peroxydicarbonates, peroxyketals, cyclic ketone peroxides and the like.

[0079] Exemplary specific radical initiators include, but are not limited to, tert-Amyl peroxybenzoate, 4,4-Azobis(4-cyanovaleric acid), 1,1'- Azob -'(cyclohexanecarbomtrile), 2,2'-Azobisisobytyronitrile (ALBN), Benzoyl peroxide, 2,2-Bis(tert-butylperoxy)butane, l,l-Bis(tert-butylperoxy)cyclohexane, other "tert- butylperoxy" initiators, tert-Butyl hydroperoxide, other "tert-Butyl" peroxides, Cumene hydroperoxide, anr other "peroxides", Peracetic acid and Potassium persulfate.

[0080] Examples of various reaction mechanisms are outlined below. These include, but are not limited to, light catalyzed reactions. In such reactions light in various spectra including both visible and/or ultraviolet can be employed to decompose various organic and inorganic compounds.

UN-Light (200nm) - 586 KJmol^"1

_C[ c_{| ►} 2 CI * Δ G^# = 243 KJmol^"1

_Sr — _{Br ►} 2 Br - Δ G^# = 192 KJmol^"1

I 1 2 I - Δ G^# = 151 KJmol^'1 [0081] Peroxide compounds can also be employed. It is contemplated that such compounds can be capable of autodecomposition or may be catalyzed by other suitable reactions. Nonlimiting examples of reaction mechanisms are set forth below.

Other Peroxide Initiators

DTBPO

[0082] Heat catalyzed reactions can include but need not be limited to Azo initiators as well as various organometallic compounds. Heat can be supplied by external sources as well as from various reaction byproducts. Non-limiting examples are listed below: AZO Initiators

Azobisisobutyronjtrile (AIBN) I

[0083] Organometallics, in which C-M bonds have low BDE, and are easily homolysed to give radicals; f"³ HEAT H₃C-Pb-CH₃ — ^ ^» Pb + 4 CH₃ ^# CH₃ π

PhjBr Mg ^► Ph Mg-Br ^ Ph-MgBr

nion

σ-imidazoyl radical Initiation using a metal in ammonia

ArX + NH3 (ArX)^" rv

Fento.ns Reaction 2+ HO— OH + Fe Fe 3+ + OH + * OH hydrogen peroxide

analysis -• r I H ^O — OH i I OH OH also, 2+ 3+ f-BuOOH + Fe t-BuO + OH + Fe [0084] It is also contemplated that various Long-lived radicals, which are typically un-reactive and considered to have limited utility in organic synthesis can be emploved herein. Nonlimiting examples are listed: Gomberg - 1900

VI

oiohenylpiciylhydraz l ratficsl, DP& vπ

[0085] Finally, various nitroxides, ring structures, and animated aromatics can also be employed as outlined below

TEMPO TMIO (red) (orange-yellow) vm

50% rx

-8 NO x

TEST METHOD [0086] Paint adhesion to opolymeric surfaces treated according to the process disclosed herein can be determined and examined by any suitable method such as that outlined in test method ASTM D3359-78, wherein the painted surface is cross-hatched; a piece of transparent tape is secured to the surface; and the tape is then peeled off at about a 90. degree angle. Paint adhesion will also examined by a variation of test method ASTM D3359-78 in which the painted surface is not cross-hatched. In the following experiments, the bath will be considered operative until subsequent painting (with 2 coats of RUST-OLEUM Gloss Protective Spray Enamel, Gloss Black 7779) and testing of sample pieces will reveal a drop of adhesiveness to paint of approximately 50% from a starting adhesiveness of >98% as measured qualitatively by visual inspection. The drop is anticipated to be generally sudden.

[0087] Contact between the polymeric surface and the treatment solution may be accomplished by dipping the polymer into a bath containing the treatment solution, it is to be also understood that the polymer may be exposed to the treatment solution by any suitable method, including but not limited to spraying a heated or unheated treatment mist onto the polymer, spraying a treatment mist onto a heated polymer, and the like.

[0088] Some alternate methods of the surface treatment process disclosed herein for treating the polymer(s) are discussed hereinbelow. The polymeric articles may be treated at other times during their processing. For example, a solution as disclosed hereinabove, or an anhydrous mixture of reagents disclosed hereinabove could be fed directly into the mouth of a press screw via a hopper or other means. The polymer beads used in processing could also be treated at the polymer manufacturer prior to shipment or further processing. As the beads are melted in the barrel or screw, the treated surfaces would be mixed throughout the polymer melt. After shooting the part, some of the treated material would be exposed, thus rendering a polymeric article paintable and/or adherable after molding without need for post-molding treatment before application of paint or the like.

[0089] Without being bound to any theory, it is believed that the surface treatment method disclosed herein enhances adhesive, polarity and/or reactivity properties in an environmentally responsible manner, and may impart unexpected and inventive properties on the polymer through polymer crosslinking, or by increasing polymer compatibility. A new type of ultra-high molecular weight branched polyethylene (PE) or other plastic may result, thereby providing for increased stiffness and impact strength. A PE capable of being blended with less expensive non-block elastomers or other polymers may also result. Further, the necessity of compatibilizer use may be reduced. [0090] For example, a polyolefin material may be prepared by submersing it in a suitable solution of the inventive oxidizing agent and activating agent, under suitable conditions, until the polyolefin is wetted. The material may then be further processed, thereby treating the polyolefin material. The treated polyolefin material may then be mixed with previously incompatible polymers, thereby producing inventive copolymer blends upon processing.

[0091] The treated polyolefin material may alternately be mixed with a reactive polymer, thereby forming inventive, highly crosslinked, strong structural polymers upon processing. Crosslinking of, for example, polyethylene, increases its strength properties and extends the upper temperature limit at which this plastic can be used.

[0092] The treated polyolefin material may alternately be mixed with several unlike polymers, thereby making them compatible.

[0093] Further, the treated polyolefin material may alternately be mixed with a reactive polymer and shipped prior to processing or after partial reaction. The inventive polymer blend may then be used as a highly crosslinked thermoset polymer.

[0094] The method disclosed herein can be advantageously employed to produce polymers suitable for use as paintable auto parts; house and garden products; medical devices coated with biocompatible materials; new manufacturing techniques involving gluing polyethylene and/or polypropylene pieces together (a replacement for heat welding and mechanical joints); use of polyethylene and/or polypropylene films as laminates to prepare chemical resistant surfaces; and for providing containers and structural components with increased physical properties.

