SA110310120B1 - Butyl rubber based compositions exhibitng antibacterial properties - Google Patents

Abstract

The invention relates to the use of butyl ionomers or butyl ionic units to which a partially halogenated group is added to reduce the number and/or prevent the accumulation of organisms. The organisms may be bacteria, algae, fungi, mollusca or arthropoda. The invention also relates to coatings of shaped articles comprising butyl ionomers.

Description

b. Butyl rubber based compositions exhibitng antibacterial properties. Reducing the number of organisms and/or preventing the accumulation of organisms. The organisms may be cbacteria © algae calgae fungi mollusca molluscs or arthropoda . The invention also relates to coatings of formed articles comprising butyl ionic units .lonomers Poly(isobutylene-co-isoprene) “Poly(isobutylene-co-isoprene) or dallas (IIR) is a synthetic synthetic elastomer known as butyl rubber that has been made since the 1940s through random cationic copolymerization Random cationic copolymerization of isobutylene with small amounts of isoprene (1-?mol 7).As a result of its molecular structure, JR has superior air impermeability i chigh loss modulus oxidative stability and extended -fatigue resistance Vo understands that butyl rubber is a copolymer of isoolefin and one or more 0 preferably It is conjugated to multiolefins as co-monomers. Co-monomers include commercial butyl, a major part of the isoolefin and a small amount; not more than 7.5 7 mol; Conjugated multiolefins. Butyl rubber or butyl polymer 0 is prepared in a thin film process. slurry process using methyl chloride as a diluent and friedelcrafts catalyst as part of the polymerization initiator. This process is also described in the U.S.

Patent No. and Ullmann's Encyclopedia of Industrial Chemistry, volume 23, 1993, 2,356,128 .pages 288-295

Functionally reactive allylic halide butyl rubber Halogenation Produces halogenation

Conventional butyl rubber halogenation processes elastomer within allylic halide rubber

Ullmann's described in; For example, butyl rubber halogenation processes

Encyclopedia of Industrial Chemistry (Fifth, Completely Revised Edition, Volume

A231 Editors Elvers, et al.) and/or “Rubber Technology” (Third Edition) by Maurice ©

Morton, Chapter 10 (Van Nostrand Reinhold Company © 1987). particularly pp. 297- 300. The presence of allylic halide functions allows nucleophilic alkylation reactions to occur. He recently presents such processing of brominated butyl rubber (BIIR) | 0 with nitrogen and/or phosphorus attached to nucleophiles in the solid state; It leads to the generation of 1000065 base 118 ion units by excitation of physical and chemical properties (see Parent, J. S.; Liskova, A.; Whitney. R. A: Resendes, R. Journal of Polymer Science, Part A: Polymer Chemistry 43, 5671). 0 5 Penciu, A.; Guillen-Castellanos, 2004, 7477-7483, 37). The function of the ionic unit: 100006 generated from the reaction of basic nitrogen or phosphorous on the nucleophile and the allylic halide site 3114 to produce ammonium or phosphonium for the ionic group, respectively. The physical properties of this BIR were attributed to the ionic units | ionomers | 00 (cgreen strength coefficient 00000105 non-ionomeric counterpart filler .non-ionomeric counterpart cand) etc. interactions butyl to the para-methylstyrene nutrient mixture He discovered Previously, the addition of (initiator as an initiator H,0 / AICI, and 17 _ of the feed mixture” with IB <MeCl) polymerization of styrenic mol styrenic groups 7 01 with a polymer limit leads to a high molecular weight of the polymer 1688285, US 6,960,632; (Kaszas et al. Rubber Chemistry and Technology, 2001, 75, 155) showed that it was uniform throughout the molecular weight distribution due to para- -methylstyrene styrene

Similarity in activity with Lisobutylene The isoprene moieties are within the butyl terpolymers that can be halogenated by conventional methods leading to the similar type II and III of Lew allylic combinations halide structures Lanxess lists halo from the current © halobutyl. The Canadian patent YEOAVEY 5 YEVAAAE describes the preparation of butyl peroxide-curable compounds having a high multiolefin content. in a specific way; Canadian patent 41787084? Continuous IIR preparation describes isoprene levels ranging from ? to A 7 mol. Level 0 halogenation of high multiolefin butyl rubber Producer Efficiency of the allylic halide ll function within rubber © (188100). With such high levels of isoprene now available; it is possible; from Where the principle is to generate BIR analogues containing allylic bromide functionalities ranging from − to LA mol.Conventional butyl rubber halogenation processes 0 are described in, for example, Ullmann's Encyclopedia of Industrial Chemistry (Fifth, “Jal Completely Revised Edition, Volume A231 Editors Elvers, et al.) and/or “Rubber Technology” (Third Edition) by Maurice Morton, Chapter 10 (Van Nostrand Reinhold ). Company © 1987, particularly pp. 297-300 Yau further ¢ butyl copolymer C4-C7 may include a cisomonoolefin 00 such as cisobutylene and a Jie “comonomer para- cpara-alkylstyrene and para-methylstrene are preferred. when halogenated; Some alkyl substituent groups present in styrene monomer units that contain benzyl halogen can incorporate additional functional groups by displacing the nucleophilic displacement Ye of the benzyl halogen. A benzylic halogen with a nucleophilic assortment as described in the US Patented £80 .0V TY lead using a tertiary amine

tertiary amines and phosphines to form butyl ionomers.

butyl base on these copolymers with improved physical properties. There has been a continuous effort over the past few decades to develop Al chemical compounds that possess inherently antifungal antibacterial and/or © antialgal properties by impregnation with antifungal Antibacterial or antifungal agent These agents are generally compounds that have a low Sia weight such as antibiotics cantibiotics carbolic acid phenols ¢jodine quaternary ammonium compounds Or heavy metals, such as silver, tin, tin, and mercury. These agents 0 may be attractive; However, limited protection is provided due to the difficulty in controlling the rate of diffusion added outside the polymer matrix. This leaching eventually renders the material ineffective; Has an environmental risk (Jaina) and creates the possibility for the interaction of the filter material with other organic substances, ad.organic substances. The release of these agents to the environment increases the microbial resistance to

.agents 10

Organic antibacterial antifungal or antialgal agents that can be combined into polymer compositions “oy compositions” being organic; They typically have a vaporization point indicating below the temperatures involved during the formation of polymer compositions. Y- Previous studies show polymer compositions that consistently contain antifungal antibacterial All polymeric compounds contain non-conventional low molecular weight addillums. Compounds offered by conventional agents Yo improves durability conditions by low liberation of toxic products to the environment; Thus, reduced losses were associated with volatilization, efficiency, increased efficiency, as well as transportation <photolytic decomposition. Additional benefits may be realized. handling safety, selectivity, and antifungal selectivity. Antifungal Led other polymeric systems Polymer systems turn to the polymer antialgal agent or antibacterial agent antibacterial most often polymer in the polymer active material Fusion of the active material polymer © that can lead to process problems The polymerization process is part of the polymerization process «7708a0. Moreover; Properties and/or loss of polymer properties may process problems of antifungal antifungal incorporation of the polymer. Modification of the polymer may result in negative effects on the properties of the least suitable antialgal agent or antibacterial agent for its intended application. polymer The natural polymer of the polymer 0 contains antibacterial agent polymeric compounds Although the prepared and tested polymer compounds discovered very few examples with antibacterial agent capabilities, a number of active compounds against (ala Adequate antibacterial capabilities

Escherichia coli such as Escherichia coli gram negative bacteria but a few of them are also effective against gram positive bacteria Salmonella and Salmonella 0

Listeria «Bacillus Staphylococcus like Staphylococcus positive bacteria .Streptococcus and Streptococcus from but] ionomers by itself; The present invention directs the use of ionic units and/or prevents the aggregation of organisms; and coatings organisms butyl in reducing the number of organisms butyl from butyl ionomers made of ionic units coatings | 00 General description of the invention butyl ionomer according to the feature of the present invention; There is provided use of the ionic unit of butyl and/or prevents aggregation of organisms at least on organisms in reducing the number of organisms on the surface of the tools. Provided for reducing the number of organisms method according to the other feature of the present invention; There is a method Yo at least on the surface of the composition; organisms and/or prevents the accumulation of living organisms

The method which includes providing the ionic unit of the butyl ionomer at least on the surface of the formulation. According to the other feature so far of the present invention, there is a surface coating provided to the tool; The coating includes the ionic unit of butyl +1000:76 butyl which is effective in reducing the number of organisms and/or preventing the accumulation of organisms on the surface of the formulation. The ionic unit of butyl:1000006 butyl may reduce the number of organisms and/or prevent the accumulation of organisms associated with cbio-fouling eg bacteria chacteria fungi fungi algae calgae Mollusca or arthropods 0 008m0: e. In particular the ionic unit:© may be useful in preventing bio-film growth at least on the surface of a composition that includes the ionomer. Inhibiting bio-film growth may include preventing the formation of a continuous layer of organisms Organisms associated with bio-fouling on more than 75 7 Jon or Ye 7 surfaces of the formulation. The jonomer ionic unit may prevent the accumulation of organisms by preventing the increase in the number of organisms 1° The ionic unit jonomer may prevent the accumulation of organisms by hindering the attachment of organisms to structure 0 in particular The part or parts of the composition that includes the ionic unit jonomer The ionic unit 265 may reduce the number of organisms by killing individual organisms (Je) for example by dying the cell membrane disruption or by preventing the reproduction of organisms (on (JU) Jus Ye by affecting cellular DNA). cgram negative bacteria such as Escherichia coli (SER) “Escherichia coli aeruginosa” or “gram positive bacteria” such as Staphylococcus aureus 25a 0 Micrococcus luteus

