US 20060041057A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0041057 A1 K0echer et al. (43) Pub. Date: Feb. 23, 2006

(54) POLYDIACETYLENE POLYMER BLENDS (22) Filed: Aug. 19, 2004 (75) Inventors: Steven D. Koecher, New Brighton, MN Publication Classification (US); Richard G. Hansen, Mahtomedi, MN (US); Jeffrey J. Cernohous, (51) Int. Cl. Hudson, WI (US) C08F 290/14 (2006.01) (52) U.S. Cl...... 525/50 Correspondence Address: 3M INNOVATIVE PROPERTIES COMPANY (57) ABSTRACT PO BOX 33427 Polymer blend compositions that include diacetylene Seg ST. PAUL, MN 55133-3427 (US) ments are provided. The polymers containing diacetylene 9 Segments are capable of a calorimetric indication in response (73) Assignee: 3M Innovative Properties Company to Stimuli, Such as heat, an analyte or exposure to certain environmental factors, despite being blended with other (21) Appl. No.: 10/922,091 materials, Such as polymers or additives. US 2006/004 1057 A1 Feb. 23, 2006

POLYDACETYLENE POLYMER BLENDS 0005. In one embodiment, the reactive emulsifying seg ment is formed from a reactive emulsifying compound BACKGROUND represented by the formula V: 0001 Polymer compositions that include polydiacetylene Segments are used for a variety of applications. Diacetylenes (V) are typically colorless and undergo addition polymerization, G-X-N-Y-G either thermally or by actinic radiation. AS the polymeriza tion proceeds, these compounds undergo a contrasting color change to blue or purple. When exposed to external Stimuli Such as heat, physical StreSS or a change of Solvents or counterions, polydiacetylenes exhibit a further color 0006 wherein G is selected from the group consisting changes produced by distortion of the planar backbone of OH, NHR and SH; each of X and Y may be the same conformation. Polydiacetylene assemblies are known to or different; each of X and Y are independently selected change color from blue to red with an increase in tempera from aliphatic organic radicals having from about 1 to ture or changes in pH due to conformational changes in the about 20 carbon atoms, free of reactive functional conjugated backbone as described in Mino, et al., Langmuir, groups, and combinations thereof; and wherein R can Vol. 8, p. 594, 1992; Chance, et al., Journal of Chemistry be hydrogen or an aliphatic organic radical having from and Physics, Vol. 71,206, 1979; Shibutag, Thin Solid Films, about 1 to about 20 carbon atoms, free of reactive Vol. 179, p. 433, 1989; Kaneko, et al., Thin Solid Films, Vol. functional groupS. 210, 548, 1992; and U.S. Pat. No. 5,672,465. Utilization of this class of compounds is known for use as biochromic 0007. In another embodiment, the reactive emulsifying indicators as discussed in U.S. Pat. No. 5,622,872 and Segment is formed from a reactive emulsifying compound publication WO 02/00920. represented by the formula IV: 0002. In addition to the polymerization of monomeric diacetylenes, it has been demonstrated that the diacetylene (IV) functionality can be incorporated in the repeat Structure of a R polymer backbone. These types of polymers undergo Solid State cross-polymerization on exposure to U.V. radiation a-x--y-g forming polydiacetylene chains. These materials have been referred to as macromonomers due to the Systematic poly merization of the diacetylene units within the backbone Structure of the initial polymer. Examples of polymers 0008 wherein G is selected from the group consisting containing the reactive diacetylene functionality in the of OH, NHR and SH; wherein Q is a negatively charged repeat Structure of the polymer backbone formed by linking moiety selected from COO and SO, or a group that the appropriate difunctional monomers together, wherein is capable of forming Such a negatively charge moiety one of which contains the diacetylene group include the upon ionization; each of X, Y and R' may be the same diacetylene-urethane copolymers described in U.S. Pat. Nos. or different; X, Y, R, and R' are independently selected 4,215,208 and 4,242,440; segmented copolymers formed from aliphatic organic radicals free of reactive func from diisocyanate reacted with elastomeric prepolymer and tional groups, preferably having from about 1 to about chain extended with a diacetylene described in U.S. Pat. No. 20 carbon atoms, and combinations thereof; R can be 4,721,769; linear block copolymers with a soft segment hydrogen; and R is optional if Q is COO and SO. (polyether, polyester, polydiene, polydimethylsiloxane) and a diacetylene-containing hard Segment (Polyurethane, 0009. As used herein, “a,”“an,”“the,”“at least one,” and polyamide, polyester, polyurea) as described in U.S. Pat. No. “one or more' are used interchangeably. Also herein, the 4,767,826; and polyamide-diacetylene copolymers as recitations of numerical ranges by endpoints include all described in U.S. Pat. Nos. 4,849,500 and 4,916,211. numbers Subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). SUMMARY 0010. The above summary of the present invention is not 0003. The present invention is directed to polymer blend intended to describe each disclosed embodiment or every compositions, and methods of making and using them, that implementation of the present invention. The description include a chromogenic copolymer comprising at least two that follows more particularly exemplifies illustrative diacetylene Segments, and an additive with at least one embodiments. functional characteristic, wherein the polymer blend exhibits chromogenic characteristics of the diacetylene-containing DETAILED DESCRIPTION OF ILLUSTRATIVE copolymer and the functional characteristics of the additive. EMBODIMENTS OF THE INVENTION The additives include, but are not limited to, plasticizers, 0011. The present invention provides polymer blend tackifiers, and/or polymer additives Such elastomers. compositions that include diacetylene Segments. In particu 0004. A chromogenic copolymer is also provided com lar, the present invention is directed to polymers containing prising at least two diacetylene Segments, a linkage Segment; diacetylene Segments that provide a polymer network and at least one reactive emulsifying Segment. A polymer capable of a calorimetric indication in response to Stimuli, blend comprising the chromogenic copolymer with at least Such as heat, an analyte or exposure to certain environmental one reactive emulsifying Segment and an additive with at factors, despite being blended with other materials, Such as least one functional characteristic is also provided. polymers or additives. US 2006/004 1057 A1 Feb. 23, 2006