[0095] It has been determined that the method disclosed herein can be used quite efficaciously to modify the surface of halogenated polymers including, but not limited to, halogenated polyethylene and halogenated polypropylene. The halogenated moieties present on at or near the polymeric surface can be converted to other chemical, organometalhc, metallic, polymeric or structural entities.

[0096] In the treatment method for halogenated polymers disclosed herein, at least a portion of the halogenated surface area of the polymeric substrate is contacted with a treatment matrix. The treatment matrix may act as a reagent and/or carry one or more chemicals suitable for surface treatment.

[0097] It is contemplated that the method disclosed herein can be successfully implemented on halogenated polymeric material which has been formed, extruded, or otherwise processed into a finished or intermediate part generally considered ready for use or other processing for which the desired surface characteristics are sought. Such characteristics can include, but are not limited to, chemical separation, growth of bio- organisms, solid supported chemical synthesis, water treatment, biocompatibility, bio activity and adhesion alteration. It is within the purview of this disclosure that the entire surface area of the halogenated polymeric substrate be contacted with the treatment matrix. However, it is also contemplated that the halogenated polymeric substrate can be masked or otherwise prepared so that only the desired portion of the surface area of the polymeric substrate to be so treated. Suitable masking and surface preparation techniques are those generally known to those skilled in the art.

[0098] As used herein, the term "surface or very near surface" refers to the surface of the halogenated polymeric object(s) or material being treated as well as the region proximate to the surface of halogenated polymeric object. The proximate region may be that region halogenated as a result of solvating portions of polymer chains located near the surface during a halogenation step or in selected regions such as regions exhibiting different amorphous/crystallinity characteristics. Thus halongenation can be concentrated in the foregoing regions.

[0099] It is also possible that the entire surface of the polymer may be somewhat solvated and it is possible that only portions of the surface may be solvated such as amorphous regions or regions exhibiting other topographical variation. It is also contemplated that none of the surface is solvated, but may contain halogens imparted by other processes such that the halogen atoms or species on the polymer surfaces are have been chemically converted to other species during the "halogenation " process such as chlorination and the like. Thus the specific location of the halogen atoms and species are not strictly limited but can be generally considered to be located at or near the surface of the polymeric object or material.

[00100] As used herein, the term "very nearly heterogeneously" refers to the possible very slight solvation of near surface polymer chains. In these locations the reaction is more homogeneous as there is a greater solvation effect. It is also possible that the entire surface of the polymer is somewhat solvated and it is possible that only portions of the surface are solvated such as amorphous regions or regions exhibiting other topographical variation.

[00101] As used herein, the term "halogen atoms or species" includes species containing a halogen entity or any species that is bound to the polymer surface as a result of a halogenation process. These can include single halogen atoms that were bound to the surface of the polymer.

[00102] As used herein the term "converted" refers to chemical exchange of the halogen atoms or other species of the halogenated polymers surface to some other entity or species. Although these species may or may not be chemical in nature, the conversion process contemplated is a chemical conversion of the general reaction classes including, but not limited to, primary nucleophilic substitution (SNi), secondary nucleophilic substitution (SN₂), or by using as a first step of the conversion either a primary elimination reaction (βi), or secondary elimination reaction (E₂). More preferably, the conversion will be through a SNi or Ei reaction mechanism and most preferably through an elimination followed by substitution reaction mechanism. For example, a halogen may be eliminated under basic conditions or through the use of UN irradiation. The resulting double bond may then subsequently have added to it a hydroxyl group or other species. Suitable chemical transformations would be those generally known to the skilled artisan. Such mechanisms are outlined in works by Solomons, Carey & Sundburg, and Larock.

[00103] Without being bound to any theory, it is anticipated that the "primary (SN/E1)" reactions should exhibit lower energies in their transition states due to the lack of steric interference is associated with a "secondary (SN E2)" process in which the backside attack is presumed blocked by the bulk polymer. It is anticipated that in order for "secondary" reactions to be most effective, the reactions will take place in amorphous or solvated regions of the halogenated polymer where the backside of alpha or beta carbons are more likely to be exposed. Sufficient heating or an appropriatematrix such as a solvent matrix may sufficiently untangle or solvate polymer chains at the surface to allow a backside attack.

[00104] Furthermore, a reaction mechanism may additionally be classifiable as more than one type of reaction. For example, if one of the halogen species attached to a surface carbon is -OC1 and it is converted to a —C-18 chain by an SNi mechanism, then the conversion is not only classified as a SNi but as a reduction. Furthermore, different disciplines in chemistry use different terms to describe similar reaction mechanisms. For example, in organometalhc chemistry an "associative" reaction mechanism is very similar to a SN₂ mechanism while a "dissociative" reaction mechanism is very similar to a SNi mechanism. Furthermore, different chemical species may exhibit different reaction mechanism types. For example, in organometallic chemistry, the range of reactions and interactions that a metal or metal-containing compound may take part in is more diverse than those of standard organic chemistry due to the presence of the larger, more complex orbital structure of the metal(s). These include, but are not limited to, oxidative-addition, reductive-elimination, insertion, complex formation and the like. Organometallic reaction mechanisms are generally known to those skilled in the art and are discussed in works by Collmam Hegedus and Norton and as well as by Atwood. [00105] As used herein, the term "chemical" refers to any entity that is comprised of an element or elements from the periodic table of the elements. Such chemicals often have an inherent reactivity or functionality that results in their ability to displace the halogen atoms or species directly or indirectly and/or add to the carbon to which the chlorine species was attached. Elements may include, but are not limited to, any organic or inorganic elements such as sulfur, phosphorous, different halogens and the like. Entities comprised of elements may include any organic molecule or organic functional group including those not incorporating carbon such as but not limited to - NO₂, -SH, -OH, -N₃, -NH₂ and the like. Functional groups contaimng carbon include but are not limited to -CHO, -CO₂H, -CO₂R, -CONH₂, and the like. Other chemical entities that may replace the halogen include but are not limited to all aromatic and aliphatic species including but not limited to -CβHs- -C₈-18 and the like. Further chemical entities include, but are not limited to, organic compounds including pharmaceuticals, and chelating agents. Preferred chemicals include those that would result in the creation of chemical synthesis medias as well as those chemicals used for combinatorial, organic, and peptide synthesis. Other chemicals of particular interest include those that may be used to prepare chiral separation medias and other chromatographic medias, and those having various biological activities that may be used in medical devices, implants, extracor oreal surfaces, drag delivery systems and the like. Still other chemicals of particular interest are those that may be used in the preparation of electronic, optic and signal transduction devices. Still further chemicals of interest that may be used as indicators for nuclear biological and chemical (NBC) entities. Still further chemicals of interest are those that exhibit specific degradative or protective properties.