A

Example: Aspergillus Jaw on fungi Fungi Organisms Organisms may include streptococcus ad «Penicillium pinophilum Sonia; Binophyllum Asperigillus Niger Chaetomium globosum or Aureobasidium pullulan 3 For example Ulothrix calgae Algae organisms Organisms may include Calothrix membranacea Ulothrix gigas © Chlorella sp. or Chlorella species “Scenedesmus obliquus” mollusca mollusc organisms may include organisms (zebra) Dreissena polymorpha bivalve mollusks valve Dreissena rostriformis or zebra mussels - (quagga mussels - (quagga mussels) bugensis 0 For example crustacean arthropoda arthropod organisms organisms may include: barnacles. seashells Jie ¢ Crustacea sp in an amount sufficient to supply one or more of the following: Prevent excess jonomer ionic unit may be supplied to the formulation when gram positive bacteria in the number of organisms of gram positive bacteria m for 7 days; 01 in gram positive bacteria incubated in the presence of 1 on the combination gram negative bacteria The increase in the number of live organisms for gram negative bacteria m l No "01 in gram positive bacteria when incubated in the presence of Gram-positive bacteria on the formula when it was incubated in the presence of fungi for days; Preventing the increase in the number of fungal organisms per day; ; Or prevent the increase in the number of living organisms of YA algae "mL 00 in fungi fungus Ya. Day YA" ML 1 dalgae on the formula when incubated in the presence of algae 0 is sufficient to reduce the number of AS in the jonomer ionic unit (ell) may supply it or add to it by at least .5 gram negative bacteria an hour. YE "m L Ve or 0 2 when incubated at 286 Ve based on cationic nitrogen jonomer may include ionic unit nitrogen derived from nucleophilic nitrogen  functional group YO nucleophilic amine based on amine nitrogen may include nitrogen based nucleophile cationic on cationic phosphorus group jonomer may include ionic unit nucleophile

phosphorous functional dependent group derived from phosphorous based nucleophile phosphorous based nucleophile may include phosphine ionic unit ionomer may have ionic content at least Jae 7 0,Y 4 + 7 mol” oN mol” 1.8 7 mol or 0 for Pale's explanation of the drawings after he summarized the invention; The preferred embodiment thereof will now be described by reference to the accompanying forms; In which: Figure 1 presents a plot of cell density against time; Imaging the decrease in 0 number of live BK organisms on the ionic unit of the butyl ionomer -surface as the cell density against time of 21158 bacteria in the control (does not contain synthetic rubber) the base polymer For example cA the base polymer of example A JET and example OY b The present invention provides a polymer composition comprising; Lage The butyl ionomer or the partially halogenated butyl ionomer formed from the reaction of crated halogenated butyl 0-005 with at least nitrogen One or a phospholipid-based nucleophile L11H<mamomum. Expressions of butyl rubber ionic unit 0 <butyl rubber ionomer The ionic unit of butyl ionomer or the ionic unit of partially halogenated butyl ionomer Lia may be referred to collectively here as the “ionomer.” “jonomer” The ionomers of the present invention may be prepared from halogenated butyl co-polymers, especially Yeo rubber co-polymers, butyl co-polymers. Chemical is generally derived from at least one isoolefin monomer on

a. at least one multiolefin monomer and optionally also a copolymerizable monomers in one embodiment; The jonomer may include repeating units derived from an isoolefin monomer and conjugated to a conjugated diene monomer ©. In the other embodiment the butyl ionomer may include repeating units units derived from isolefin monomer 150018117 and styrenic monomer in the other embodiment yet; The butyl ionic unit may include ©1000 repeating units derived from isolefin monomer 050016110 conjugated to a conjugated diene monomer and a styrenic monomer. repeating units derived from conjugated diene monomer “number of olefin bonds derived from such units may include a quantity as high as at least 7.7 7 mol” 2.0 7 mol” 5.1 7 mol Ov 1.0 esa ll 7 mol” 77.0 mol” 7/9.9 mol” or LA mol. The butyl polymer is not determined to a specific isoolefin. i.e., isoolefin 0, as it is known to the expert; The contemplator of the present invention including isoolefins would have; GAO range from; to IT a carbon atom. In one embodiment of the present invention, Al isoolefins having 4-7 carbon atoms are predicted to be Atal 5 isoolefins for use in the present invention include isobutene <isobutene ? - 2-methyl-1-butene netweb-1- Jie ¢ = methyl-1 3-methyl-1-butene (sits Y= 0-methyl-7?-butene 2-methyl-2-butene 4-methyl-1-pentene and blends. isoolefin isobutylene 15001606 is preferred in the same way; butyl polymer is not specified to polyolefins The designated multiolefin A multiolefin copolymer with isoolefins (cisoolefins as known to ual) can be used in the practice of the present invention. Conjugated diene multiolefin monomers are Preferred Examples of such multiolefins include; for example JE those with in the range of 4 - 04 carbon atoms Examples of suitable multiolefins include xX

isoprene cisoprene butadiene 7"-methylbutadiene 2-methylbutadiene ) 4-dimethylbutadiene 2,4-dimethylbutadiene piperyline 7-methyl-0-7-pentadiene-3 (methyl- 1,3-pentadiene 7 4-hexadiene 4-hexadiene < .2 ?-neopentylbutadiene -2 (Y= {iY neopentylbutadiene ©-hexadiene lao «Y 2-methly-1,5-hexadiene © methyl- 4-hexadiene 2,5-dimethly-2,4-hexadiene 7-methyl-11; 1,6-heptadiene cyclopentadiene amethyleyclopentadiene cyclohexadiene 1-vinyl-cyclohexadiene and mixtures

So. Preferably multiolefins that include isoprene p1500:©60.

01 In another embodiment of the present invention; Butyl co-polymer The co-monomer may include the additional co-monomer as well; It is known to the expert; Except for the multiolefins referenced above. Co-monomers include copolymer monomers with isoolefins and dienes. Co-monomers include Co-monomers suitable for use in the present invention; on

Ve, for example; styrenic monomers; Calkyl-substituted vinyl aromatic co-monomers including but not limited to the alkyl substituted styrene ,©-. Specific examples of such co-monomers include; For example; alpha styrene ca-methyl styrene Jie m- methyl styrene p-methyl styrene chlorostyrene

0 | cyclopentadiene and methylcyclopentadiene . in this embodiment of the present invention; butyl polymer may include; For example; Random copolymers for isobutylene, cisobutylene, isoprene, and para-Jia styrene.

In another embodiment aad is now the present invention; Isoolefin monomer mono 50016050 as

Yo described above; polymerized with a styrenic monomer; For example, the “alkyl-substituted vinyl aromatic co-monomer” includes but is not limited to the alkyl 01-04 C1-Cy alkyl substituted

styrene Specific examples of styrenic monomers include, for example; Alpha styrene, p-methyl styrene, cchlorostyrene, eyclopentadiene, and methylcyclopentadiene. In this embodiment of the present invention; butyl polymer may © include »; For example, (JUN) random copolymers for isobutylene isoprene and para-methylstryene.

Butyl polymers chemicals. As described above.” A mixture of monomers is described here. In one embodiment the monomer mixture includes a monomer mixture of about Av 7 to about 99 7 wt. isoolefin monomer 5001650 or 0 0 wt. In the other embodiment the monomer mixture includes from about Ae 7 to about 7 594 by weight of isoolefin monomer and from 1 Mea #7 to Vo 7 by weight of polyolefin monomer 010100150. In The verified embodiment of the present invention may employ three .monomers in this embodiment; The monomer mixture includes about Av 7 0 to Jes 99 7 weight of cisoolefin monomer from about 0.8 7 to about © 7 weight of multiolefin monomer and from about 0,5 7 to about vo J. Weight of a monomer A third copolymer with an isoolefin or a multiolefin monomer in the caalgll embodiment The monomer mixture includes a mixture of From about 7 AS to about 7 94 by weight of an isoolefin monomer From about 7 0.5 to about 0 © / weight of an isoolefin monomer From about 7 0.8 to about JAAR by weight of a monomer tertiary copolymer with isoolefin or umultiolefin monomer | monomer in the other embodiment yet; The monomer mixture includes from about A 7 to about 4 #7 the weight of isoolefin monomer

-styrenic monomer The weight of the styrenic monomer Ye is up to 1 7 and from about the monomer may (monomer mixture of the butyl polymer mixture when the butyl polymer forms Yo to form the halogenation process to the halogenation process butyl polymer The halobutyl polymer or the halogenated butyl polymer undergoes the halogenated butyl polymer yr or the bromination process The bromination polymer can perform the procedures described (JE) according to the known process expert as in; for chlorination