0012. The diacetylene segments self assemble to form 0016. The ability of polydiacetylene-containing poly ordered assemblies that can be polymerized using any mers to undergo a visible color change upon exposure to a actinic radiation Such as, for example, electromagnetic variety of elements, including ultraViolet light, physical radiation in the UV or visible range of the electromagnetic StreSS, a change in Solvent and a change in counter ion, for Spectrum. The ability of the diacetylene Segments to Self example, make them ideal candidates for the preparation of assemble into ordered assemblies allows the polymerization various Sensing devices. Such Sensing devices can employ to proceed topochemically. The Self-assembly of diacety the diacetylene-containing polymers in Solution or in their lenes depends in large part on two factors: the molecular Solid State. architecture of the diacetylene Starting materials, and the 0017. The structural requirements of diacetylenic poly nature of the copolymer Segment. The diacetylene Starting mer for a given Sensing application are typically application materials of this invention are designed to have a molecular Specific. Features Such as overall chain length, Solubility, architecture which not only enhances but directs their ability polarity, crystallinity, and the presence of functional groups to Self-assemble, by providing an “engineered’ intermolecu for further molecular modification all cooperatively deter lar affinity for the diacetylene molecules to aggregate into mine a diacetylene containing polymer’s ability to Serve as ordered assemblies. An example of a copolymer Segment for the diacetylene materials is a polyurethane polymer System a useful Sensing material. that contributes to the self-assembly of the diacetylenes by 0018. The diacetylene compounds can be easily and providing a hydrogen bonding template for the formation of efficiently polymerized into polydiacetylene-containing polymers that develop a color, Such as blue or purple, as the ordered assemblies of diacetylenes. polymerization proceeds. The polydiacetylene-containing 0013. It is believed that the diacetylene-containing poly polymers can further undergo desired color changes in mers exhibit a color development based on the propensity of response to an external Stimulus Such as heat, a change in the copolymer to Self-assemble at the molecular level into Solvent or counterion, if available, or physical StreSS. ordered morphologies. Consequently, the diacetylene moi 0019. Both the color development of the polydiacetylene eties contained within the polymer backbone are aligned to containing polymer and the Secondary color response of the Such a degree that cross-linking can occur acroSS the polydiacetylene-containing polymers to Stimuli is a function diacetylene functionality, resulting in a conjugated network. in part of the inherent degree of Self-assembly, or ordering, The ensuing observed color development can be a direct of the system at the molecular level. The desired level of indication of the degree of conjugation that exists in a Self-assembly can be facilitated by hydrogen bonding of the particular system. The cross-linked diacetylene in the poly copolymer Segment, Such as polyurethanes. A polymer Sys mer network provides two material attributes that are desir tem that does not drive ordering, Such as a material lacking able in many applications: 1) enhanced integrity, 2) a color hydrogen bonding Sites for Spontaneous assembly, is leSS development. desirable from a Self-assembly perspective. 0.014 Polymerization of the diacetylene components 0020. The present invention provides blends of polydi result in polymerization reaction products that have a color acetylene-containing polymers with other materials that in the visible spectrum, i.e., in the wavelength between 400 retain chromogenic characteristics. It may be desirable to nm and 600 nm of varying intensity as measured by chroma blend the polydiacetylene-containing polymers with other (C) and hue as measured by hue angle (h) depending on materials to meet the objectives of a desired application. In their conformation and exposure to external factors. L*, C general, the polymer blend will contain the functional char and h are measurements often used in the paint and textile acteristics of the additive while retaining the chromogenic industry to quantify the observed colors and to monitor lot characteristics of the diacetylene-containing polymer. AS to lot consistency. L* is the lightness of the color on a Scale used herein, the term “functional characteristics,” means from 0, or pure black, to 100, or pure white. C* (chroma) is physical characteristics of the additive Such as rheological the Saturation or a measure of the intensity of a particular properties (e.g., viscoelasticity, elasticity), mechanical prop hue or observed color. Chroma may also be defined more erties (rigidity hardness), thermal properties, and adhesive formally as the distance of departure of a chromatic color properties (shear strength, adhesion). For example, diacety from the neutral (gray) color of the same value. The chroma lene-containing polymers may be blended with tackifiers Scale begins at Zero, but has no arbitrary end. AS the C* and/or acrylic polymers to form a pressure Sensitive adhe value increases, the relative Saturation also increases. Sive with a chromogenic response to external Stimuli. Chroma may be best thought of as a quantity, as in a measure Depending on the choice of both the diacetylene-containing of how much of the particular color is present. Hue (h) polymer and the materials added, the color development of represents the hue angle of the color represented and ranges the resultant blend can be affected. Polymer blends of the from O to 360. invention are further described below, with reference to 0.015 Polymers containing diacetylene components can certain terms understood by those in the chemical arts as exhibit a reversible color change and/or a three State color referring to certain hydrocarbon groups. Reference is also change. For example, after polymerization the resulting made throughout the Specification to polymeric versions blue-phase polymer network can change color to a reddish thereof. In that case, the prefix “poly” is inserted in front of orange State upon exposure to heat, a change in Solvent or the name of the corresponding hydrocarbon group. counterion, or physical StreSS. This reddish-orange polymer 0021 Except where otherwise noted, such hydrocarbon network can then change color to a yellowish-orange State groups, as used herein, may include one or more heteroat upon further exposure to heat, a change in Solvent or oms (e.g., oxygen, nitrogen, Sulfur, or halogen atoms), as counterion, or physical StreSS. Additionally, polymer net well as functional groups (e.g., Oxime, ester, carbonate, WorkS disclosed herein can cycle between these reddish amide, ether, urethane, urea, carbonyl groups, or mixtures orange and yellowish-orange States in a reversible manner. thereof). US 2006/004 1057 A1 Feb. 23, 2006