[00106] As used herein, the term "organometallic" refers to organic compounds such as those referred to herein in which at least one metal is attached to, bound or otherwise associated with at least one carbon atom.

[00107] As used herein, the term "metal" refers to any metal defined as such and listed in the periodic table of the elements. [00108] As used herein, the term "polymeric" refers to any polymer such as those listed hereinabove and throughout this disclosure. More specific polymers include those that would find utility in having their polymeric surfaces altered in such a manner so as to achieve a desired surface characteristic that is different from the characteristic of the un-converted or virgin polymer. Non-hmiting examples converted polymers that, when converted, would exhibit significantly altered surface adhesiveness, hydrophilicity and polarity, biopolymers, polymers that would act as chelating agents and the like.

[00109] As used herein, the term "structural" refers to any entity that maintains a macro-molecular 3-dimentional configuration or the ability to react with a functional group on a macro-molecular entity such as those hereinabove described or that will ultimately be reacted in such a manner so as to form a macro-molecular 3-dimentional structure or structural component. Non-limiting examples of small structural entities include but are not limited to dendrimers, nano-tubes, Bucl y balls, printed circuits and the like. Nonlimiting examples of medium sized structural entities include but are not limited to chromatography packings, water treatment medias, biological and chemical synthesis supports, and the like. Nonlimiting examples of large structural entities include but are not limited to air, land and sea vehicle structural components, medical devices and the like.

[00110] As used herein, the terms "matrix", "reaction matrix" and "conversion medium" refer to the environment in which conversion takes place. Since, by necessity, the_. chemical reaction is at least nearly a 2-phase reaction, the phase of the matrix is believed to be of less importance than its composition. The matrix may be a gas with gasses including but are not limited to air, nitrogen, argon, helium, or more reactive gasses such as oxygen, or still more reactive gasses such as ozone, hydrochloric acid and the like alone or in combination. These gasses may be simple reagent carriers, may assist in the conversion, or may comprise a reagent or species that will become attached to the halogenated polymer. The matrix may be a liquid with representative liquids including but not limited to water, toluene, chloroform, hexane and ethers or more reactive liquids such as acetone, methanol, ethanol, isopropanol and ethylacetate or still more reactive liquids such as acetic acid and sulfuric acid and the like alone or in combination. These liquids may be simple reagent carriers, may assist in the conversion, or may comprise a reagent or species that will become attached to the halogenated polymer. The matrix may be a slurry with slurries including but not limited to slurries of the halogenated polymer(s) with water, toluene, chloroform, hexane and ethers and oils or more reactive liquids such as acetone, methanol, ethanol, isopropanol and ethylacetate or still more reactive liquids such as acetic acid and sulfuric acid and the like, alone or in combination. These slurries may be simple reagent carriers, may assist in the conversion, or may comprise a reagent or species that will become attached to the halogenated polymer. The matrix may be an emulsion wherein representative emulsions include but are not limited to emulsions of the halogenated polymer with water in combination with toluene, chloroform, hexane and ethers or more reactive emulsions such as non-polar organic solvents in combination with acetone, methanol, ethanol, isopropanol and ethylacetate or still more reactive emulsions such as non-polar organic solvents in combination with acetic acid and sulfuric acid and the like or any combination thereof. These emulsions may be simple reagent carriers, may assist in the conversion, or may comprise a reagent or species that will become attached to the halogenated polymer. Other emulsions include but are not limited to emulsions wherein one phase is a monomer such as styrene, butadiene, or any of the enumerated emulsion polymerizable monomers presented in works by G. Odian and A. Rudin.

[00111] As used herein, the term "very slightly soluble" is used to refer to polymer chains at or very near the surface of the halogenated polymer wherein heat and/or certain matrices may permit portions of some or all surface polymer chains the ability to move and reorient such that they may be considered somewhat solvated.

[00112] As used herein, the term "slightly soluble" is used to refer to the solubility of reaction components or reagents and the like other than the halogenated polymer being considered. [00113] Alternate chemical methods for converting the halogenated polymer(s) are discussed hereinbelow. The halogenated polymeric articles may be treated at various times during their processing. For example, a solution or an anhydrous mixture of reagents could be fed directly into the mouth of a press screw via a hopper or other means The halogenated polymer beads used in processing could also be converted at the polymer manufacturer prior to shipment to the OEM or other manufacturer. As the converted polymer beads are melted in the barrel or screw, the treated surfaces would be mixed throughout the polymer melt. After shooting the part, some of the treated material would be exposed, thus rendering a polymeric article exhibiting the desired surface characteristics after molding without need for post-molding treatment before application of paint or the like.

[00114] Without being bound to any theory, it is contemplated that the method disclosed herein imparts may impart unexpected and novel properties on the polymeric surface through polymer crosslinking, or by increasing polymer compatibility. A new type of ultra-high molecular weight branched polyethylene (PE) or other plastic may result, thereby providing for increased stiffness and impact strength. A PE capable of being blended with less expensive non-block elastomers or other polymers may also result. Further, the necessity of compatibilizer use may be reduced. It is also contemplated that the method promotes or enhances adhesion properties of the polymeric surface.

[00115] The converted polyolefin material may alternately be mixed with a reactive polymer, thereby forming novel, highly crosslinked, strong structural polymers upon processing. Crosslinking of, for example, polyethylene, increases its strength properties and extends the upper temperature limit at which this plastic can be used.

[00116] The converted polyolefin material may alternately be mixed with several unlike polymers, thereby making them compatible. Further, the converted polyolefin material may be mixed with a reactive polymer and shipped prior to processing or after partial reaction. The novel polymer blend may then be used as a novel, highly crosslinked thermoset polymer. [00117] In certain applications, the converted polymer that results can exhibit outstanding stereoselective properties when used as a synthetic or chromatographic media due to one face of the converted polymer substituents being sterically blocked by the polymer surface. An analogous situation exists in the preference for syn-reduction of alkenes using palladium on carbon (Pd/C) (see Beholz and Cook). In this, the hydrogen molecules used in the reduction process are adsorbed onto the surface of the Pd/C. When the alkene approaches the Pd/C, addition of the hydrogen across the double bond occurs only from the side of the Pd/C. Although it is believed that the opposite effect would be exhibited by the herein disclosed invention, the concept is analogous.