Rubber Technology, 3rd Ed.. Edited by Maurice Morton, Kluwer Academic in Publishers, pp. 297 — 300 and further documents cited therein in one embodiment of the present invention; The ionomers may be prepared from the halogenated butyl polymer having from 1.8 to 7.7 # mol the monomer Sqaamnetln. For example; The halogenated butyl for use in the present invention includes halogenated butyl having isobutylene and less than 7.7 mol percent isoprene commercially available 0 from Lanxess Deutschland GmbH and sold under the name 0 In embodiment AY of the present invention; Ionomers may be prepared from a halogenated butyl polymer having a higher multiolefin el ccontent of eg more than Ye 7 mol. In the other embodiment so far; Ionomers may be prepared from a halogenated butyl polymer having a multiolefin content of more than 1,7 mol. still in other incarnations; The multiolefin content of the halogenated butyl polymer is more than 5.0 7 mol. In the “SAY” embodiment, the multiolefin content of the halogenated butyl polymer is more than 7.0 7 mol. The preparation of a suitable high level 0-butyl polyolefin rubber polymer; for use in the present invention; Described in the polymer co-pending application Canadian patent YEYAAAE; United here by reference. During halogenation of the butyl polymer Jie “containing conjugated dienes isoprene ©1500 some or all of the multiolefin content of the butyl polymer is converted to allylic halides Yo This allylic halide locates a site in the halobutyl polymer leading to the repeating units derived from the multiolefin monomers originally dissolved in the butyl polymer may not exceed

Ve halobutyl total allylic halide content total allylic halide content starting multiolefin content starter polymer content allylic halide 2:601 pm. The allylic sites of the butyl polymer allow the original butyl to not contain the halobutyl polymer to the nucleophile with the chemical allylic halides on halobutyl polymers halobutyl 5 chemical compounds derived from halobutyl polymers for example; halo-butyl compounds; benzyl halides; Formed by halogenation ¢ styrene monomers and isobutylene styrene monomer may react to form the ionic unit 006 instead of a styrenic monomer of a benzylic styrenic monomer for 1 ale. The same logic applies to benzyl halides and ionomeric moieties. The total amount of ionic moieties as callylic halides is 0. benzylic halides can exceed the available amount of benzyl halide or allylic benzyl halide sites. halide in one embodiment of the present invention; an allylic halide reactant with at least one halobutyl polymer of a benzylic halide nucleophile containing one phosphorus or phosphorus nitrogen having the following formula;

Ry™ OR, in which; and +¢phosphorus or nitrogen is A Ye.

C1-Crs selected from the group that includes linear or branched alkyl substituents of R35 182 8 which is an aryl substituent of or branched :-0 alkyl substituents and or atom “fused C4-Cs rings” or It consists of Z-0 rings, united monocyclic. and 8 © «Si » 0 NN » 3 was chosen from; For example, a different hetero atom for use in the present invention; for examples; Nucleophiles including one Yo or a neutral nitrogen phosphorus center having at least one neutral nitrogen nucleophiles va

phosphorus center has a lone pair of electrons, which is electronically accessible to participate in nucleophilic substitution reactions

appropriate nucleophiles; For use in the present invention includes; for examples; Trimethylamine drimethylamine triji amine triethylamine triisopropylamine

© driisopropylamine 0-butylamine ctri-n-butylamine ctrimethylphosphine etriethylphosphine ctriisopropylphosphine tri-"-butylphosphine tri-n-butylphosphine Triphenylphosphine ctriphenylphosphine = 2-dimethylaminoethanol 1-dimethylamino ¢1-dimethylamino-2-propanol Js Y= 7-(isopropylamino)ethanol-2 “(isopropylamino)ethanol 0 T-Dimethylamino-1-propanol “3-dimethylamino-1-propanol [1-methyldiethanolamine” N-methyldiethanolamine 7-(diethylamino)ethanol-2 ¢(diethylamino)ethanol 7 1-dimethylamino-1-methyl-1-2-dimethylamino-2-propanol

2-2 Jol meno)litoxy fo fw “-(di[-7 ¢methyl-1-propanol 4-(dimethylamino)-launatob-1-(dimethylamino)-4” (dimethylamino) ethoxy] ethanol

“I-butanol 0l1-ethyldiethanolamine” “N-ethyldiethanolamine” triethanolamine “7-diethylamino-1-propanol 3-diethylamino-1-propanol ?-(di-J) amino)-1"-propanediol (3-(diethylamino)-1,2-propanediol 7-([ 7-(di-Jie)

Amino (ethyl]methylamino) ethanol “2-{[2-(dimethylamino)ethyl]methylamino} ethanol 5 -

Diethylamino-7-butyn-1-ol cd-dicthylamino-2-butyn-T-ol 7-(di-si)propyl

N-Diacetatolamine J 550 N Aminto(Eqatol 1 Musamta” (MSNSHARM 011500:0)-2”0-Lethium(-17”N-rerr-butyldiethanolamine L-7-tert-diethanolamine cbutyldiethanolamine

Phenylamino ethanol “2-(methylphenylamino)ethanol and alcohol ?-(dimethylamino)benzyl-3-(dimethylamino)benzyl hydration” 1-7[-(dimethylamino)-phenyl[ethanol-4] 2-“(dimethylamino)phenyl]ethanol 7-(71- ethylanilino)ethanol “2-(N-ethylanilino)ethanol

© [<-benzyl-71-methylethanolamine “N-benzyl-N-methylethanolamine 7+-phenyldiethanolamine” N-phenyldiethanolamine 7-(dibutylamino)ethanol —Y “2-(dibutylamino) ethanol (77-ethyl -!1-(“-toluidino (2-(N-ethyl-N-m-toluidino)ethanol 7 7) -methyl

Jd imino)diechanol ¢2.2'-(4-methylphenylimino)diethanol tris[-)1-(methoxyethoxy)ethyl]amine ctris[2-(2-methoxyethoxy)ethylJamine 7-(dibenzyl amino)-1-propanol 3-(dibenzylamino)-1-propanol and mixtures thereof. In one embodiment of the present invention; The amount of nucleophile that has reacted with the 0-butyl [buy] polymer may be in the range from 1.05 to stoichiometric m. In another embodiment the amount of all the nucleophile that has reacted with the butyl polymer may be in the range of *,; to 4 moles stoichiometric. In the other embodiment thus far, the ratio of the nucleophile that reacted with the butyl polymer is 1 to ? Mueller equivalent. The ratios of nucleophile to butyl polymer are based on the 0 total molar amount of allylic halide or benzyl halide present in the .halobutyl polymer as above; Je lay nucleophile with 1 allylic halide or benzylic functionally from halobutyl polymer leading to Cu jonomeric moieties allylic or benzyl halide halide Yo functional find on halobutyl polymer The total content of half the jonomeric moiety in the ionic unit of the butyl ionomer may not exceed the starting amount of 2 or benzyl halide allylic or benzylic halide in the chalobutyl polymer however it may be; The remaining allylic halides of Mason; The remaining benzylic halides and/or polyolefins are 0 residual residual present. In the embodiment of the present invention substantially all of the allylic or benzylic halides sites interacting with the “nucleophile” unit | The butyl rubber ionomer in embodiment is less than the sites of all the ALY or benzylic halide sites interacting with the cnucleophile. The partially halogenated butyl ionic unit of the butyl ionomer. Y© in one embodiment of the present invention; The resulting ionomer has an ionic content of at least 0.8 7 mol of the -lonomeric moiety in i.

The embodiment (AY) “a fonomer has an ionic content of at least ve/mole half of an ionic unit moiety of 1000:16. In the other embodiment so far; An ionic unit 10000062 has an ionic content of at least 0.1 7 moles of half an ionic unit moiety ©1000601. In the other embodiment so far; An ionic unit © ionomer has an ionic content of at least V,0#7 mole half of an ionic unit

.ionomeric moiety present in residual allylic halides in some cases the remaining allylic halides may be original allylic AVI mol to an amount not exceeding the original halide content 7 0.1 quantity of used to produce the ionic unit halobutyl polymer From halo-butyl polymer, halide content residual. In another embodiment, the remaining polyolefin may be the ionomer of butyl Ve mol to an amount not exceeding the original content of the polyolefin 7 1,1 present in an amount of multiolefin 1 and that used to produce a polymer from the butyl polymer original multiolefin content Olefins 0071 H 1010. in one embodiment; Residual content of poly-butyl halo polymer 7 7 at least jonomer of ionic unit residual multiolefin content olefins residual multiolefin content residual multiolefin content JAY) mol. In embodiment 05 at least 0.16 7 mol. In the other embodiment so far; The jonomer content of the ionic unit is less than the jonomer of the ionic unit residual multiolefin content The remaining of the residual polyolefins mole. In the other embodiment so far; Residual content of polyolefins 7 Ad and mol. In the other embodiment, 7 0. 1 no less ionomer of ionic unit multiolefin content than ionic unit residual multiolefin content now; The remaining content of polyolefins. 0 now; The remaining content of the multi aad mol. In the other embodiment, 7 7,0 “reduce: at least the olefins of the ionic unit are less than 10,7 7 mol. In the other embodiment so far; Content on the ionomer of the ionic unit residual multiolefin content of the remaining polyolefin

least 4.0 7 mol.