0022. The term “aliphatic group” means a saturated or 0034) 3. Anionic polymerization using bifunctional ini unsaturated, linear, branched, or cyclic hydrocarbon group. tiatorS Such as Sodium naphthalene which produce reactive This term is used to encompass alkyl, alkylene (e.g., oxy end groups that can be subsequently fitted with -OH, alkylene), aralkylene, and cycloalkylene groups, for -COOH, -COCl end groups by reaction with electro example. philes Such as ethylene oxide, carbon dioxide, and phosgene, respectively. 0023 The term “alkylene group” means a saturated, linear or branched, divalent hydrocarbon group. Particularly 0035 4. Step growth polymerization with a slight excess preferred alkylene groups are oxyalkylene groups. of the monomer containing the functional group desired at the end of the molecule. For example, to obtain -NH 0024. The term "oxyalkylene group” means a saturated, end groups an excess of the diamine would be used when linear or branched, divalent hydrocarbon group with a polymerized with a diacid. terminal oxygen atom. 0036) The segmented copolymers are then formed by the 0.025 The term “aralkylene group” means a saturated, reaction of a prepolymer and a diacetylene monomer con linear or branched, divalent hydrocarbon group containing at taining Suitable reactive end groups. For example, the fol least one aromatic group. lowing are common functional groups that react to form 0026. The term “cycloalkylene group” means a saturated, linkage Segments in a polymer chain: alcohol--carboxylic linear or branched, divalent hydrocarbon group containing at acid=ester linkage, alcohol-isocyanate=urethane linkage; least one cyclic group. amine--isocyanate=urea linkage, amine--carboxylic acid= amide linkage; carboxylic acid--isocyanate=amide linkage. 0027. The term “oxycycloalkylene group” means a satu 0037. The ability of the diacetylene-containing copoly rated, linear or branched, divalent hydrocarbon group con mer to exhibit color development will be influenced by the taining at least one cyclic group and a terminal oxygen atom. Structure of the linkage Segment contributed by the prepoly 0028. The term “aromatic group” means a mononuclear mer. In Some embodiments, the prepolymer Segment is aromatic hydrocarbon group or polynuclear aromatic hydro phase Separable or is incompatible with the diacetylene carbon group. The term includes arylene groups. containing segment as described in U.S. Pat. No. 4,721,769. 0029. The term “arylene group” means a divalent aro 0038. In addition to the selection of the diacetylene matic group. component, the type of polymer used may affect the prop erties, Such as color development, of the resultant diacety Diacetylene-Containing Polymer lene-containing copolymer. Both the flexibility and the 0030 Polyurethane systems are one example of a system distribution of Segments is impacted based on the polymer that can provide the Self-assembly characteristics necessary matrix chosen. The Structure of the Segments, i.e., the ring to contribute to color development during polymerization Substitution and linearity, may also affect the properties, and contribute to a chromogenic response in the resulting Such as color development, of the diacetylene-containing polymer. One polymerization method that can be used to copolymer. prepare the diacetylene-containing polymer is the polyure 0039. In many embodiments, the diacetylene-containing thane-based System described in applicant's copending polymer may contain at least one reactive emulsifying application entitled “Polydiacetylene Polymer Composi compound. The reactive emulsifying compound contains at tions and Methods of Manufacature, U.S. Ser. No. s least one anionic-functional group, cationic-functional filed the same date herewith, Attorney Docket No. group, a group that is capable of forming an anionic 58201 US002. Another example of urethane-based diacety functional group or cationic-functional group, or mixtures lene-Segmented copolymer is the two-step Solution polymer thereof. AS used herein, the term “reactive emulsifying ization technique described in Miller, J. A., Lin, S. B., compound” describes a compound that acts as an internal Hwang, K. S., Wu, K. S., Gibson, P. E., and Cooper, S. L., emulsifier because it contains at least one ionizable group. MACROMOLECULES, 18, (1985). 0040. Reactive emulsifying compounds are capable of 0031. Other ways of preparing the diacetylene-containing reacting with at least one of the components to become polymer are disclosed in U.S. Pat. Nos. 4,849,500; 4,721, incorporated into the diacetylene-containing polymers. 769; and 4,767.826. Prepolymers fitted with suitable reac Thus, the reactive emulsifying compound contains at least tive end groupS. Such as hydroxyl, carboxyl, amino, etc., can one, preferably at least two, active hydrogen-reactive (e.g., be readily prepared using a number of well established hydroxy-reactive) groups. Hydroxy-reactive groups include, Synthetic techniques. For example, the prepolymers can be for example, isocyanate, hydroxyl, mercapto, and amine synthesized by: groupS. 0.032 1. Free radical polymerization of vinyl monomers 0041. The incorporation of a reactive emulsifying com with initiators that supply -OH or -COOH end groups pound in the polymer improves the hydrophilicity of the Such as 4,4' azobis (4-cyano-n-pentanol) and 4,4'-azobis resulting polymer. For example, the reactive emulsifying (4-cyanovaleric acid). compound in the polymer allows for water dispersibility of the resulting polymer. Furthermore, Such dispersions do not 0.033 2. Cationic polymerization of monomers using generally require external emulsifiers, Such as Surfactants, dichloro compounds Such as p-di(2-chloropropyl) benzene for stability. which function as both initiators and transfer agents to produce -Cl end groups which can be readily converted to 0042 Preferably, a sufficient amount of reactive emulsi -OH end groups. fying compound is reacted Such that an external emulsifier US 2006/004 1057 A1 Feb. 23, 2006 is not necessary for preparing a Storage-Stable diacetylene containing polymer comprises about 0.5 to about 5 weight (V) percent, more preferably about 0.75 to about 3 weight G-X-N-Y-G percent, of Segments derived from the reactive emulsifying compound. If polyols containing polyethylene oxide are used, the amount of reactive emulsifying compound used in this preferred embodiment may be less to form a stable wherein G is OH, NHR or SH. Each of X and Y may be the dispersion. same or different. X, Y, and R are independently selected from aliphatic organic radicals free of reactive functional 0043. In certain embodiments, the reactive emulsifying groups (e.g., alkylene groups that are free of reactive func compound contains at least one anionic-functional group or tional groups), preferably having from about 1 to about 20 group that is capable of forming Such a group (i.e., an carbon atoms, and combinations thereof, with the proviso anion-forming group) when reacted with other polymer that R can be hydrogen. components. The anionic-functional or anion-forming 0048 Depending on the desired application, anionic or groups of the reactive emulsifying compound can be any cationic reactive-emulsifying compounds may be prefer Suitable group that contributes to ionization of the reactive able. For example, when used in biological applications, it emulsifying compound. For example, Suitable groups may be preferred that the reactive emulsifying agent contain include carboxylate, Sulfate, Sulfonate, phosphate, and Simi a cationic-functional group. In those circumstances, the lar groups. cationic feature of the polymer may minimize the potential for interaction with other additives, Such as antimicrobials. 