[00118] The conversions described herein may be executed using any suitable continuous or batch processing apparatus. Suitable apparatus can include the use standard chemical and manufacturing equipment such as those that would normally be used to prepare other bonded phases, pre-treat automotive components, and the like.

[00119] In one embodiment of the halogented polymer treament method disclosed herein, an automotive fascia prepared from impact-modified CPE can be hydrolyzed to replace the chlorine atoms or species with hydroxyl groups in an acetone/water matrix using dilute sulfuric acid (H₂SO₄). The hydrolysis matrix is stirred and heated slightly. Slightly solubilized polymer chains containing primary and secondary chlorine atoms or species react by an SN₂ mechanism while tertiary chlorines react quickly by an SNi mechanism and some react by an Ei mechanism as well. TJnsolubilized secondary chlorine atoms or species slowly react by a SNi reaction mechanism while the unsolubilized primary chlorine atoms or species have a very difficult time reacting due to the activation energy associated with attainment of the primary carbocation. Ultimately, the PE is sufficiently hydroxylated to exhibit the surface characteristics of a very polar and hydrophilic polymer. The automotive fascia can be painted with a suitable paint such as polyurethane automotive paint.

[00120] In another embodiment, a tractor roof prepared from impact-modified CPP. The roof is hydrolyzed to replace at least a portion of the chlorine atoms or species with hydroxyl groups using H₂SO₄ at 10% in a water matrix. The resulting article exhibits hydroxylated polypropylene at the surface and near surface region. The tractor roof is painted with a polyurethane paint and demonstrates good adhesion.

[00121] In another embodiment, a lattice prepared from CPP can be hydrolyzed to replace the chlorine atoms or species with hydroxyl groups using H₂SO at 8% in a water matrix. The resulting PP is hydroxylated at and near the polymeric surface. The lattice is painted with a latex paint and demonstrates good adhesion

[00122] In another embodiment, to military vehicle components prepared from CPP are added to silica. The extremely hydrophobic surfaces are very difficult for biological agents to attach to and wash readily.

[00123] In another embodiment, particulates comprised of highly branched HPP having significant secondary and tertiary halide character are hydrolyzed according to the method disclosed herein to replace the halogens with hydroxyl groups in an acetone/water matrix using concentrated tertiarybutyl hydroxide (t-BuOH). The mixture or slurry is stirred and heated at reflux. The slightly solubilized secondary and tertiary chlorines preferentially react by an E₂ mechanism forming double bonds on the surface of the particulates. The particulate material is treated with sulfuric acid to add hydrogen sulfates to the surface creating an ion-exchange resin.

[00124] In another embodiment, a CPE powder can be converted according to the method disclosed herein such that /w-nitro phenol was added to methyl iodine (Mel), the CPE equivalent, in the presence of sodium bicarbonate (Na₂CO₃) and a water/ethanol matrix. The yield of the conversion was 94%. The nitro-groups of the attached aromatic tethers are then reduced to amines, to form a linker onto which other entities are attached for the preparation of a media for solid phase chemical synthesis.

[00125] In another embodiment, a CPE powder can be converted according to the method disclosed herein in which /w-methoxy aniline was added to benzyl bromide, (BnBr), the CPE equivalent, in the presence of sodium bicarbonate (Na₂CO₃) in a water/ethanol matrix. The yield of the reaction was 48%. The methoxy-groups of the attached aromatic tethers are hydrolyzed and chiral molecules are attached to the resulting hydroxyls to produce a media for the separation of pharmaceutical enantiomers.

[00126] In another embodiment, a CPP can be converted according to the method of Petal et. al. wherein, (R)-citronnellol was added to BnBr, the CPP equivalent, in the presence of sodium hydride (NaH) in a tetrahydrofuran (THF) matrix. The yield of the reaction was 99%. This method can also be used to prepare chromatographic media for the separation of enantiomers.

[00127] In another embodiment, a CPP powder can be converted according to the method of Beholz wherein, indole-N-MgBr was added to allylbromide, the CPP equivalent, in an ether matrix. The product was 3-allyl indole in 58% yield. The indole functionalized polymer is used as a chromatographic stationary phase.

[00128] In another embodiment, a CCP, powder can be used as a Merrifield resin. A polypeptide is prepared that will ultimately be used as a catalytic antibody.

[00129] In another embodiment, a CCP powder can be reacted with 1,2- diamino ethane to form a media with extensive primary amine functionality. This media is packed into an air filter to remove sulfonyl chloride based chemical warfare agents from air entering a barracks.

[00130] In another embodiment, a CCP film can be hydroxylated and 1,2- dichlorofluoroscein is bound to it to render the colorimetric detection component of a medical device for monitoring heparin concentrations in whole blood.

[00131] In another embodiment, according to the method of Beholz bromobenzene, a CPP equivalent, can be converted to phenyl-MgBr and added to allylbromide, a CPE equivalent in an ether matrix. In similar fashion, low density CCP- MgBr is intimately mixed with low density CPE and poured into a mold which is compressed slightly to provide intimate contact between all of the powder particulates. Diethylether containing a catalytic amount of iodine is forced under pressure into the mold which is then gently heated. The CPP and CPE powders react with one another to form a very low density plastic structural foam part.

[00132] In another embodiment, the chlorine species on CPE catheters are converted to polyetherarethane polymers. By the method of Heyman, the urethane bonds are hydrolyzed with NaOH to introduce both hydroxyl and amine groups. The free amine groups are further reacted and coupled to l-ethyl-3-(3-dimethylaminopropyl) carbodimide (EDC) activated heparin to yield heparin coated catheters.

[00133] In another embodiment, CPE converted to carboxcylic acid and sulfate functionalized PE, by the method of Larsson et al., was then treated with an aqueous solution of PEL Partially degraded heparin was then coupled covalently to the amine groups in the presence of sodium cyanoborohydride by the method of Arnander.

[00134] In another embodiment, benzylalcohol (BnOH) was added to the surfaces of several halogenated polymer structural automotive components with the intent of drastically improving its adhesiveness to epoxies for the purpose of gluing. The very adhesive parts were glued together using epoxy glue.

[00135] In another embodiment, chlorines on the surface of CPE military aircraft components were converted to epoxy polymers for vastly improved adhesiveness. The components were then painted with a radar deflecting paint.

[00136] In another embodiment, the bromine atoms of brominated PP particles are converted to poly(acrylamide-co-acrylic acid) polymers for the purpose of preparing a water treatment media that will be used to remove phosphates from water. The converted media is packed into a housing whereby phosphate contaminated water is passed through and rendered free of phosphates. [00137] In another embodiment, the halogen species on an HPE surface is converted to epoxy polymers. To this is applied silver impregnated epoxy in patterns for the purpose of making/connecting electronic circuits.