Yo in one embodiment of the present invention” may include an ionic unit: 1,000,006 repeating units derived from at least one isolefin monomer at least 15,001,650 monomer 0,5 7 repeating units derived of at least daly a polymonimer

VA

One or more approved nucleophilic nitrogen and at least a cmultiolefin monomer butyl olefins by means of the phosphorous based nucleophile partially halogenated butyl ionomer or the partially halogenated butyl ionomer and a multi-isoolefin, which includes the isoolefin monomer mixture formed by preparing the monomer mixture “polymer” to form a monomer mixture. .nucleophile polymer with halo functional sites The halo functional sites interact according to the present invention; may include one or a filler (polymer composition)

Glia suitable for use in the present invention consist of more fillers. filler 5 clay silicates metal; like; For example; Al-Silika (PBUH): 59:1; Silicates 0211168 | 0 Titanium dioxide, calumina, aluminum oxide, gypsum, gypsum » (bentonite) and the like, in addition to mixtures thereof. The suitable tale ctitanium dioxide includes: Other fillers for grouting Aly) prepared as an example: by precipitating a solution of Lindl silicas to a large extent silica flame hydrolysis or silicate solutions Ye 00 to 10 preferably 0001 in surface areas designated # to chalides (©506015); And with basic particle sizes surface area dime meters 'grams (887 surface areas are present silicas to nanometers; silica can be 10 primary particle sizes Jie other metal oxides mixed with metal oxides oxides also by choice as oxides ¢ Tiy Zr «Zn «Ba »Ca aq 0 aluminum silicate Jie synthetic silicates industrial silicates - ¢ alkaline earth metal silicate calcium silicate or silicate Calcium magnesium silicate - marg/1 m tov to 00 of 9060156 surface areas BET surface markers to 00 nm; 01 of primary particle diameters Basic Molecular Diameters Ye silica and the other silica kaolin as kaolin ¢natural silicates natural silicate - naturally occurring;

- natural clays such as montmorillonite and other naturally occurring clays ¢tnaturally occurring clays - organophilically modified clays such as organophilically modified montmorillonite clays (example ©: Cloisite® Nanoclays available from Southern Clay Products and other naturally occurring clays ¢modified naturally occurring clays - glass fibers and glass fiber products (matting extrudates) Or central particle glass ¢glass microspheres - metal oxides Jie cmetal oxides zine oxide, calcium oxide 0, magnesium oxide, aluminum oxide - metal carbonate Emetal carbonates such as magnesium carbonate, calcium carbonate, and calcium carbonate ¢zinc carbonate: - Cmetal hydroxides, for example: aluminum hydroxide and magnesium hydroxide or combinations of ve it. In one embodiment of the present invention; The mineral filler is silica in the other embodiment; The mineral filler is silica prepared by carbon dioxide precipitation of sodium silicate. Dryed amorphous silica particles are suitable for use as mineral fillers. Under the present invention it may have a mean agglomerate particle size in the range of 1 to 100 microns. In daly of an embodiment of the present invention; Dried amorphous silica particles have an agglomerate particle size of 10680 in the range of 10 to 50 microns. In another embodiment of the present invention; The dried amorphous silica particles Ye have a mean agglomerate particle size in the range from +)5 YO microns. In one embodiment of the present invention; Considered to be less than 10 percent the size of agglomerate particles under microns or more.

0 microns in size. suitable amorphous dried silica for example; BET surface area measured under (1 German Industrie Standard TTY) (Deutsche Industrie Norm between +8 and 490 jie squared per aba and absorbance DBP while measured under OTT) DIN between 5100 £10g for 1001g of silica 5 ; drying loss; As measured according to DIN 787/11 150 from 0 to 10 percent by weight. Suitable silica fillers are sold commercially under the names 210 HiSil 233 ¢HiSil HiSil 243 available from PPG Industries Inc. Also suitable 5 Vulkasil Ns Vulkasil commercially available from Bayer AG Metallic fillers (Mineral fillers as used in the present invention; 0 can also be used alone or in combination with known non-mineral fillers, such as: - carbon blacks “and printed” carbon blacks Appropriate is preferable to lamp black, furnace black, or gas black process atomization and designated BET surface areas from 0.010 to Yeo m 'crime; eg' SAF less than FEF (HAF) or carbon blacks GPF: Vo 0 - arubber gels are preferred over polybutadiene butadiene styrene copolymers Butadiene / acrylonitrile copolymer copolymers and polychloroprene. Balk 001686 etc. With an aspect ratio of at least 1 : . Fillers may include circular or nonisometric materials with needle-like flat mounting »AA-066016. The ratio of length to width aspect ratio is defined as the ratio of the average diameter circle of the same area as the face of the plate to the average thickness Yo of the plate The length to width ratio of the needle and fiber shaped fillers alll formed is the ratio of the length to diameter. In one embodiment of the present invention; The dle aspect ratio fillers have an aspect ratio of at least 1 : 5.

YY

high aspect ratio fillers in the other embodiment of the present invention; Aspect Ratio Filler Aspect Ratio However, in other embodiments, the Aspect Ratio is at least 7:1 aspect ratio 1 to 1:1 aspect ratio High has aspect ratio fillers Aspect for display under the present invention may have; For example; Fillers particle size? Padding 0: microns in the other embodiment 001 to 0.000 “let” in the range of medium particle size © crack “” in the range of 0.5608 and 5603 particle size medium Ayia has a size fillers in mean particle size medium particle ana has micron fillers. in the other embodiment; Filling surface area BET has the appropriate Lay filler and 10 microns. Padding 1.00 range from 3231171 (Deutsche Industrie Norm German Industrie (DIN standard) measured under carea between © and 0007 square meters per gram. 0 in one embodiment of the present invention; padding ratio of length to width Ale aspect ratio fillers include nano-size clays such as; for example (JU) naturally-modified nano-size clays. The present invention is not limited to a specific nano-size clay; however, Ground natural smectite clays; such as sodium or calcium montmorillonite or calcium montmorillonite “made by you”; or synthetic clays such as hydrotaleite and laponite suitable as starting starting primers materials in one embodiment; aspect fillers sda high profile includes naturally modified montmorillonite nanoclays clays may be modified by a transition metal substitute for the conium ion as known in call to provide surfactant 00 with a surfactant functionality to the clay that helps in the dispersion of the clay within the hydrophobic polymer environment in general. In one embodiment of the present invention; The basic onium jon phosphorus ions (for example: phosphonium ions and basic nitrogen (for example: ammonium 1 ions) and contains functional groups for it (NR; MMT) (for example: carbon atoms Yo carbon from? to YO nanometer jie for example; in particle sizes as nanoscale clays may provide clays less than ©7 micrometers in size. In Single embodiment; particle size Jie over 500; particle sizes

YY particle size (JAY) in micrometers. In the embodiment © 0 and 1 in the range of particle size in 00111018 particle size ana (GY) aad μm. In the other embodiment "01 and 1 in the range of the range from ? and 15 micrometers. Some fraction also nanoclays in addition to silica 511168" Clay may contain nanoclays lll in one embodiment Clay may contain nanoclays in one embodiment Volume of alumina as alumina © Clay may contain in (GAY) in embodiment alumina Weight of alumina 7 10 to 1.1 in however in alumina from 5 to © 7 Weight of alumina nanoclays sill asa to 7 7 Weight of oxide 1 of nanoclays Other embodiments Clay may contain nanosize alumina a ssie NY. Commercially available suitable naturally modified nanoclays Examples of clay In nano size 0 Al-Alia includes; aspect ratio fillers In one embodiment, the aspect ratio filler Lor 25A may be added to form a component of the pre-formed butyl ionomer to the ionic unit of the preformed butyl in an amount from ? to 0 8. In the other embodiment a ratio amount Filling nanocomposite nano size © from Al Aaly nanocomposite in a component in nano size aspect ratio fillers length to width aspect ratio fillers «1m. In the other embodiment so far; Amount of filler aspect ratio 71 to -phr Ye © to high ana nanocomposite in ionic unit:1000016 may or may not cure. when you treat; The ionic unit may include the system, the dallas, the selection of the system, which is derived from the treatment of the system, the components #Assada: the components 0 The appropriate use is not specifically specified and within the range of vision of the expert. In embodiment, the curing system sulfur-based may be the sure curing system of the present invention; The treated system is sulfur-based. sulfur-based accelerator at least (iii) s elemental sulfur ~~ vo curing in the component treatment system as a component metal oxides The appropriate use of zine is zinc metal oxide famous in art. Metal oxide system vv

coxide which may be used in an amount from about 1 to about .01 in the other embodiment of the present invention; Zinc oxide may be used in an amount of about to about ©; Parts by weight per hundred parts by weight of the butyl polymer [buy] polymer A component in nanocomposite size Elemental sulfur Elemental sulfur includes component (ii) component of 0 Preferred curing system Typically used in quantities from about 1.7 to about 2 parts by weight; per hundred parts by weight of the butyl polymer I in the composition. Appropriate sulfur-based accelerators (iii component of the preferred curing system) may be used in quantities of about +0 to about © parts by weight per hundred parts by weight of butyl polymer in 0 abl .composition other than specifying sulfur-based accelerators | Useful sulfur-based accelerators may choose from thiuram sulfides, Jie thiuram sulfides, tetramethyl thiuram disulfide ((TMTD) tetramethyl thiuram disulfide thiocarbamates such as zinc dimethyl dithiocarbamate (ZDC) zine dimethyl dithiocarbamate and a thiazyl and benzothiazyl compound as mercaptobenzothiazyl disulfide © (MBTS) in one embodiment of the present invention;