0044) The preferred structure for reactive emulsifying This may be a particular concern, for example, in medical compounds with anionic-functional groups is generally rep applications. resented by Formula IV: 0049 Other useful compounds for the reactive emulsify ing compounds include those described as water-Solubiliz (IV) ing compounds in U.S. Pat. No. 5,554,686, which is incor R porated herein by reference. Those of ordinary skill in the art will recognize that a wide variety of reactive emulsifying o-x--y-g compounds are useful in the present invention. Polymer Additives 0050. The diacetylene-containing polymer can be wherein G is OH, NHR or SH and wherein Q is a negatively blended with other polymers, Such as elastomers, to obtain charged moiety Selected from COO and SO, or a group a resultant blend with the desired functional characteristics that is capable of forming Such a negatively charge moiety of both the diacetylene-containing polymer and the polymer upon ionization. Each of X, Y, and R' may be the same or additive. In general, the diacetylene-containing polymer different. X, Y, R, and R' are independently selected from comprises greater than 5 wt % of the polymer blend. In aliphatic organic radicals free of reactive functional groups preferred embodiments, the diacetylene-containing polymer comprises greater than 10 wt % of the polymer blend. The (e.g., alkylene groups that are free of reactive functional amount of diacetylene-containing polymer in the resultant groups), preferably having from about 1 to about 20 carbon blend can be affected by the number of diacetylene Segments atoms, and combinations thereof, with the provisos that: (i.) in the diacetylene-containing polymer or the propensity of R can be hydrogen; and (ii) R' is not required if Q is COO the diacetylene-containing polymer to Self-assemble. and SO. 0051 Specific examples of suitable materials include 0045. As an example, dimethylolpropionic acid (DMPA) polyethylene naphthalate (PEN) and isomers thereof (e.g., is a useful reactive emulsifying compound for certain 2,6-, 14-, 1.5-, 2,7-, and 2,3-PEN), polyalkylene terephtha embodiments of the invention. Furthermore, 2,2-dimethy lates (e.g., polyethylene terephthalate, polybutylene tereph lolbutyric acid, dihydroxymaleic acid, and Sulfopolyester thalate, and poly-1,4-cyclohexanedimethylene terephtha diol are other useful reactive emulsifying compounds. late), polyimides (e.g., polyacrylic imides), polyetherimides, atactic polystyrene, polycarbonates, polymethacrylates (e.g., 0046. In certain embodiments, the reactive emulsifying polyisobutyl methacrylate, polypropylmethacrylate, poly compound contains at least one cationic-functional group or ethylmethacrylate, and polymethylmethacrylate), polyacry group that is capable of forming Such a group (i.e., a lates (e.g., polybutylacrylate and polymethylacrylate), Syn cation-forming group) when reacted with other polymer diotactic polystyrene (SPS), Syndiotactic poly-alpha-methyl components. The cationic-functional or cation-forming Styrene, Syndiotactic polydichlorostyrene, copolymers and groups of the reactive emulsifying compound can be any blends of any of these polystyrenes, cellulose derivatives Suitable group that contributes to ionization of the reactive (e.g., ethyl cellulose, cellulose acetate, cellulose propionate, emulsifying compound. In most embodiments, the reactive cellulose acetate butyrate, and cellulose nitrate), polyalky emulsifying compound is an amine. lene polymers (e.g., polyethylene, polypropylene, polybu tylene, polyisobutylene, and poly(4-methyl)pentene), fluori 0047 The preferred structure for reactive emulsifying nated polymers (e.g., perfluoroalkoxy resins, compounds with cationic-functional groups is generally polytetrafluoroethylene, fluorinated ethylene-propylene represented by Formula V: copolymers, polyvinylidene fluoride, and polychlorotrifluo US 2006/004 1057 A1 Feb. 23, 2006 roethylene), chlorinated polymers (e.g., polyvinylidene polyfunctional isocyanate with a polyol according to well chloride and polyvinylchloride), polysulfones, polyetherSul known reaction mechanisms. Useful diisocyanates for fones, polyacrylonitrile, polyamides, Silicone resins, epoxy employment in the production of a polyurethane include resins, polyvinylacetate, polyether-amides, ionomeric res 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocy ins, elastomers (e.g., polybutadiene, polyisoprene, and neo anate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexylene prene), and polyurethanes. Also Suitable are copolymers, diisocyanate, and 4,4'-diphenylmethane diisocyanate. Com e.g., copolymers of PEN (coPEN) (e.g., copolymers of 2,6-, binations of one or more polyfunctional isocyanates may 1,4-, 1.5-, 2,7-, and/or 2,3-naphthalene dicarboxylic acid, or also be used. Useful polyols include polypentyleneadipate esters thereof, with (a) terephthalic acid, or esters thereof; glycol, polytetramethylene ether glycol, polyethylene gly (b) isophthalic acid, or esters thereof; (c) phthalic acid, or col, polycaprolactone diol, poly-1,2-butylene oxide glycol, esters thereof; (d) alkane glycols; (e) cycloalkane glycols and combinations thereof. Chain extenders, Such as butane (e.g., cyclohexane dimethane diol), (f) alkane dicarboxylic diol or hexanediol may also be used in the reaction. Useful acids; and/or (g) cycloalkane dicarboxylic acids (e.g., cyclo commercially available urethane polymers include hexane dicarboxylic acid)), copolymers of polyalkylene MORTHANE L424.167 (MI=9.7), PN-04 or 3429, from terephthalates (e.g., copolymers of terephthalic acid, or Morton International (Seabrook, N.H.), and X-4107 from esters thereof, with (a) naphthalene dicarboxylic acid, or B.F. Goodrich Co. (Cleveland, Ohio). esters thereof; (b) isophthalic acid, or esters thereof; (c) 0055. Useful polyolefins include homopolymers of eth phthalic acid, or esters thereof; (d) alkane glycols; (e) ylene, propylene, and the like, as well as copolymers of cycloalkane glycols (e.g., cyclohexane dimethanel diol), (f) these monomers with, for example, acrylic monomers and alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxy other ethylenically unsaturated monomers, Such as Vinyl lic acids (e.g., cyclohexane dicarboxylic acid)), and Styrene acetate and higher alpha-olefins. Such polymers and copoly copolymers (e.g., Styrene-butadiene copolymers and Sty merS may be prepared by conventional free radical poly rene-acrylonitrile copolymers), 4,4'-bibenzoic acid and eth merization