[00138] In another embodiment, the iodine atoms of an iodinated soluble polymer are converted to functionality susceptible to ionizing or UN radiation. An integrated circuit pattern is formed in this substrate after adhering to a silicon substrate. The portion of the polymer exposed to the radiation undergoes crosslinking (a negative resist). Later, the unexposed polymer is dissolved away revealing the integrated circuits pattern.

[00139] In another embodiment, the chlorine atoms of one CPE automotive structural component are converted to epoxy resin polymers. The chlorine atoms of the complimentary CPE automotive structural component are converted to epoxy "hardener" functionality. The parts are pressed together and are thus bonded by an epoxy weld.

[00140] To further illustrate the processes disclosed herein, the following examples are given. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the present invention.

EXAMPLE 1 [00141] In order to evaluate the surface treatment method disclosed herein, a 200 mL solution was prepared comprising a sodium hypochlorite oxidizing agent. The sodium hypochlorite is maintained in an aqueous solution at a concentration of about 7.5% by volume with the addition of a catalytic amount of iodine (<0.0001% by weight). The oxidizing solution was heated to 40°C with stirring. 10 -1 inch X 1 inch pieces of virgin HDPE were added to the solution and 2-4 mLs of HC1 were added over a period of approximately 30 seconds. Two (2) of the HDPE pieces were removed at each interval 1,2,4,6 and 10 minutes. Subsequent adhesion to paint (RustOleum) was tested and it was determined that the adhesion increased over the first 4 minutes providing at 4 minutes outstanding adhesion. Similar results were exhibited at 60°C although unexpectedly, excellent adhesion could not be achieved even after 10 minutes in a 90°C treatment solution. The results are depicted in Fig. 1. Interestingly too, treatment using HCl as an activator appeared to provide more consistent and predictable adhesion results than through the use of 10% acetic acid as the activator.

200 mLs 7.5% Bleach, l₂, Variable ml_s HCl at 90, 60 and 40°C. 4 = Excellent - 1 = Poor, 5 November 2004

Time (min.)

EXAMPLE 2 [00142] To further evaluate the surface treatment method disclosed herein, a 5 L solution was prepared comprising a sodium hypochlorite oxidizing agent. The sodium hypochlorite was maintained in an aqueous solution at a concentration between about 7.5% by volume. A catalytic amount of iodine was added. To this solution was added 12 4 inch X 12 inch panels. 500 mLs of acetic acid was then carefully added with mixing. The parts were allowed to remain under quiescent conditions at ~20°C for 3.5 hours. Subsequent painting and cross-hatch testing of 6 of these panels by Technical Finishing Inc. indicated excellent adhesion as no paint was lifted from the treated panels. Additional comparative in-house testing indicated that the use of the iodine catalyst reduced the treatment time at 20°C from approximately 72 hours to under 4 hour, an increase in reaction rate of 18 times.

EXAMPLE 3 [00143] A 5 L solution was prepared comprising a sodium hypochlorite oxidizing agent according the to surface treatment method disclosed herein. The sodium hypochlorite is maintained in an aqueous solution at a concentration at 7.5%% by volume. To this was added a catalytic amount of iodine. To this solution was added 7- 4 inch X 6 inch HDPE panels. At ambient temperature, 100 mLs of phosphoric acid was carefully added with stirring over a period of several minutes. The parts were allowed to remain solution under quiescent conditions. After approximately 16 hours, the panels were removed and rinsed with tap followed by DI water. Outstanding water adhesion was noted. The panels were then painted with Krylon "Fusion" paint. After being allowed to dry the panels were tested as in Example 1 above. Again, outstanding adhesion was exhibited as no paint could be lifted from the treated panels.

EXAMPLE 4 [00144] To further evaluate the surface treatment method, a solution is prepared comprising a sodium hypobromite oxidizing agent and is heated to about 60° C, followed by addition of the inorganic activating agent. The sodium hypobromite is maintained in an aqueous solution at a concentration of about 7.5% by volume. Twelve pieces of polyethylene are immersed in the heated solution followed immediately by the addition of a 10 mL solution containing 2 mLs of concentrated HCl and 4 mLs of acetic acid. The pieces are treated for approximately two minutes. The treated pieces are painted with RUST-OLEUM Gloss Protective Spray Enamel, Gloss Black 7779. The painted pieces are suspended from the upper rack of a dishwasher and run through 100 cycles on the "pots and pans" setting. Little to no loss in adhesion is noted, as determined by the ASTM D3359-78 cross-hatch method defined hereinabove. EXAMPLE 5 [00145] In order to further evaluate the surface treatment method, a 1 L solution was prepared containing 7.5 % sodium hypochlorite. The solution was heated to approximately 80°C with stirring. To this solution was added a basket, fashioned from a polyethylene wash bottle and nylon screen, that was % filled with expanded foam polyethylene pellets. The basket was shaken vigorously while 5 mLs of concentrated HCl was slowly added over 1 minute. The basket and its contents were shaken vigorously for an additional 3 minutes after which the basket and components were rinsed with copious amounts of water then DI water. The foam pellets were poured from the basket, blotted dry, and dried over gentle heat for approximately 24 hours. The portion of the foam was then poured into a polyethylene mold with drainage holes in the bottom, fashioned from the bottom of a 50 mL bottle. Over this mixture was poured a solution of polyurethane caulk that had been dissolved in THF (approximately 4 grams of caulk in approximately 20 mL of THF). The sample was allowed to dry for 48 hours and was removed from the mold. Manipulation of the part indicated that the caulk could be pulled from the caulk with far greater ease than the caulk could be pulled from the expanded foam pellets. Samples were independently analyzed and found to be able to adhere together. The ability to adhere these pellets together is significant and indicates that they can be used in such various applications as automotive bumper interiors and outdoor drainage applications such as under sporting field liners.

EXAMPLE 6 [00146] Spray application is used for application of the adhesion alteration reagents. The temperature of the solution of Example 5 is prepared at the exit of a heated spray gun nozzle. The solution is raised to 100 ° C. and is applied to various samples of expanded foam materials composed of polyolefinic materials such as expanded polyethylene. The hot solution is applied throughout a period of 1 minute to each sample. [00147] The resulting chlorinated expanded polyethylene pellets were coated with an epoxy resin and packed into a bumper form and cured to fabricate an impact resistant bumper interior.