-mercaptobenzothiazyl disulfide A gly based accelerator may also be Peroxide based curing systems Peroxide based curing systems A peroxide based curing system (JU) is suitable for use in the present invention. For example peroxide curing Peroxide based curing systems may include di-tert-butyl edicumyl peroxide (JU) eg 0 "bis (tert-7 cbenzoyl peroxide") di-tert-butyl peroxide 2,2'-bis (tert.-butylperoxy diisopropylbenzene) —0 Absorbent 7 #-dimethyl-peroxide benzoyl peroxide «(Vuleup® 40KE) 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne- di(tert-butylperoxy)-hexene - ?-2,5-dimethyl-2,5- (benzoyl peroxy) sho methyl-7; glo 7 3 Yo *-bis(tert-butyl oF)methylhexane glo (Y= di(benzoylperoxy) hexane and ¢(2,5-bis(tert. -butylperoxy)-2,5-dimethyl hexane)-*;

Like. Such a peroxide curing agent as the Jedd peroxide i agent is dicumyl peroxide and is available commercially under the name DiCup 40C in one embodiment; Peroxide curing agent used in quantity from 1.7 to 17 | Parts per hundred parts of rubber (phr) hundred parts of rubber in the other embodiment The peroxide curing agent Sele is used in an amount from 1 to 6 ophr in the other embodiment so far » The peroxide curing agent Sele peroxide curing agent used in an amount of about; «: 1 pm. Peroxide curing co-agents can also be used in the present invention. Suitable peroxide curing co-agents include, for example, tri-all isocyanurate ((TAIC) triallyl isocyanurate 0 commercially available under the name DIAK 7 from DuPont or -(- N'-m-phenylene dimaleimide aka HVA-2 (DuPont Dow); Tri Jl cyanurate (TAC) triallyl cyanurate or liquid polybutadiene aka 153 Ricon D (2534) by Ricon Resins dallas may use peroxide curing co-agents in equivalent quantities

Ve to peroxide curing agent or less. In some embodiments of the present invention, “cstabilizers, anti-oxidants, viscosity agents, ctackifiers, and/or other additives as known to the expert may also be added in the normal way and in normal quantities to form the ionic units of butyl.”

butyl ionomers of the present invention.

Cionomer The ionic unit polymer composition in the embodiment where the polymer composition includes 0. and/or other add-ons; Curing agents, fillers, conventional compounding | Together by using traditional compounding techniques ingredients on “conventional compounding techniques Appropriate compounding techniques include techniques together with using ingredients of the composite Mixing the components of the two compounds Banbury Jie cinternal mixer e.g. Yo Yo internal mixer or Haake mixer Jie miniature internal mixer Good mixing extruder supplied with roll mill mixer or roll mill mixer "Brabender mixer vo also; allows for shorter mixing times. It is possible to carry out mixing in two or more stages; the different; eg single stage in apparatus and mixing can work in apparatus and single stage in extruder «00108 © Internal mixer for more information

Encyclopedia of Polymer Science see “compounding techniques on compounding techniques as is oa .m. Technologies 66 et seq. (Compounding) Vol. 4 row Engineering ° .compounding known to expert; more suitable for composition to the ionomer formed composition in one embodiment of the present invention may form the ionic unit in place of the .ionomer of the Li ionic unit or introduced to the existing composition. May make the composition Part of the composition may include the ionic unit:©:10000. The ionic unit: 1000316 may be supplied on the cell surface of the formulation only. The ionic unit: 100008 may pour integrally to the surface or bind 0 the unit may provide Gayla fasteners to the surface; For example in adhesive form or on -plastic Compound material As part of a composite material 1011006 dng Polypropylene polyethylene May include polyethylene plastic Plastic may include nylon polymer or nylon polymer ©0014 polymer EPDM <EP polymer EP thermoplastic on thermoplastic vulcanizate composite material comprising Ve plastic and the butyl ionomer comprising the butyl ionic unit vulcanizate 1080161 of the instrument. surface coating as a surface coating jonomer may supply the ionic unit may be on the surface coating surface coating paint may include surface coating chemical coating (any suitable thickness) » chemical vapor precipitate applied membrane Applied film form | 0 Lad plastic The cover may include .powder coating or vapor deposit -plastic coating or other; Provided that no coating as part of the ionomer encapsulation may supply the ionic unit additionally or antibacterial antifungal antifungal agents may be present; Especially since such agents are antialgal agents, anti-algae. You mean A cyonomer. The coating may essentially include the ionic unit, coating that percolates outside the coating.

To include fillers or curative agents that may be present as part of the onomer ionic unit.

The composition may include: a jie fluid conduit a hose or a pipe ¢pipe a container such as an aud aud calculator a ctote a storage tank etc. ; container closure© or lid ¢lid seal or sealant ¢gasket or awls ¢caulking Jie material handling apparatus auger or belt cconveyor belt Jail Jie cmarine vessel or structure (dig) cdock or oil drilling platform drilling platform; Cooling tower tcooling tower metal working apparatus or any apparatus 0 contact with metal working fluids tmetal working fluids engine component (Jia) fuel lines cfuel filters fuel tanks fuel storage stacks gaskets seals eseals etc. Membrane for fluid filtration or tank sealing ¢ or footwear Especially the shoe parts

footwear that came into direct contact with the foot. Vo Additional examples where butyl ionomers or coatings may be used include; But it is not limited to the following: Number of applications Baby products; bathroom furniture <bathroom fixtures <bathroom safety <bathroom safety <flooring> food storage; the garden; kitchen furniture; kitchen products; office products; Pet products, sealants, sealants, mineral baths, grouts, filtration, water storage, water filtration, storage 0 0, equipment, laying, food preparation surfaces 20, equipment, equipments, shopping carts, cshopping carts, applications surface applications; storage containers; the shoes; protective clothing; sporting gear; buggies; dental appliances; door handles»; dress; telephones; allll catheterized fluids in hospitals”; decks of ships and tubes; wrappers; food preparation; biomedical tools; ve filters; additions; calculators; ship hulls;

ow metering of pipes; storage vessels » measuring systems soft drink machines soft drink machines liners filter housings accessories; filter housings; fittings; valves; Compositions ¢systems -barrier coatings and inhibitor coatings «linings antifungal anti-jonomer in one feature of the invention; The unit exhibits ionic and/or anti-algae properties 8[1g80081. This feature of the unit antibacterial antibacterial 0 is believed to be a result of the ionic nature of the ionic unit :1000076 Problem. jonomer ionic Although the inventors do not intend to be associated with the theory; It is believed that the unit ionic feature and/or antibacterial and antifungal properties conferring antifungal halogenated butyl fonomer is not observable in the ideally antialgal antialgal fonomer polymer 0. and/or antibacterial antifungal additives as discussed above; antipathy may be attractive; However, it is determined that their protection is short-lived in most of the antialgal rate of diffusion sometimes due to difficulties in controlling the rate of diffusion out of the antialgal and/or additive antibacterial antifungal polymer. This filtration of additives outside the polymer matrix polymer matrix 05 risk leaching which returns the material unaffected at the end. in addition; Matrix organic leached material filtration creates a potential environmental and risk of covalent reaction of the leached material to the other 1001© group polymer column. The group of substances ionomers, as in the present invention, “remove ionic units (polymer backbone) anti-microbial efficacy additive that filters out issues in addition to antimicrobial efficiency 0 -handling safety of the polymer Selectivity and treatment of polymer safety Sad increasing pre-existing polymer here is useful for sending the modification of the polymer jonomer description of the ionic unit polymer molecular weight and geometry polydispersity allows to control the degree of multiple scattering that can be affected sometimes when the amolecular weight and polymer topology Antialgal agents or antibacterial antifungal Yeo ionomers Describe additional polymerization ionic units during polymerization Not only antialgal agents; but also original polymer properties shown here It does not retain the properties of the original polymer

TA

green power enhanced cadhesion; Adhesion filler Jie interaction Improved natural; Applied coatings (p:p. These properties are useful in forming formed articles and covers with adhesive strength. By means of microorganisms, the present invention is very useful against The following microorganisms are mentioned without imposing any restriction to the microorganisms example “butyl” microorganisms in which the properties of the ionic unit of butyl microorganisms are effective immediate microorganism species: jonomer “chlorarachniophytes” <glaucophyta “ rhodophyta «chlorophyta 'Algae' dinoflagellates «cryptomonads <haptophyta <heterokonts ceuglenids candida botrytis «basidiomycetes »aspergillus <Alternaria : Fungii Ye «drechslera curvularia »cladosporium 7e scephalosporium »albicans emonilia <humicola <helminthosporium |<geotrichum fusarium «<epicoccum rhodotoruld crhizophus «pullularia «phoma «penicillium 117870570076» neuspora verticillium and unocladium «richoderma cstemphylium wscopulariopsis