or catalysis of Such ethylenically unsaturated ylene glycol. monomers. The degree of crystallinity of the polymer may 0.052 Exemplary non-fluorinated polymers include vary. The polymer may, for example, be a Semi-crystalline polyamides, pololefins, polyethers, polyurethanes, polyes high density polyethylene or may be an elastomeric copoly ters, polyimides, polystyrene, polycarbonates, polyketones, mer of ethylene and propylene. Carboxylic acid, anhydride, polyureas, acrylics, and mixtures thereof, and the like. In or imide functionalities may be incorporated into the poly Some embodiments, a non-fluorinated polymer may be a mer by polymerizing or copolymerizing functional mono non-fluorinated elastomer, Such as acrylonitrile butadiene mers, Such as acrylic acid or maleic anhydride, or by rubber (NBR), butadiene rubber, chlorinated and chlorosul modifying the polymer after polymerization, e.g., by graft fonated polyethylene, chloroprene, ethylene-propylene ing, by oxidation, or by forming ionomers. Examples monomer (EPM) rubber, ethylene-propylene-diene mono include acid modified ethylene acrylate copolymers, anhy mer (EPDM) rubber, epichlorohydrin (ECO) rubber, poly dride modified ethylene Vinyl acetate copolymers, anhydride isobutylene, polyisoprene, polysulfide, polyurethane, sili modified polyethylene polymers, and anhydride modified cone rubber, blends of polyvinyl chloride and NBR, styrene polypropylene polymers. Such polymers and copolymers butadiene (SBR) rubber, ethylene-acrylate copolymer rub generally are commercially available, for example, under the ber, and ethylene-vinyl acetate rubber. Suitable ethylene trade designations ENGAGE (Dow-DuPont Elastomers, vinyl acetate copolymers include ELVAX, available from E.I Wilmington, Del.) or EXACT (ExxonMobil, Linden, N.J.). du Pont de Nemours and Co. (Wilmington, Del.). Suitable anhydride modified polyethylene polymers are 0053. Many polyamides that are useful as non-fluorinated commercially available from E.I. du Pont de Nemours and polymers are generally commercially available. For Co. (Wilmington, Del.), under the trade designation BYNEL example, polyamides, Such as any of the well known nylons co-extrudable adhesive resins. are available from a number of sources. Particularly desir 0056 Useful acrylics include polymers of acrylic acid, able polyamides are nylon-6, nylon-6,6, nylon-11, and methyl acrylate, ethyl acrylate, acrylamide, methacrylic nylon-12. It should be noted that the selection of a particular acid, methyl methacrylate, ethyl methacrylate, and the like, polyamide material should be based upon the physical and mixtures thereof. requirements of the particular application for the multi-layer article. For example, nylon-6 and nylon-6.6 offer better heat 0057 Useful polycarbonates include aliphatic polycar resistance properties than nylon-11 and nylon-12, whereas bonates, Such as polyester carbonates, polyether carbonates, nylon-11 and nylon-12 offer better chemical and moisture and bisphenol A-derived polycarbonates, and the like. resistance properties. In addition, other nylon materials, 0058 Useful polyimides include polyimide polymers Such as nylon-6,12, nylon-6.9, nylon-4, nylon-42, nylon-4, made from the anhydride of pyromellitic acid and 4,4'- 6, nylon-7, and nylon-8 may be used, as well as ring diaminodiphenyl ether, available from E.I. duPont de Nem containing polyamides, Such as nylon-6, T and nylon-6, 1. ours and Co. under the trade designation KAPTON. Varia Suitable nylons include VESTAMID L2140, a nylon-12, tions include KAPTON H, KAPTON E, and KAPTON V, available from Creanova, Inc. (Somerset, N.J.). Polyether among others. containing polyamides having the trade designation 0059 Additional examples of useful non-fluorinated PEBAX, available from Atochem North America (Philadel polymers, as noted above, include polyesters, polycarbon phia, Pa.) may also be used. ates, polyketones, and polyureas. Exemplary commercially 0.054 Useful polyurethanes include aliphatic, available polymers include polyesters having the trade des cycloaliphatic, aromatic, and polycyclic polyurethanes. ignation SELAR (E.I. du Pont de Nemours and Co.), poly These polyurethanes are typically produced by reaction of a carbonates having the trade designation LEXAN (General US 2006/004 1057 A1 Feb. 23, 2006

Electric Co., Pittsfield, Mass.), polyketones having the trade trade designation, KEVLAR), and the like can be added, designation KADEL (Amoco Corp., Chicago, Ill.), and generally in amounts up to about 50 parts per hundred parts polyureas having the trade designation SPECTRIM (Dow by weight of the diacetylene-containing polymer, provided Chemical Co., Midland, Mich.). that Such additives are not detrimental to the properties 0060 Exemplary commercially available elastomers desired in the final PSA composition. include those having the trade designations NIPOL 1052 0065 Other additives such as dyes, inert fluids (e.g., NBR, HYDRIN C2000 epichlorohydrin-ethylene oxide rub hydrocarbon oils), pigments, flame retardants, stabilizers, ber, and ZETPOL hydrogenated NBR (Zeon Chemical, antioxidants, compatibilizers, antimicrobial agents (e.g., Louisville, Ky.); HYPALON 48 chlorosulfonated polyeth Zinc oxide), electrical conductors, thermal conductors (e.g., ylene rubber and VAMAC ethylene-acrylate elastomer (E.I. aluminum oxide, boron nitride, aluminum nitride, and nickel du Pont de Nemours and Co., Wilmington, Del.); NORDEL particles), and the like can be blended into these composi EPDM (R.T. Vanderbilt Co., Inc., Norwalk, Conn.); tions, generally in amounts of from about 1 to about 50 KRYNAC NBR, PERBUNAN NBR/PVC blend and percent by total volume of the composition. THERBAN hydrogenated NBR (Bayer Corp., Pittsburgh, Pa.); SANTOPRENE thermoplastic elastomers (Advanced Applications Elastomer Systems, Akron, Ohio); KRATON thermoplastic 0066 Once the polymer blend is formed, it is easily elastomers (Shell Chemical Co., Houston, Tex.); and applied to a Substrate and then dried to form a coating. KELTAN EPDM (DSM Elastomers Americas, Addis, La.). Drying can be carried out either at room temperature (i.e., 0061 The desired properties of the diacetylene-contain about 20° C.) or at elevated temperatures (e.g., about 25 C. ing polymer blend must be balanced. Increased amounts of to about 150° C.). Drying can optionally include using the polymer additive can cause a dilution affect that may forced air or a vacuum. This includes the drying of Static weaken the color development of the resulting diacetylene coated Substrates in ovens, Such as forced air and Vacuum containing polymer/additive blend. This dilution effect can Ovens, or drying of coated Substrates that are continuously be minimized by increasing the relative diacetylene Seg conveyed through chambers heated by forced air, high ments in the diacetylene-containing polymer. On the other intensity lamps, and the like. Drying may also be performed hand, excessive amounts of diacetylene-containing