EXAMPLE 7 [00148] Hot vapor application is employed for alteration of the adhesion alteration reagents. The solution in Example 5 is prepared and flash heated to form a reactive vapor. Structural articles formed from a conventionally unpaintable polypropylene and polyethylene material respectively are exposed to the reactive vapor for 2 minutes. The articles are examined for paint adhesion. It is found that improved paint adhesion is imparted on the articles treated with the reactive vapor, as determined by the ASTM D3359-78 cross-hatch method defined hereinabove.

EXAMPLE 8 [00149] In order to investigate treatment of halogenated polymeric material, six chlorinated HDPE pieces (4 inches X 6 inches) were suspended in a stirring 2 L 20 % aqueous NaOH solution. The pieces were heated to 120°C for 6 hours and allowed to cool over night. The pieces were then removed and were found to be extremely hydrophilic. The pieces were rinsed with copious amounts of water and placed in a 4 L 2% acetic acid solution. The solution containing the parts was stirred for 48 hours at ambient temperature. The pieces could be stained using the Bradford Reagent, a reagent used to stain proteins. Pieces were found to be extremely lubricious and were found to have potential utility as joint replacement material.

EXAMPLE 9 [00150] In a manner analogous to that in EXAMPLE 1, 4 pieces of chlorinated HDPE were hydrolyzed and subsequently protonated using H₃PO₄ as the acid. The resulting pieces demonstrated lubricousness similar to that found in the previous example. EXAMPLE 10 [00151] In a manner analogous to that in Example 1, 6- 1 inch X 1.5 inch pieces of ethylene-tetrafluoroethylene copolymer (ETFE) mesh (nominal aperture 70um, monofil diameter 80 um, threads/cm 66.7, open area 21%, plain weave mesh purchased from Goodfellow Cambridge Limited, Huntingdon PE29 6WR, England) was treated, hydrolyzed and protonated. The resulting hydrophilic mesh appears o exhibit suitable biocompatible characteristics making it a suitable functionalized, biocompatible replacement for PTFE in materials used for devices such as stents.

[00152] While preferred embodiments, forms and arrangements of parts of the invention have been described in detail, it will be apparent to those skilled in the art that the disclosed embodiments may be modified. Therefore, the foregoing description is to be considered exemplary rather than limiting, and the true scope of the invention is that defined in the following claims.

Claims

What is claimed is:

1. A method for improving characteristics of a polymeric material, the characteristics of the polymeric materials including at least one of adhesion, polarity and reactivity, the method comprising the steps of: contacting the polymeric material with a composition containing at least one oxidizing agent, said oxidizing agent present in a kinetically degrading state producing at least one chemical intermediate reactive with the polymeric substrate in a controlled reaction mechanism for an interval sufficient to impart functional groups derived from said oxidizing agent into the polymeric material.

2. The method of claim 1 further comprising the step of: reacting said oxidizing agent with a primary activating agent, the primary activating agent reacting with said oxidizing agent to produce said at least one intermediate compound reactive with the polymeric substrate, the primary activating agent optionally including at least one of an inorganic acid and an inorganic acid precursor.

3. The method of claim 2 wherein the activating agent further may include at least one of an organic acid and an organic acid precursor.

4. The method of claim 2 wherein said reacting step occurs in at least one of an aqueous environment, an anhydrous environment, and a vaporous environment.

5. The method of claim 2 wherein reaction between said oxidizing agent and said activating agent occurs at a rate essentially equal to reaction between said polymeric substrate and the reaction intermediate; and wherein said oxidizing agent is a bivalent compound including at least one of oxycompounds of chlorine, oxycompounds of bromine, oxycompounds of iodine, oxycompounds of boron, oxycompounds of nitrogen.

6. The method of claim 5 wherein said bivalent oxygen compound is selected from the group consisting of: oxycompounds of chlorine including at least one of hypochlorous acid, alkali metal salts of hypochlorous acid and hydrates thereof, alkaline earth metal salts of hypochlorous acid and hydrates thereof, perchloric acid, alkali metal salts of perchloric acid and hydrates thereof, chloric acid, alkali metal salts of chloric acid and hydrates thereof, alkaline earth metal salts of chloric acid and hydrates thereof; oxycompounds of bromine including at least one of hypobromous acid, alkali metal salts of hypobromous acid and hydrates thereof, alkaline earth metal salts of hypobromous acid and hydrates thereof, bromic acid, alkali and alkaline earth metal salts of bromic acid and hydrates thereof; oxycompounds of iodine including at least one of iodic acid, alkali and alkaline earth metal salts of iodic acid and hydrates thereof, periodic acid, alkali and alkaline earth metal salts of periodic acid and hydrates thereof; oxycompounds of boron including at least one ofboric acid, alkaline earth and alkali metal salts and hydrates thereof, alkali perborates and hydrates thereof, alkaline earth metal perborates and hydrates thereof; oxycompounds of nitrogen including at least one of nitric acid, alkali and alkaline earth metal salts of nitric acid and hydrates thereof; and mixtures thereof.

7. The method of claim 2 wherein the primary activating agent is composed of inorganic acid or acids or inorganic acid precursors including at least one of binary acids, Bronsted acids, hydrohalic acids, oxyacids such as hypohalous acids (HXO), Halous Acids (HXO₂), Halic Acids (HXO₃), Perhalic Acids (HXO₄), Paraperhalic Acids (HsXOβ), Lewis acids, mineral acids, polyprotic acids, ternary acids, electrophiles, pseudohalide acids and pseudohalogens and salts thereof.

8. The method of claim 2 wherein the primary activating agent is composed of an inorganic acid including at least one of Arsenic, Arsenious, o-Boric, Carbonic, Chromic, Germanic, Hydrocyanic, Hydrogen Sulfide, Hydrogen Peroide, Hypobromous, Hypochlorous, Hypoiodous, Iodic, Nitrous, Periodic, ø-Phosphoric, Phosphorous, Pyrophosphoric, Selenic, Selenious, rø-Selicic, o-Selicic, Sulfuric, Sulfurous, Telluric, Tellurous, and Tetraboric.