Neisseria “Shigella” Salmonella: Gram-negative bacteria Yo “Escherichia coli “Haemophilus influenzae” Neisseria meningitidis “gonorrhoeae -Pseudomonas aeruginosa” Klebsiella “Staphylococcus “Listeria” Bacillus: Gram-positive bacteria “Mycoplasma “Sarcina “Epulopiscium” Clostridium “Enterococcus” Streptococcus “Propionibacterium” Corynebacterium “Lactobacillus” Ureaplasma “Spiroplasma 000 -Nocardia 5” Actinomyces “Streptomyces Frankia” Gardnerella According to the present invention, it may also be used in polymer compositions, jonomer, thermoplastic ionic units. therapist and non-therapist; Thermoplastic elastomer compositions polymer compositions cre-moldable polymer compositions for remolding ALE celastomeric polymer compositions, etc. coatings Yo coatings

Yq The particular embodiment of this invention is described above for illustrative purposes; It will be clear to the expert in the art; Numerous variations of the particulars of the present invention may do without departing from the invention as defined in the appended claims. The following examples will be used to depict the particular embodiment of the invention. : 1 c of © triphenylphosphine allylic bromide content (ll bromide content) at room temperature for 3 minutes. Then it is passed “11 XT” by mixing on a mill (TPP) for product analysis The final mixture of LV Te in twin screw extruder through a two-roll extruder into BB2030 type of allylic bromide confirmed the complete conversion of all allylic bromide by THNMR of “,+7 mol. ionic content Corresponding to ionic content fonomeric species ionic units 0 gram positive The sample is poured into 100 °C for a period of minutes and its resistance to gram positive growth tests The samples were placed on triplicate in triplicate (Staphylococcus aureus (Staphylococcus aureus) A cell was added, placed in a plate and then 1 01 where approximately (SDA) Sab Dex agar plates were observed on 7” bacterial growth after 7 days; no bacterial growth 0 placed in the incubator in inhibition of butyl-based sample; Blocking 0-butyl-based phosphonium ions exposes the growth of jonic functionality 7 A+b phosphonium ionomer -growth of gram positive bacteria. Gram-positive to Gram-negative bacteria 1 The problem is in the example of jonomer Example?. The resistance of the ionic units was tested using the same procedure as Escherichia coli gram negative bacteria observed on the sample; bacterial growth after 7 days; no bacterial growth1 as summarized in the example of Ye inhibition of butyl Lithobla -based displays the inhibition of ionic units of phosphonium based on the growth of jonic functionality bacteria mol ionic function 7 +A b phosphonium ionomer -gram negative bacteria to a group of 1 bacteria formed in Example jonomer eg “Ion resistance and lotus Staphylococcus aureus gram positive bacteria Yo calif 17 after 1. Summed up in example WS tested using the same procedure ( micrococcus luteus No bacterial growth observed on the specimen; exhibits inhibition of butyl-based phosphonium ions

+ 0,8 inhibition of butyl-based phosphonium ionomer #7 mol ionic function to the growth of a variety of -gram positive bacteria eg;. The resistance of the jonomer ionic units formed in Example 1 to a group of gram negative bacteria (S&B Escherichia coli (Pseudomonas aruginosadyla)l°) was tested using the same procedure as summarized in Example 1. After 3 days » no bacterial growth is observed on the sample; the inhibition of butyl-based phosphonium ionomer B +,A 7# mole ionic function indicates the growth of a variety of negative bacteria Gram .gram negative bacteria, for example, Lo, the resistance of the ionic units, jonomer, formed in Example 1, to the ELE fungus, Asperigillus Niger Ve. Tested in triplicate. The samples were placed on a plate of barley agar ( Malt agar plate followed by adding approximately IE of spores of the fungus Asperigillus jax aad Niger to the sample; placed in the plate and then placed in the incubator at 0 *"m. after YA day; no mold growth growth note on dell Displays antifungal nature of butyl-based phosphonium ionomer B +,A 7 mol 0 ionic functionality Example 6. Unit resistance The ionic jonomer formed in Example 1 to a group of fungi was tested in triplicate. The samples were placed on a malt agar plate +888; Tracked by adding approx. ty of spores from the fungus Asperigillus niger Chaetomium globosum s < Aureobasidium pullulan Penicillium pinophilum to -0 sample; It is placed in the dish and then placed in the incubator at 0 "" m. After cag YA no mold aad growth on the sample; Displays the antifungal nature of a butyl-based phosphonium ionomer with 0.8 7 mol jonic functionality to a different type of fungi example 7. Ion resistance The ionomer formed in example 1 to a group of algae, Yo algae, was tested in triplicate. The samples were placed on a malt agar plate, followed by the addition of approximately 01 A of the concentration of a group of Calothrix. Ulothrix gigas sp 5 «Scenedesmus obliquus »membranacea 0010:©012. to the sample; Then put it on the plate

m placed in the incubator at 0 7"m. After YA day; no algae growth was observed on the sample; it displayed an antialgal nature of butyl-based phosphonium ionomer B + A / mol ionic function to a different type of -algae ° Example A approximately 1 g of Example 1 covered in 7 55 ethanol for sterilization After that, it was placed in a 10 ml Scintillation vial, where 10 ml of M9 medium was added.The colony of bacteria 11150 (strain of bacterium Escherichia coli) is gram-negative (gram-negative). And suspended to a salt solution from medium 149. Then; 0 μL some bacteria 11150 is added to each tube Rubber with less dallas Rubber- 74 and 01 8 4 60 used as control and samples 90 μL were tested In less treatment Ye and acid stain cytometry generated using flow Bacterium counts per hour.

X 001 using the following procedure: 1 μl of nucleic acid stain SYBER Green “nuclear” £90 μl of the sample was added to concentrate DMSO (suspended in SYBER Green) 11 min. They are placed in the incubator in the dark for approx. 1 final SYBER Green® 1 and then placed on a flow cytometer. The percentage of dead cells was measured using flow cytometry and nucleic acid stain “57106 after 74 hours More than 60 7 bacteria were killed showing the bactericidal nature of the biocidal nature of the butyl-based phosphonium ionomer with A + 7 mole ionic function. See Fig. 1. Ye Example 18 YYV c of LANXESS BB2030 and 7.15 c Y) + molar equivalent based on allylic bromide (TPP) wiphenylphosphine content Pre-mixed on a “11 +” mill at room temperature for ? minutes. Then the mixture is passed through a twin screw extruder at 100 m. Final product analysis by 2ST THNMR having Y , + 7 moles of phosphonium ionic groups To

Micrococcus and Staphylococcus aureus (Staphylococcus aureus) positive bacteria

Sab Dex lal sala The samples were placed on triplicate plates in triplicate (luteus ry

AT cell added; placed in the dish and then placed in the incubator at '01 where approximately (SDA) is observed on the sample; Ionic units inhibit bacterial growth days later; No bacterial growth 7 7b inhibition of butyl-based phosphonium ionomer .gram positive bacteria Mole ionic function to the growth of gram-positive bacteria formed in Example 9 to a group of jonomer resistant bacteria 01. Example Escherichia coli SE gram negative bacteria days; V was tested using the same procedure as summarized in Example 8 after Pseudomonas aeruginosa is noted on the sample; Inhibiting bacterial growth 7+,Y function inhibition of butyl-based phosphonium ionomer -gram negative bacteria exposes the growth of a variety of onic bacteria ionic functionality 0 to a group of 9 JUL formed in jonomer resistance of ionic units 11. Example samples placed on a triplicate agar plate tested in triplicate Asperigillus fungi from spores from the spores of Ty. followed by the addition of approx. (Malt agar plate, barley, Chaetomium globosum 3 < Aureobasidium pullulan «Penicillium pinophilum» Niger day; no YA template growth after Fd is applied to the sample; It is placed in the dish and then placed in the incubation Ve for units of antifungal nature, noted on the sample; Displays antifungal nature mold growth with 7 mol butyl-based phosphonium ionomer Jui saad) ionic fungi to different type of fungi jonic functionality ionic function Molar equivalent dependent on (11) C 1, EV 5 LANXESS 13132030 Example “1: 71777 C of triphenylphosphine (allylic bromide content ll bromide content Yo) at room temperature for ? minutes. Then pass 11 XT mixing by on a mill (TPP) at 100” m Final product analysis from twin screw extruder mixture through a two-roll extruder phosphonium ionic Cole gana mol of 7 1.7 before 1111148 confirmed The presence of a gram sample is poured into 100 tm for a period of minutes and its resistance to Gram-positive growth groups is tested

Micrococcus and lotus Staphylococcus aureus (Staphylococcus aureus positive bacteria Yeo

Sab Dex lal The samples were placed on plates of triplicate material in triplicate (Tuteus °F cells were added; placed in the plate and then placed in the incubator at 01 where approx. (SDA)

