TW201000010A - Antimicrobial compositions and methods of making same - Google Patents

Abstract

This invention relates to a process of making a group of sylilated poly(N-alkyl-4-vinylpyridinium) quaternized salts suitable for use as coating materials for the treatment of substrate surfaces to impart an antimicrobial effect. The method includes a step of combining a hydrocarbyl halide and a ploy(4-vinylpyridine) in a one-pot reaction mixture, whereby a silylated quaternized salt having antimicrobial property is obtained.

Description

201000010 IX. INSTRUCTIONS: The cross-references of the present invention are as follows: US Provisional Application No. _46, 347, Fine Year June Day #' and US Temporary Application No. _46,9 ,, 2〇〇 The invention is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in its entirety in the extent of the disclosure of the disclosure. TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing a decaneated poly(anthracene-alkyl-4-vinylpyridinium) quaternary ammonium salt group, decane-polymerized poly(Ν_alkyl_4_B The quaternary ammonium salt group is suitable as a coating material for treating the surface of the substrate to have an antibacterial effect. [Prior Art] The 4-stage polymer of 4-vinylpyridine has been confirmed to have anti-mite properties in an aqueous solution and to remove air-mediated microorganisms upon contact with the surface when applied to a surface. See, for example, Pr〇c. Nat 1. Acad. Sci. USA, 98, 5981 (2001); C&EN, May 28, 2001, page 13; Biotechnol. Lett., 24, 801 (2002);

Biotechnol. Bioeng., 79, 466 (2002); and Polymeric Materials: Science & Engineering, 91, 814 (2004) 荨 Literature. A method of functionalizing a surface to impart antimicrobial efficacy is disclosed, for example, in U.S. Patent Publication No. US-2003-0091641 - A1, which comprises the step of: depositing a layer of Si 2 nanoparticle on a substrate. Material, 2) profit

201000010 Amination of the surface with 3-aminopropane trimethoxy decane, clarification of the surface bromine using iota, 4-dibromobutane, and then 4) using alkyl-polyvinyl pyridine in the presence of a bromo alkane Derivatization is carried out on the brominated surface. The above-mentioned method using 1'4-dibromobutane has the disadvantage that bidirectional products are inevitably produced (the reaction of the main chain of the (four) reactants is all reacted), causing the surface groups to crosslink and fail to proceed. The functionalization is carried out under the reaction, and the reaction is made to achieve economic benefits. SUMMARY OF THE INVENTION There is a high demand for products having an antimicrobial surface. These surfaces preferably exhibit an antibacterial effect against Gram positive bacteria (eg, Cong) and "negative bacteria (Youcan·). The surface of the present invention having antibacterial properties after treatment, including glass (Tao f Stone) surface and fabric surface (such as cotton or synthetic fiber), the above surface shows that the antibacterial layer is very durable, and the system is (4) tolerate repetitive, cyclic cleaning/cleaning. Avoid St.: Antibacterial surface, but can be cross-linked, for example, before the surface group functionalizes. The molecular part is called the molecular part as the antibacterial surface Θ化 ^ t ^ 佳 贯 施 — — — 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备The method further provides a new antibacterial agent. According to the present invention, a polymer material 201000010 which is resistant to test is provided, which comprises a polymer formed by repeating a unit of the chemical formula shown below;