polymer at reduced (i.e., less than ambient) pressure. may minimize or mask the desired properties of the polymer 0067. A coating of the diacetylene-containing polymer additive. blend can be formed on a wide variety of substrates. For example, the coating can be applied to sheeting products Pressure Sensitive Adhesives (e.g., decorative, reflective, and graphical), labelstock, and 0062) The diacetylene-containing polymer, or the tape backings. The Substrate can be any Suitable type of diacetylene-containing polymer blend, can be blended with material depending on the desired application. Typically, the tackifiers and plasticizers to form preSSure Sensitive adhe Substrate comprises a nonwoven, paper, polymeric film (e.g., Sive compositions (PSA) without compromising the inherent polypropylene (e.g., biaxially oriented polypropylene chromogenicity of the diacetylene-containing polymer. For (BOPP)), polyethylene, polyurea, polyurethane, or polyester example, compatible tackifiers and/or plasticizers may be (e.g., polyethylene terephthalate)), or release liner (e.g., added to aid in optimizing the ultimate tack and peel Siliconized liner). properties of the diacetylene-containing PSA. In general, the 0068. Where post-crosslinking of the coated polymer is diacetylene-containing polymer, or its polymer blend, com desirable, aminosilanes can be used. Upon coating and prises at least 30% of the PSA composition. drying the polymer blend, the aminosilanes will allow 0.063. The use of such tack-modifiers is common in the crosslinking to occur. art, as is described in the Handbook of Pressure Sensitive 0069 Exposure of the diacetylene-containing polymer, Adhesive Technology, edited by Donatas Satas (1982). and/or the polymer blend, to radiation results in a color Examples of useful tackifiers include, but are not limited to, development from clear to typically red or blue. Radiation rosin, rosin derivatives, polyterpene resins, coumarone-in dene resins, and the like. Plasticizers which may be added to Sources include UV, gamma, electron-beam (e-beam), and the adhesive of the invention may be selected from a wide solar sources. In most embodiments, an ultraviolet (UV) variety of commercially available materials. Representative radiation Source is used to cure the polymers. The color plasticizers include polyoxyethylene aryl ether, dialkyl adi development observed in the polymer is independent of the pate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphe irradiation Source utilized, but color intensity, i.e., chroma, nyl phosphate, 2-ethylhexyl adipate, toluenesulfonamide. is determined in part by the dosage applied. dipropylene glycol dibenzoate, polyethylene glycol diben 0070 The polymer can exhibit a post-radiation, or sec Zoate, polyoxypropylene aryl ether, dibutoxyethoxyethyl ondary chromogenic, in response to Stimuli Such as to formal, and dibutoxyethoxyethyl adipate. UV stabilizers as Solvents (Solvatochromism), temperature change (thermo known in the art may also be added. chromism) and applied stress (piezochromism). Upon expo Sure to the Stimuli, the polymer network undergoes yet 0064. Other materials may also be added to obtain desired characteristics in the diacetylene-containing PSA. another color change from the developed color to a Second For example, fillers, Such as fumed Silica, fibers (e.g., glass, ary color, Such as yellow. This Secondary color change may metal, inorganic, or organic fibers), carbon black, glass or be reversible, depending on the Selection of the Starting ceramic beads/bubbles, particles (e.g., metal, inorganic, or materials. organic particles), polyaramids (e.g., those available from 0071 Time for development of color may affect the DuPont Chemical Company; Wilmington, Del. under the Selection of Starting materials. For those applications where US 2006/004 1057 A1 Feb. 23, 2006 rapid color development is not critical, longer time to allow 0076 Each sample so prepared was tested for 180 peel Self-assembly of the polymer System may allow the use of a adhesion using an IMASS slip/peel tester (Model 3M90, greater range of Starting materials. commercially available from Instrumentors Inc., StrongS ville, Ohio) at a rate of 2.3 meters/minute (90 inches/minute) 0.072 Objects and advantages of this invention are further using a two Second data collection time and/or at a rate of illustrated by the following examples, but the particular 30.5 centimeters/minute (12 inches/minute) using a five materials and amounts thereof recited in these examples, as Second data collection time. Two Samples of each compo well as other conditions and details, should not be construed Sition were tested. The reported peel adhesion value is an to unduly limit this invention. average of the peel adhesion value from each of the two EXAMPLES Samples. 0073. These examples are merely for illustrative pur Shear Strength poses only and are not meant to be limiting on the Scope of the appended claims. All parts, percentages, ratios, etc. in the 0077. This shear strength test is similar to the test method examples and the rest of the Specification are by weight, described in ASTM D 3654-88. PSA tapes, prepared as unless noted otherwise. described above, were cut into 1.27-centimeter by 15-cen timeter Strips. Each Strip was then adhered to a Stainless Steel 0.074. Furthermore, molecular weights in the examples panel Such that a 1.27-centimeter by 1.27-centimeter portion and the rest of the Specification are weight average molecu of each Strip was in firm contact with the panel and one end lar weights, unless noted otherwise. Solvents used were portion of the Strip hung free. obtained from Aldrich Chemical Company; Milwaukee, Wis. 0078. The panel with the attached strip was placed in a rack such that the panel formed an angle of 178 with the 180 Peel Adhesion extended free end of the strip. The strip was tensioned by 0075. This peel adhesion test is similar to the test method application of a force of one kilogram applied as a hanging described in ASTM D 3330-90, Substituting a glass substrate weight from the free end of the strip. The 2 less than 180 for the stainless steel Substrate described in the test. This test was used to negate any peel forces, thus ensuring that only will be referred to as the “glass substrate peel adhesion test” Shear Strength forces were measured, in an attempt to more for the purposes of this document. PSA tapes, were cut into accurately determine the holding power of the tape being 1.27-centimeter by 15-centimeter strips. Each strip was then tested. adhered to a 10 centimeter by 20 centimeter clean, solvent 0079 The elapsed time for each tape sample to separate washed glass coupon by passing a 2-kilogram roller once from the test panel was recorded as the shear Strength. Each over the strip. The bonded assembly dwelled at room test was terminated at 10,000 minutes, unless the adhesive temperature for about one minute. failed at an earlier time (as noted).