YY

notes on the sample; Ionic unit inhibition of bacterial growth displays days; No bacterial growth 1 after / 1b inhibition of butyl-based phosphonium ionomer -gram positive bacteria ionic functionality 1 The problem with the jonomer example is the resistance of VE ionic units. Example AL Sa and Escherichia coli ((gram negative bacteria) © calf 17 Summarized in example 4. After WS Tested using the same procedure (Pseudomonas aeruginosa) noted on the sample; showing inhibition of bacterial growth by ionic units of butyl-based phosphonium ionomer J,1b -gram negative bacteria to the growth of a variety of gram-negative bacteria functionality to a group of 11 resistance to ionic units 1000006 formed in example Ve example ve samples were placed on an agar plate triplicate tested in triplicate fungi “Asperigillus Niger from afiha from Ty. Lu; followed by adding Malt agar plate from barley Chaetomium globosum s “Aureobasidium pullulan Penicillium pinophilum day”; No template growth is observed after YA. m*0 1 sample; It is placed in the dish and then incubated in antifungal nature phosphonium ionic units on the sample; Displays antifungal nature Vo ionic b 1 / mol ionic function butyl-based phosphonium ionomer butyl fungi to different type of fungus functionality to a group of 11 JU formed in jonomer resistance ionic units A Example Samples placed on a triplicate agar plate tested in triplicate algae “Ulothrix gigas” from a group concentration of 1 0; Follow by adding approximately Malt agar plate, barley, Y. It is placed in the “dill” and 80 0:©118l00. to “Scenedesmus obliquus ¢Calothrix membranacea algae growth is observed a day; No YA algae growth on the dish and then placed in the incubator at 10”C. dimension of phosphonium ionic units antialgal nature exhibits antialgae nature (diel) on ionic mole ionic function 7 1,6 b butyl-based phosphonium ionomer butyl-algae to Different type of algae functionality Yo in twin screw extruder through a two-roll extruder Lanxess 0 passes VY example Mole of 7 groups 1,8 confirmed THNMR m. Final product analysis by 7 ve

ionic phosphonium. The sample is poured into 100 "C for a period of minutes and its resistance is tested for the growth of gram-positive bacteria (Staphylococcus aureus) gram positive bacteria in triplicate. The samples were placed on plates of agar (SDA) Sab Dex, where approximately 01 A cell added 0 placed in the plate and then incubated at 0 am After 17 days no bacterial growth oo observed on the sample exhibiting inhibition of phosphonium ionic units based on butyl butyl-based ammonium ionomer b8/mol ionic function to the growth of gram-positive bacteria

.gram positive bacteria to gram negative bacteria 11 problem in example jonomer resistance to ion units LV A example tested using the same procedure as summarized for (Escherichia coli) gram negative bacteria shown to prevent all notes over bacterial growth days; No bacterial growth Vo after .17 Example 0 inhibition of butyl-based ammonium ionomer gram negative ionic functionality 7 + A b

. 8168

Ex.11 US Patent 00017/07187455; united here by reference; Describes the preparation of 0-isoprene Yo. dle isoprene BIR C of brominated high isoprene butyl and A+ c) VY molar equivalent based on allylic bromide content of BIIR isoprene with added high bromine Triphenylphosphine (TPP) triphenylphosphine was previously mixed on an 11" XT mill at room temperature for ? minutes. Then the mixture was passed through a twin screw extruder 0.10 m. Final product analysis THNMR confirmed the complete conversion of all allylic bromide of BB2030 into a corresponding ionomeric species with an ionic content of 1.8 7 mol. Minutes and their resistance to gram-positive growth (Staphylococcus aureus) gram positive were tested in triplicate The samples were placed on plates of (SDA) Sab Dex agar, where approximately »m cell (Cail Ye) placed in The plate and then placed in the incubator at 10 C. After V days, no bacterial Bad growth on the sample, showing inhibition of ionic units of phosphonium based on butyl isoprene va ionic functionality mol ionic function 7 +, A B butyl-based phosphonium ionomer

Growth of gram positive bacteria, example .71. Resistance of ionic units:©::00e: The problem in example 19 to gram negative bacteria (Escherichia coli) gram negative bacteria was tested using the same procedure as summarized in © Example V4 after 17 days; No bacterial growth is observed on the sample; Inhibition of high isoprene butyl-based phosphonium ionomer with 1.8 7 mol presents an ionic function to growth

Gram-negative bacteria Example 1 Ld.

YY c from example 1 is covered in 7 40 ethanol for sterilization 0 and then put into a 10 ml scintillation vial where 10 ml of MO medium is added. A colony of 01150 strain of Gram-negative Escherichia coli (negative bacteria) is selected and suspended to a salt solution of MO medium then; 9000 μl some bacteria is added to each tube. Cured rubber Jil was used as a control and 90 µL samples were tested at 0 01 oA of 7 h. Visceral bacteria were counted using flow cytometry and SYBER Green “nucleic acid stain” using the following procedure: © 0 µL of X 001 SYBER Green dye (suspended in DMSO) was added to 90 μl of sample; for a final SYBER Green concentration of 1. Samples were incubated in the dark for approximately 1 vo min and then placed on Flow cytometer The percentage of dead cells was measured using flow cytometry and nucleic acid stain Ye 98710292 after 4 hours More than 0 5 7 bacteria were killed showing the nature of ABE Bacteria have high isoprene butyl-based phosphonium ionomer 7 mol ionic functionality.

Example YY; International Patent 00101/01115977; United here by reference. Describes the preparation of a brominated butyl terpolymer consisting of isobutylene “isoprene” and para-methylstyrene 001. para-methylstyrene c from brominated terpolymer and 5c) YY molar equivalent of Adina on allylic bromide content

The content of isoprene 13118 with a high bromine additive) triphenylphosphine (TPP) triphenylphosphine was mixed by mixing on an AVY X + mill at room temperature for yt minutes. Then the mixture was passed through a two-roll extruder twin screw extruder at 1000 C. Analysis of the final product by THNMR confirmed complete conversion of all allylic bromide of © 332030 into an identical type of ionic unit with an ionic content of 1.8 7 mol. for 0 minutes and their resistance to gram positive growth tests (Staphylococcus aureus) in triplicate at 01011681. The samples were placed on agar (SDA) Sab Dex plates where approximately 10' cells were added; placed in plate and then incubated at 1 0 C. After 1 days, no bacterial growth is observed on the sample; Ve exhibits inhibition of butyl terpolymer-based (i sual} phosphonium ionomer B A 7 mol ionic function to the growth of gram-positive bacteria example YY resistance of the ionic units formed in example YY to gram-negative bacteria (Escherichia coli ) gram negative bacteria tested using the same procedure as summarized in Example YY 5 after 7 days; no bacterial growth observed on the sample; The inhibition of butyl terpolymer-based phosphonium exposes 0.8 Sionomer / mol of ionic functionality to the growth of gram-negative bacteria. Example 4? . Example 1 Mix Carbon Black N660 in a Brabender blender at 10 m and 0 speed of 01 rpm for 11 minutes. The resulting material was poured into 100 °C for 10 minutes and its resistance to gram-positive growth (Staphylococcus aureus) gram positive (concentration - 01") was tested in triplicate according to JTS 2801:00 7, which is incorporated herein by reference. According to this method cmethod antibacterial activity measured by determining the survival of bacterial cells carried in deep contact Vi sad hour in Vo © with the surface of the formulation to be tested. antibacterial effect measured by comparing the survival of bacteria on the formulation to be tested with that achieved on the control.In all trials the control included a polyethylene layer there was at least a reduction of rv of bacteria showing the antibacterial nature of the unit compounds ionic from daly record carbon-black filled phosphonium ionomer -gram positive bacteria to growth of gram positive bacteria 465 formed in example; 7 to gram negative bacteria jonomer resistance to ionic units Yo Example tested using the same procedure as summarized for (Escherichia coli) gram negative bacteria © clog reduction of bacteria showing at least one log reduction of bacteria VE example of compounds of phosphonium ionic units loaded antibacterial nature The antibacterial nature of carbon-black filled phosphonium ionomer composites with black ionomer 0 gram negative bacteria at 0 m and two rotating speeds Brabender in blender Hi Sil 233 Mix with 1 lie .