9. The method of claim 2 wherein the primary activator inorganic acid of the primary activator includes at least one of HF, HCl, HBr, HI, H₂SO₃, H₂S0 , F£NO₂, HNO₃, HFO, HFO₂, HFO₃, HFO₄, H₅FO₆, HClO₂, HClO₃, HClO₄, H₅ClO₆, HBrO₂, HBrO₃, HBrO₄, H₅BrO, HIO₂, ffl0₃₎ HIO₄, H5IO₆, H₂SeO₃, H₂SeO₄, H₃PO₃, H₃PO₄, SO₂, HSO₃; H₂SO₃, HSO₄; H₂SO₄, H₂S₂O₃, HNO₃, NO₂, N₂O₅, HMnO₄, H₂Cr₂O₇, PC1₃, PC1₅, POCls, P Oιo, H₃PO₃, H₃PO₄, HCN, HCNO, HNCO, HSCN, HSeCN, H TeCN, HN₃, HSCSNs, H₂S, H₂Se, H₂Te, A1C1₃, FeCl₃, FeBr₃, HSiO₃, ILSiO^ H₆Si₂θ₇,BF₃, BF₃-etherate, BC1₃, SnCl₄, H CO₃, and CO₂.

10. The method of claim 3 wherein the organic acid includes at least one carboxylic acid having the general formula:

wherein x and y are integers between 0 and 20 inclusive, with the sum of x and y being an integer of 20 or less, wherein R is a functionality selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups, branched or unbranched alkyl groups, the alkyl group having between 1 and 27 carbon atoms, and mixtures thereof, and wherein each variable R¹, R", R'" and R"" is a functionality selected from the group consisting of hydrogen, amines, hydroxyl, phenyl, phenol radicals, and mixtures thereof, each of the above-mentioned R variable functionalities being chosen independently of the other R variable functionalities, and wherein R" includes at least one of anhydrides, halide salts, selenic acid salts, perchloric acid salts, boric acid salts, and mixtures thereof; and dicarboxylic acid having the general formula: R'

HO- -OH

R wherein x is an integer between 1 and 20 inclusive and R and R' are functionalities selected from the group consisting of hydrogen, hydroxyl radicals, amines, phenyl radicals and mixtures thereof; and mixtures thereof.

11. The method of claim 1 wherein said contacting step occurs at a temperature between about 20° C. and a temperature at which decomposition of the polymeric material commences.

12. The method of claim 1 wherein the polymeric material is selected from the group consisting of: addition polymers selected from the group consisting of polyethylene, polypropylene, polystyrene, polyisobutylene, polyvinyl chloride, polyacrylonitrile, polymethyl acrylate, polymethyl methacrylate, polytetrafluoroethylene, polyformaldehyde, polyacetaldehyde, polyisoprene, and mixtures thereof; condensation polymers selected from the group consisting of polyamides, polyesters, polyurethanes, polysiloxanes, polyphenolformaldehydes, ureaformaldehydes, melamine formaldehydes, celluloses, polysulfides, polyacetates, polycarbonates, and mixtures thereof; thermoplastic elastomers selected from the group consisting of styrene-isoprene- styrene, styrene-butadiene-styrene, copolyesters, copolyester ethers, silicone-polyamides, silicone-polyesters, silicone-polyolefins, silicone-styrenes, aromatic polyether-urethanes, alpha cellulose filled ureas, polyvinyl chloride-acetates, vinylbutyrals, and mixtures thereof; co-polymers selected from the group consisting of polyester-polyethers, polyether-polysiloxanes, polysiloxane-polyamides, polyesteramides, copolyamides, ethylene-tetrafluoroethylene, nylons, and mixtures thereof; and mixtures thereof.

13. The method of claim 12 wherein the polymeric material is selected from the group consisting of polyethylenes, polypropylenes, polyesters, thermoplastic elastomers, plastomers, isotactic and syndiotactic polymers and mixtures thereof.

14. The method of claim 13 wherein the polymeric material is a polyester selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, and mixtures thereof.

15. The method of claim 10 wherein the reaction between said oxidizing agent and said activating agent occurs at a rate essentially equal to reaction between said polymeric substrate and the reaction intermediate.

16. The method of claim 10 wherein the oxidizing agent is maintained in an aqueous solution at a concentration between about 0.25% and 25% by volume, and wherein the primary activating agent is maintained in an aqueous solution at a concentration between 0.02% and 10% by volume, with an inorganic activator being present in an amount between 0.2 and 2.0% by volume.

17. The method of claim 16 wherein the inorganic activator is maintained at a concentration between about 0.2% and about 2% by volume.

18. The method of claim 1 wherein the polymeric material is a moldable polymeric material composed of at least one of virgin polymeric material and regrind polymeric material.

19. The method of claim 1 wherein the contacting step is carried out by spraying the composition onto at least one of a virgin polymeric material and a polymeric substrate with at least one of a heated spray gun, an atomizer and a steam generator.

20. The method of claim 1 wherein the composition is flash heated to form a reactive vapor, and the contacting step is carried out by exposing a polymeric substrate to the vapor for a period of time sufficient to render the substrate adhesive.

21. The method of claim 10 wherein the oxidizing agent and the activating agent are each in solid form, and wherein the method further comprises the step of placing the solid forms at the mouth of an injection molding press, wherein the contacting step occurs during molding of a virgin polymeric material into a polymeric substrate.

22. The method of claim 10 wherein the oxidizing agent and the activating agent are in an aqueous solution; and wherein the method further comprises the step of spraying the composition onto the inner core of a tool of an injection molding press, wherein the contacting step occurs during molding of a virgin polymeric material into a polymeric substrate.

23. The method of claim 10 wherein the composition is flash heated to form a reactive vapor, and wherein the vapor is forced into a molding tool substantially immediately before closing the tool, wherein the contacting step occurs during molding of a polymeric material into a polymeric substrate.

24. The method of claim 10 wherein the primary activating agent is selected from the group consisting of HCl, H₂SO₄, and mixtures thereof and wherein the organic acid is acetic acid.

25. The method of claim 10 wherein the oxidizing agent is selected from the group consisting of sodium hypochlorite, calcium hypochlorite, calcium hypochlorite tetrahydrate, and mixtures thereof.

26. The method of claim 10 further comprising the step of adding a radical initiator, the radical initiator including at least one compound capable of initiating kinetic degradation of the oxidizing agent.

27. The method of claim 26 wherein the radical initiator includes at least one of iodine, Group LA, Group ILA, Group B metals, metals in ammonia, iron in combination with peroxides, salts of metals, diphenylpicrylhydrazyl radical (DPPH), Azo-type radical initiators and nitroxides.

28. The method of claim 26 wherein the radical initiator is physical phenomena in at least one of visible and nonvisible spectra and heat.