Table of Abbreviations

Abbreviation or Trade Designation Description ACCLAIM 422ON A polyethylene oxide-capped polypropylene oxide diol with an approximate molecular weight of 4,000 grams/mole and an OH equivalent weight of approximately 2,000 grams/mole, commercially available from Bayer Corp., Pittsburgh, PA DBTDL Dibutyltindilaurate, commercially available from Aldrich Chemical Company; Milwaukee, Wisconsin HDI Hexamethylene diisocyanate, commercially available from Aldrich Chemical Company; Milwaukee, Wisconsin DAD Diacetylene diol with the structure HO(CH),C=CC=C(CH), OH defined by the value of n. THF Tetrahydrofuran Shell L-2203 A polyethylene/polybutylene dihydroxy terminated oligomer with an approximate molecular weight of 3500 grams/mole available from Shell Chemical Co., Houston, TX. Escorez, 1310 An aliphatic hydrocarbon resin available from Exxon Chemical; Houston, TX. Hercules R1125 A fully hydrogenated hydrocarbon resin with ~5% aromaticity available from Hercules Inc.; Wilmington, DE Hercules R9100 A partially hydrogenated hydrocarbon resin with ~5% aromaticity available from Hercules Inc.; Wilmington, DE Block Copolymer A high molecular weight (>1,000,000 grams/mol) styrenefisoprene star block copolymer comprised of radially extending polyisoprene chains possessing a polystyrene tail. The polystyrene comprises --9% of the bulk. PBHTO Polybutadiene dihydroxyl terminated oligomer Meq Milliequivalents FPM Feet per minute PEG Polyethylene glycol oligomer of 400 molecular weight US 2006/004 1057 A1 Feb. 23, 2006

-continued

Table of Abbreviations

Abbreviation or Trade Designation Description H-12 MDI 4,4'-methylenebis(cyclohexylisocyanate) PET Polyethylene terephthalate

SYNTHESIS EXAMPLE 1. was 0.58 med and the amount of total NCO was 0.60 med. 0080. To facilitate handling, Shell L-2203 was placed The resultant polymer had a molecular weight M of 90,700. into a convection oven at about 40 C. for about 45 minutes. A glass reaction vessel containing a magnetic Stir bar and EXAMPLES 1-9 AND COMPARATIVE fitted with a thermometer and a reflux condenser was purged EXAMPLE C1 with nitrogen and a nitrogen inlet was placed on the con denser. To this vessel was added Shell L-2203 (41.12 grams, Part I: Optical Screening of PSA Blends 23.85 meq), DAD n=4 (i.e. 5,7-dodecadiyn-1,12-diol) 0084. To test the optical properties of blends of the (0.9720 grams, 10.02 meq) and THF (dried by passing polymer prepared in Synthesis Example 1 with tackifiers, through basic alumina) (200 milliliters). The mixture was samples of the polymer and the polymer blended with stirred with gentle heating to dissolve the diols and HDI (2.85 grams, 33.87 meq) and 1 drop of DBTDL was added. tackifier were prepared as 20% solids solutions in THF as The mixture was allowed to react under reflux conditions described in Table 1. The dispersions described in the (-65 C.) for about 19 hours. The resultant polymer had a following examples were coated using a knife coater on number average molecular weight (M) of 34,000. nitrogen corona treated PET to a dry film thickness of 51 micrometers (2 mils). The coated films were dried at 70° C. SYNTHESIS EXAMPLE 2 for ten minutes and stored at 23° C. and 50%. R. H. overnight. The films were UV irradiated using a 300 W H 0081. A glass reaction vessel containing a magnetic stir bar and fitted with a thermometer and a reflux condenser was lamp, one pass at 80 FPM. The color of the coating before purged with nitrogen and a nitrogen inlet was placed on the and after UV irradiation was noted as well as the Chroma condenser. To this vessel was added toluene (purified by values. Chroma values (C) were determined before and passing through basic alumina) (30 milliliters) and HDI after exposure using a X-Rite Spectrodensitometer, model (1.262 grams, 15.0 meq). Into an argon purged addition #528L (C* is representative of the amount of color present funnel, was placed toluene (purified by passing through in a Sample). basic alumina) (15 milliliters) and PBHTO (7.5 grams, 7.5 med). The addition funnel was attached to the reaction TABLE 1. vessel, 1 drop of DBTDL was added to the HDI solution, the Ratio of Polymer PBHTO Solution was added dropwise to the HDI solution from Synthesis over a period of about one hour and the reaction vessel was Example 1/ Color pre- Color post heated to reflux temperature (about 110° C). The mixture Tacklifer Tackifier UV UV was allowed to react under reflux conditions for about 3 Example Identity (by weight) (C*) (C*) hours. DAD n=4 (i.e. 5,7-dodecadiyn-1,12-diol) (0.7275 1. Escorez, 1310 50/50 O 13.78 2 Escorez, 1310 66.7/33.3 O 29.37 grams, 7.5 med) was added to the reaction vessel and the 3 Escorez, 1310 80f2O O 43.79 contents were allowed to react an additional 3 hours at about 4 Hercules 50/50 O 36.04 60° C. The resultant polymer had a number average molecu R1125 lar weight (M) of 8,300. 5 Hercules 66.7/33.3 O 48.27 R1125 SYNTHESIS EXAMPLE 3 6 Hercules 80f2O O 59.20 R1125 7 Hercules 50/50 O 25.93 0082) A stock solution of ACCLAIM 4220N and DAD R91OO n=4 (i.e. 5,7-dodecadiyn-1, 12-diol) was prepared in THF in 8 Hercules 66.7/33.3 O 44.65 a weight ratio of ACCLAIM 4220N:DAD of 97.3. A stock R91OO solution of HDI in THF was also prepared. These stock 9 Hercules 80f2O O 57.26 Solutions were attached via canulas to a Bohdan combina R91OO torial reactor. The stock Solutions were used to deliver the C1 None 1OO/O O 68.63 desired quantity of OH (combination of ACCLAIM 4220N and DAD) and NCO (HDI). The amount of total OH was 0.60 med and the amount of total NCO was 0.60 meq. The Part II: PSA Tape Testing resultant polymer had a molecular weight Mn of 22,500. 0085 Tape samples of the polymer from Synthesis Example 1 and the blends of the polymer from Synthesis SYNTHESIS EXAMPLE 4 Example 1 and tackifiers described above were prepared and 0.083. The same procedure described for Synthesis tested for 180 Peel and Shear Strength using the test Example 3 was followed except that the amount of total OH methods described above, the data are presented in Table 2. US 2006/004 1057 A1 Feb. 23, 2006