YY Example 100 m 001 poured into the resulting material min. The resulting material is 15 for 01 rpm of rotor speed (01 - concentration Staphylococcus aureus) for © minutes and its resistance to gram positive growth is at least one log reduction of one log JIS 7 2801 according to triplicate Tested in triplicate of antibacterial nature; Displays the antibacterial nature of bacteria reduction silica-filled phosphonium ionomer ionic units of 1 -gram positive bacteria to the growth of Gram-positive composites to Gram-negative bacteria Ye formed in the example of jonomer Resistance to ionic units .717 Example tested using the same procedure as summarized for (Escherichia coli) gram negative bacteria Displays sbacteria of bacteria at least one log reduction daly YT log reduction Example compounds Ionic units of antibacterial nature - 0 gram to the growth of silica-filled phosphonium ionomer composites with silica .negative bacteria "m and two rotating speeds 01 in a Brabender in a blender Cloisite 15A mixed with 1 example YA example M001 poured into the resulting material per minute. Gram-positive growth Yo according to 2801 2 115. At least one log reduction triplicate tested in triplicates (01) - Concentration showing antibacterial nature ¢ bacteria one log reduction

YA ionomer of nanocomposites aaa components in ye antibacterial nature hall to the growth of clay-filled phosphonium from clay-filled .gram positive bacteria to YA gram-negative bacteria formed in an example Jonomer resistance to ionic units LY 4 Example Tested using the same procedure as summarized for (Escherichia coli) gram negative bacteria © displays “bacteria of bacteria one log reduction als at least log reduction YA Example, nanocomposites from components in nano size antibacterial nature to the growth of silica-filled phosphonium ionomer of ionic units of phosphonium filled with silica -gram negative bacteria c of triphenylphosphine Ye combines with Exxpro 3745 c of You ve Example Ve milled at room temperature for ? minutes. The mixture is passed through triphenylphosphine and then purified (01 rpm) miniature twin screw extruder analysis of the resulting material on a mill at room temperature followed by analysis of the benzylic polymer bromide to confirm the complete conversion of NMR benzylbromide groups by the conformer This displays jonomeric species to parent polymer 0 gram positive ionic species resistant to growth of gram positive bacteria modified polymer modified polymer fungi, algae, algae, gram negative bacteria ¢ bacteria described butyl ionomer from a surface covered with “aa Yr” ions like zebra for a week. The number of aquarium in a tank The thickness of zebra mussels is shown to 1 in the example of the surface attached to it calculated and compared with the control that was not coated with butyl ionic units. mussels V+ if zebra mussels succeed in preventing the accumulation of butyl ionomer ionic units of butyl sale that from the control it expects 7 5 0 mostly jonomer on ionic units zebra mussels Jae rubber will be effective in reducing the number or preventing the butyl ionomer that ionic units of butyl and / or insects (arthropods) 2058 mollusca approved Increases in the number of molluscs and dependent on algae, algae, fungi, fungi and bacteria on previous observations with Ye bacteria in particular; He expects that mechanistic behavior the same way as in va insects and mollusca ion units: 1000016 would be effective in preventing contact with arthropoda molluscs (1) arthropods Polypropylene (pli) from poly phr 50 mixes with 1 of an example phr 001 iY JU Tddo N 001 of 1010© speed "m" and two rotary speeds 088 internal mixer specify tensile properties pouring and tensile properties ‎ resulting material 5 « growth of gram positive bacteria. phr 01 combines with Example 1 of phr 001 : FY Example Pentayln for a minute; track by adding rpm VV of rotor speed "m and two rotor speed 1 in Banbury mixing for ; minutes Additional Vulkacit DM/C (1.3 phr) 5 “Sunpar (7 phr) <A sleep 0 smell) V) stearic acid o(phr +,9) sulfur sulfur - curatives Processors, two roll 10” x 20” mill, then add (phr 1,0) zine oxide and zinc oxide to be processed in 10016 m. This resulting mixture is exposed at room temperature. The resulting mixture is gram-positive bacteria. The treated formulation is resistant to the growth of gram-positive fungi, algae, and gram-negative bacteria. Gram 0

Claims (1)

protection elements 1.1 A composition that includes ionic units of butyl jonomer reduces the number of organisms Y and or prevents the accumulation of organisms at least on the surface of the article composition. LY 1 is the composition according to the protection element (0) in which the jonomer ionic units prevent xi accumulation, the increase in the number of organisms. 1 2©. The lah combination of claimant 1; in which the jonomer ionic units prevent accumulation Y by obstructing the connection of organisms to the composition . 1 4. The composition according to which Claim 1 to ?; In which the ionic units, jonomer ¥, reduce the number of living organisms by killing individual organisms ~~ or repressing reproduction Ji inhibiting organisms. 1 *. the composition according to any of Claims 1 to 4; Which organisms include bacteria: 1) Composition according to GY protection element 1 to 4; The organisms Y organisms include fungi or algae. Ly) the structure Lab for any of the protection elements 1 to of which the organisms ¥ include molluscs mollusca or insects (arthropoda). A) the structure according The oY protective element that living organisms have includes zebra .mussels |" 1 40. The composition according to any of the claims 1 to A in which the ionic units ionomer Y is prepared in an amount sufficient to expose one or more of the following: 0. ior prevented the increase of an “antigen” and in the number of gram positive bacteria ¢ on composition article when incubated 100068160 in the presence of gram positive bacteria in 01 done for 1 day; 7 APA prevention of an increase in the number of gram negative bacteria V on formula article when placed in incubator 100008160 in the presence of gram positive bacteria A in 01 then for all 1 1 When article in the number of fungi on the composition prevention of an increase c. prevent excess 4; or tase YA "m for a period of 01 in fungi in the presence of incubated mushrooms placed in the incubator 00 placed in the incubator Laie article on the formula algae d._preventing the increase in the number of algae 0 days YA 510 Presence of Algae 188 in 8incubated | 01 to 9; Which Ionic Units 1 Composition According to Any Protective Element 1.01 Supplied in sufficient quantity to offer a reduction of «600000: in Number of Gram Negative Bacteria jonomer per incubated when incubated 7 0s by at least gram negative bacteria ¥ h. 1 according to any of the claim elements pictrl_.11 1 mol. 7 0.7 at least an ionic content jonomer |" have a jonomer content of the composition according to the claim; Which has ionic units .0 1 at least 1 7 mol. At least anionic content ionic "has ionic units OF to 1 according to any of the protective elements" .14 0 cationic nitrogen based including jonomer " nitrogen based nucleophile Derived from a nitrogen-based nucleophilic functional group ¥ having ionic units OY to 1 according to any of the protective elements ASE oe 1 cationic phosphorus based including jonomer Y -a phosphorus based nucleophile Derived from phosphorus-based nucleophilic functional group V It has ionic units from G3 to 1 according to any of the protective elements ASH OT 1 isoolefin Includes repeat units derived from isoolefin monomer Butyl β-isoolefin: 000 conjugated diene monomer and diene monomer v monomer isoolefin having isolefin monomer OT the composition according to claim 1017 1 conjugated isoprene including isoprene diene monomer including isobutylene and butyl diene monomer having Ionic units of butyl OY or 16 18._The composition according to the protection elements 1 -styrenic monomer from repeating units derived 1 . Turkish according to the claim OA in which the styrenic monomer includes para-methyl ¥ styrene .para-methylstyrene dS LY. 1 according to any of the claims 1 to 90; of which the ionic units 0 jonomer 7 include at least 7,7 7 mol sane multiolefin bonds derived from a diene paired in The polymer backbone. styrenic monomer s 001 77._the composition according to claim 71 of which isoolefin monomer ¥ includes isobutylene and styrenic monomer includes includes para-methylstyrene YY 1 Composition pursuant to any of Claims 1 to 7?, which has ionic units of "butyl ionomer", which are supplied as part of the composition material| Composite material, including plastic v 6 by 18 m. 1 74. The composition according to Claim 77 in which the plastic includes polyethylene; "Polypropylene cpolypropylene polymer EP; polymer (EPDM) or nylon polymer nylon .polymer Y¥ 1 5?._composition according to any of the claims 1 to YE having ionic units of butyl ionomer also includes sale filler 1 71 ._The composition according to the protective element YO in which the composition article filler includes carbon black, silica, talc, or clay 1 77._The composition according to pate GY From protection elements 1 to YY which have the composition article ¥ include a fluid conduit, container closure, or sealant to let the tool handle device material handling apparatus; simarine vessel installation structure » cooling tower ¢ metal working apparatus ¢ metal working apparatus engine component “membranes Li&” enginecomponent or 1 footwear sy which prevents accumulation TY to 1 formulation according to any of the protection elements YA 1 formation of a includes preventing the formation of a continuous layer of living organism illlaccumulation from the surface of the composition Lon on larger than organisms continuous layer 1 .surface of the article ¢ Where the YA to 1 ionic units make up the composition according to any of the claims of .79 1 . article on the composition surface coating surface coating (4 jonomer Y coating; sasurface coating with which the surface coating (V4) composition according to claim LY. 1 “chemical vapor deposit (CVD) Sue vapor deposition) capplied membrane Applied Membrane ¥ .powder coating Powder Coating 5 T is a surface coatin of composition according to Clause 79 with which the surface coating 1. 1 paint Y cured 7 “with which 1 is treated Claims 79 to oY Composition according to 27. 1. butyl 160002: "ionic units of butyl" having butyl ions. FY *©._Composition according to claims 9? to 1 -plastic including composite material supplied as part of the composition material butyl ionomer polyethylene plastic, including the one containing the plastic FY©, _composition according to claim 1 EPDM polymer © polymer EP polymer <polypropylene polyethylene Y .nylon polymer or nylon polymer EPDM ¥ composite material Sill which has a material (FE) the composition according to the age of protection?? or, Lye 1 -thermoplastic vulcanizate including thermoplastic vulcanizate ¥ combination according to any claim 74 to 5”; Which has a coating, 1. 3. butyl ionomer that essentially contains butyl ion units, surface coating, Y surface