29. A method for altering at least one characteristic of a polymeric material, the characteristic including at least one of adhesion, polarity, and reactivity, the method comprising the steps of: contacting the polymeric material with a composition containing at least one oxidizing agent, said oxidizing agent present in a kinetically degrading state which produces at least one chemical intermediate reactive with the polymeric substrate in a controlled reaction mechanism for an interval sufficient to impart functional groups derived from said oxidizing agent into the polymeric material; and reacting said oxidizing agent with an activating agent which preferentially reacts with said oxidizing agent to produce said the at least one intermediate reactive with the polymeric substrate; wherein said oxidizing agent is a bivalent oxygen compound selected from the group consisting of oxycompounds of chlorine, oxycompounds of bromine, oxycompounds of iodine, oxycompounds of boron, oxycompounds of nitrogen and mixtures thereof; and wherein the primary activating agent is selected from the group consisting of an inorganic acid, acids or inorganic acid precursors including at least one of binary acids, Bronsted acids, hydrohalic acids, oxyacids such as hypohalous acids (HXO), Halous Acids (HXO₂), Halic Acids (HXO₃), Perhalic Acids (HXO₄), Paraperhalic Acids (HiKOβ), Lewis acids, mineral acids, polyprotic acids, ternary acids, or weak or strong inorganic acids or acid salts and acids formed from the class of pseudohalides and pseudohalogens.

30. The method of claim 29 wherein the primary activating agent is an inorganic acid such as Arsenic, Arsenious, o-Boric, Carbonic, Chromic, Germanic, Hydrocyanic, Hydrogen Sulfide, Hydrogen Peroide, Hypobromous, Hypochlorous, Hypoiodous, Iodic, Nitrous, Periodic, o-Phosphoric, Phosphorous, Pyrophosphoric, Selenic, Selenious, m- Selicic, o-Selicic, Sulfuric, Sulfiirous, Telluric, Tellurous, and Tetraboric.

31. The method of claim 29 wherein the primary activating agent is an inorganic acid such as HF, HCl, HBr, HI, H₂SO₃, H₂SO₄, HNO₂, HNO₃, HFO, HFO₂, HFO₃, HFO₄, H₅FO₆, HClO₂, HC10₃, HClO₄, H₅ClO₆, HBrO₂, HBrO₃, HBrO₄, H₅BrO, HIO₂, HIO3, HJ.O4, H5IO₆, H₂SeO₃, H₂SeO₄, H₃PO₃, H₃PO₄, SO₂, HSO₃ ^_, H₂SO₃, HSO₄ ^", H₂SO₄, H₂S₂O₃, HNO3, NO₂, N₂O₅, HMnO₄, H₂Cr₂O₇, PCI3, PC1₅, POCl₃, P₄Oι₀, H₃PO₃, H₃PO₄, HCN, HCNO, HNCO, HSCN, HSeCN, HTeCN, HN₃, HSCSN₃, H₂S, H₂Se, H₂Te, AICI3, FeCl₃, HSiO₃, H₄Si0₄, H₆Si₂O₇, BF₃-etherate, BC1₃, SnCl₄, H₂CO₃, CO₂, and the like.

32. The method of claim 29 wherein the optional organic acid consists essentially of: at least one carboxylic acid or acids having the general formula:

wherein x and y are integers between 0 and 20 inclusive, with the sum of x and y being an integer of 20 or less, wherein R is a functionality selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups, branched or unbranched alkyl groups, the alkyl group having between 1 and 27 carbon atoms, and mixtures thereof, and wherein each variable R', R", R'" and R"" is a functionality selected from the group consisting of hydrogen, amines, hydroxyl, phenyl, phenol radicals, and mixtures thereof, each of the above-mentioned R variable functionalities being chosen independently of the other R variable functionalities, and wherein R" may also be selected from the group consisting of anhydrides, halide salts, selenic acid salts, perchloric acid salts, boric acid salts, and mixtures thereof; at least one of the dicarboxylic acid having the general formula: R^*

HO- -OH

R wherein x is an integer between 1 and 20 inclusive and R and R' are functionalities selected from the group consisting of hydrogen, hydroxyl radicals, amines, phenyl radicals; and mixtures thereof.

33. The method of claim 29 wherein the primary activating agent is selected from the group consisting of HCl, H₂SO₄, and mixtures thereof in combination with an organic acid such as acetic acid, succinic acid, oxalic acid, and organic acid precursors such as acetic anhydride, succinic anhydride, and oxalic anhydride.

34. The method of claim 29 wherein the oxidizing agent is selected from the group consisting of sodium hypochlorite, calcium hypochlorite, calcium hypochlorite tetrahydrate, and mixtures thereof.

35. A method for converting the surface and/or very near surface halogen atoms or halogen-containing species of halogenated polymers comprising the step of: contacting the halogenated polymeric material with a conversion medium; adding at least one reagent to the conversion medium; and maintaining contact between the conversion medium containing the added reagent for an interval sufficient to convert at least a portion of the halogen and/or halogen containing species to at least one of an organometallic, metal, polymeric, or chemical entity.

36. The method of claim 35 wherein the reaction matrix is at least one of a gas, liquid, slurry, emulsion thereof in which the halogenated polymer is, at most, only very slightly soluble therein but the chemical entity displacing or replacing the halogen atom or species is at least slightly soluble therein.

37. The method of claim 35 wherein the halogenated polymer is at least one of halogenated polyethylene and halogenated polypropylene.

38. The method of claim 35 wherein the chemical conversion is executed at an elevated temperature.

39. The method of claim 38 wherein the temperature is between 100°C and 200°.

40. The method of claim 36 wherein the gas contained in the matrix is at least one of air, nitrogen, argon, helium, or oxygen, ozone, and hydrochloric acid.

41. The method of claim 36 wherein the liquid contained in the matrix is at least one of water, toluene, chloroform, hexane, ethers, acetone, methanol, ethanol, isopropanol, ethylacetate, acetic acid and sulfuric acid.

42. The method of claim 36 wherein the slurry contained in the matrix is a halogenated polymer slurried with at least one of water, toluene, chloroform, hexane, ethers, acetone, methanol, ethanol, isopropanol, and ethylacetate, acetic acid, and sulfuric acid.

43. The method of claim 36 wherein the emulsions contained in the matrix is a halogenated polymer with water in combination with at least one of toluene, chloroform, hexane, ethers, with nonpolar organic solvents in combination with at least one ofacetone, methanol, ethanol, isopropanol, ethylacetate, acetic acid, and sulfuric acid. The method of claim 1 whereby replacement of the halogen atoms or species by other entities is an SNi, SN₂, or as a first step an Ei, or E₂ mechanism.