wherein the polymer blend exhibits chromogenic charac TABLE 2 teristics of the diacetylene-containing copolymer and the functional characteristics of the additive. Peel before Shear Strength Peel after Shear Strength UV cure before UV cure UV cure after UV cure 2. The polymer blend of claim 1, wherein the additive is Example (N/dm) (minutes) (N/dm) (minutes) a tackifier. 3. The polymer blend of claim 1, wherein the additive is 1. 24.5 10,000 14.9 10,000 a polymer. 2 34.1 8,422 25.4 5,188 3 24.1 3,498 12.7 2,351 4. The polymer blend of claim 1, wherein the chromoge 4 1.1 10,000 0.4 10,000 nic characteristics are reversible. 5 5.9 10,000 2.8 10,000 5. A polymer blend of claim 4, wherein the diacetylene 6 15.3 10,000 9.6 9,528 7 31.3 10,000 32.4 10,000 Segments are linked by urethane linkages. 8 40.3 7,546 34.4 4,634 6. A polymer blend of claim 4, wherein the diacetylene 9 21.0 5,812 12.3 4,390 Segments are linked by ester linkages. C1 5.3 10,000 2.8 10,000 7. A polymer blend of claim 4, wherein the diacetylene Segments are linked by amide linkages. 8. The polymer blend of claim 1, wherein the functional EXAMPLE 10 characteristic is an adhesive characteristic of the additive. 0.086 A Solution of 95 parts by weight of Block Copoly 9. The polymer blend of claim 8, wherein the adhesive mer and 5 parts by weight of the polymer prepared in characteristic is Selected from the group consisting of tensile Synthesis Example 2 was prepared in toluene, coated onto a Strength, adhesion, peel Strength, and cohesive Strength. silicone release liner, dried for 10 minutes at 70° C. and UV 10. A chromogenic copolymer comprising irradiated using a 600W cure line, one pass at 80 FPM. The at least two diacetylene Segments, material turned blue. a linkage Segment; and EXAMPLES 11-15 at least one reactive emulsifying Segment. 0087. A series of blends of the polymers of Synthesis 11. A polymer blend, comprising the chromogenic Example 3 and Synthesis Example 4 were prepared in copolymer of claim 10, and toluene according to the ratios shown in Table 3. The blends were coated onto a Silicone release liner, dried for 10 an additive with at least one functional characteristic; minutes at 70° C. and UV irradiated using a 600W cure line, wherein the polymer blend exhibits chromogenic charac one pass at 80 FPM. The observed color change is listed in teristics of the diacetylene-containing copolymer and Table 3. the functional characteristics of the additive. 12. The polymer blend of claim 11, wherein the additive TABLE 3 is a tackifier.

Relative amount of Relative amount of 13. The polymer blend of claim 11, wherein the additive Polymer from Polymer from is a polymer. Synthesis Example 3 Synthesis Example 4 14. The polymer blend of claim 11, wherein the chro Example (parts by weight) (parts by weight) Color change mogenic characteristics are reversible. 11 2 1. Blue 15. A polymer blend of claim 10, wherein the diacetylene 12 2 Blue Segments are linked by urethane linkages. 13 1. 3 Blue 16. The copolymer of claim 10, wherein the diacetylene 14 1. 4 Blue Segments are linked by ester linkages. 15 1. 6 Light Blue 17. The copolymer of claim 10, wherein the diacetylene Segments are linked by amide linkages. 0088. The complete disclosures of the patents, patent 18. The polymer blend of claim 11, wherein the functional documents, and publications cited herein are incorporated characteristic is an adhesive characteristic of the additive. by reference in their entirety as if each were individually 19. The polymer blend of claim 18, wherein the adhesive incorporated. Various modifications and alterations to this characteristic is Selected from the group consisting of tensile invention will become apparent to those skilled in the art Strength, adhesion, peel Strength, and cohesive Strength. without departing from the Scope and Spirit of this invention. 20. The polymer blend of claim 10, wherein the reactive It should be understood that this invention is not intended to emulsifying Segment is formed from a reactive emulsifying be unduly limited by the illustrative embodiments and compound represented by the formula V: examples Set forth herein and that Such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the (V) claims set forth herein as follows. G-X-N-Y-G What is claimed is: 1. A polymer blend, comprising: a chromogenic copolymer comprising at least two wherein G is Selected from the group consisting of OH, diacetylene Segments, NHR and SH; and an additive with at least one functional characteristic, wherein each of X and Y may be the same or different; US 2006/004 1057 A1 Feb. 23, 2006

wherein each of X and Y are independently selected from preferably having from about 1 to about 20 carbon aliphatic organic radicals having from about 1 to about atoms, and combinations thereof; 20 carbon atoms, free of reactive functional groups, and combinations thereof, and R can be hydrogen; and wherein R can be hydrogen or an aliphatic organic radical R" is optional if Q is COO and SO. having from about 1 to about 20 carbon atoms, free of 22. The copolymer of claim 10 wherein the diacetylene reactive functional groups, and combinations thereof. Segment comprises the general Structure 21. The copolymer of claim 10, wherein the reactive emulsifying Segment is formed from a reactive emulsifying compound represented by the formula IV: wherein n is 1 to 9. 23. The polymer blend of claim 15 wherein at least 80% of the linkages between diacetylene Segments are urethane (IV) R and urea linkages. 24. The polymer blend of claim 23 wherein at least 95% a-x--y-g of the linkages between diacetylene Segments are urethane and urea linkages. 25. A pressure Sensitive adhesive comprising the copoly mer of claim 10. wherein G is Selected from the group consisting of OH, 26. A pressure Sensitive adhesive comprising the polymer NHR and SH; blend of claim 11. wherein Q is a negatively charged moiety Selected from 27. The pressure sensitive adhesive of claim 26, wherein COO and SO, or a group that is capable of forming the adhesive exhibits a chromogenic response when exposed Such a negatively charge moiety upon ionization; to an external Stimulus. 28. The copolymer of claim 10, wherein the copolymer is each of X, Y and R' may be the same or different; water dispersible. X, Y, R, and R' are independently selected from aliphatic organic radicals free of reactive functional groups,