Wherein R is a substituted or unsubstituted phenyl group; A is a Cm alkyl chain; D is a Cm alkyl chain; X is a halogen; and η is at least 2. In a specific embodiment, R is a phenyl group. In another embodiment, X is gas. In yet another embodiment, X is bromine. In another embodiment, the lanthanum is selected from the group consisting of methylene and ethylene. In yet another embodiment, D is a brace. In another embodiment, 'R is a phenyl group substituted with -(E)m-Si(-0-Alk)3, wherein each Aik is a 匕-6 alkyl group, and E is m carbon atoms. The hydrogen-based divalent carbon group ' and m of the atom are 〇 to 12, for example, '-(E)m-Si(-0-Alk)3 is a para-substituent on the phenyl group, wherein each Aik is a methyl group And its ~(Ε)ΠΤ· is a lower alkylene chain, or E is a group having the chemical formula ^Ρ2Ι1ι~αί2-(:Η2-, wherein Ph is a phenyl group. In the specific embodiment, 'η is 2 to 1000, or 50 to 200. In another embodiment 7, 201000010, a surface comprising a polymeric material having an antibacterial effect, such as a glass surface, a stone surface, and a a wood surface, a polymeric material, a fabric surface, or at least one natural fiber such as cotton fiber. The present invention provides a method of preparing a polymeric material having an antibacterial effect, the method comprising: hydrogen-based divalent carbon-based chloride, The chloroalkyl decane is combined with poly(4-vinylpyridine) in a single reaction mixture to obtain a methacrylated quaternary salt having antibacterial properties. In a specific embodiment, the hydrogen-based divalent carbon group has the formula CnH2n+1-X, wherein η is 1 to 18, and X is chlorine or bromine. In yet another embodiment, the hydrogen-based divalent carbon group The chloride is selected from the group consisting of chlorobutane, 1-bromoheptane, 1-bromooctane, chlorinated benzene, vaporized ethylbenzene, and chlorinated propylene. In one embodiment, the haloalkyl decane has the formula ( Alk-0-)3Si(-(E)m-Hal), wherein each Aik is a Ci-6 alkyl group, 'E is a hydrogen-based divalent carbon group containing m carbon atoms, m is 0 to 12, Hal In another embodiment of this aspect, the haloalkyl decane is gamma-chloropropane tridecyloxydecane. In yet another embodiment, the molecular weight of the poly(4-vinylpyridine) is about 10 000 MW to about q 180,000 MW, or a molecular weight of about 20,000 MW. In one embodiment, at least 50% of the polymeric material having an antibacterial effect is quaternized. In the present invention, a preparation is provided. A method of polymerizing a material having an antibacterial effect, the method comprising incorporating a hydrogen-based divalent carbon-based chloride and a poly(4-vinylpyridine) into a single reaction mixture, thereby having an antibacterial property a decaneated quaternary salt. In a particular embodiment, the fluorenyl divalent carbon-based chloride has the formula CnH2n+1-X, wherein η is from 1 to 18, wherein X is chlorine or bromine. The hydrogen-based divalent carbon-based chloride is selected from the group consisting of 1-chlorobutane, 1-bromoheptane, 1-bromooctane, chlorobenzene, ethylbenzene chloride, and chlorinated propylene. In a particular embodiment, the poly(4-vinylpyridine) has a molecular weight of from about 10,000 MW to about 16,000 MW, or about 20,000 MW, and at least 5% of the polymeric material having an antimicrobial effect is quaternized. The present invention further provides a method for making a surface resistant to bacterial growth, the method comprising incorporating by using a hydrogen-based divalent carbon-based chloride, a chloroalkyl group, and a poly(4-ethyl-n-n-ratio) a polymeric material having an antibacterial effect obtained by reacting the mixture once; and coating the polymeric material having an antibacterial effect onto the surface of an article to thereby impart an antibacterial effect to the surface. In this particular embodiment, the surface of the article is a cotton fiber surface. In another embodiment, the surface of the article is a glass surface or a stone surface. In a specific embodiment of this aspect, the microorganism is a Gram-negative bacterium, such as Escherichia Coli, Pseudomonas aeruginosa, or e/a /we (10). In one embodiment of this aspect, the microorganism is a Gram-positive bacterium, such as 5 dying 5/?/?/7 (9 匸〇£^" 5 ai/rei/5. 〇 The present invention further provides a Method for surface-energy-resistant growth 'This method comprises using a polymeric material having an antibacterial effect by incorporating a hydrogen-based divalent carbon-based chloride with poly(4-vinylpyridine) into a single reaction mixture; and polymerizing the polymerization The material is applied to the surface of an article to impart an antibacterial effect to the surface. In one embodiment, the surface of the article is a cotton fiber surface. In another embodiment, the surface of the article is a glass or stone surface. In one embodiment, the microorganism is a 201000010 Gram negative bacteria, such as Fsaherj'cMa CoJj., Pseudomonas aeruginosa, ο>τ Klebsi el a pneumoniae. In another embodiment, the microorganism is a Gram positive Type bacteria, such as Staphylococcus aureus. To enable a further understanding of the features and technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings. The following description and examples are intended to be illustrative of specific embodiments of the present invention. Other variations and modifications are possible within the scope of the invention. Therefore, the description of the specific exemplary embodiments should not be construed as limiting the scope of the invention. Quaternized antibacterial 丨 丨 锢 锢 锢 锢 锢 锢 锢 锢 锢 锢 锢 锢 锢 制备 制备 制备 制备 制备 制备 制备Anti-Pit Chest G^ ^ A simplified method for preparing quaternary salts of anti-coupling reaction. Functionalization reagent, 曱矽浐 ^ ^ ^ ^ Lu Yue b Sword 丫 four-stage salt (II) system (1) , with chlorinated bases, said that the base of the brine base) (2) and poly (4, E women / gas propylene trimethyl sulphate f. ~ (3) in the absence of water - reaction 201000010

C"_H2rH^CI + (CHqO:^-Si-C3He-CI +(-CH2.CfH- CH2V (1) C2) P ol y(4 -vi nylp yrid in e) (3)

Si(OCH3\

Silylated PVP Quaternized Salts (II) ❹ Alternatively, the above reaction can be carried out in two stages. The alkyl halide (1) is reacted with poly(4-vinylcridine) (3) to produce a partially quaternized PVP salt (I). The partially quaternized PVP salt (I) itself can be used as an antibacterial agent which is very washable to textiles without having to be made with a chloroalkyl group (for example, γ-chloropropane tris oxide) Further functionalization, or further reacted with a chloroalkyl-containing decane (such as γ-chloropropane trimethoxy decane) (2) to produce a decylated PVP quaternary salt (II).

CnH2n-ri n 2"丨爿

Partially Quaternized PVF' Salt (I)

Si(OCH5)3

Silylated PVP quaternized Salts(II) ❹ ❹ 201000010 1 碁 偿 偿 偿 偿 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H And X is a group selected from the group consisting of F, cl, Br, and 1 =, wherein 卩 π is particularly preferred. The term "hospital base" is used herein to refer to it as a generalist. Known by the user (not limited to special definitions), and in the non-limiting interpretation, refers to 1 2 3'4,5,6,7,8,9,10, m,13, 14,15,16,'17 a linear or branched, cyclic or acyclic, saturated or unsaturated aliphatic carbohydrate of 18 or more carbon atoms (for example, Ci ig alkyl). "Lower aikyi" has The same definition of silk, but = 1, 2, 3, 4, 5, or 6 carbon atoms (such as c 6 alkyl). "Higher alkyi", with the same definition as silk, two broad Containing 7 or 8 'up to about 18 or more carbon atoms (eg, 仏-]8 alkyl). Representative linear alkyl groups include methyl, ethyl, n-propane, including 'n-hexyl and the like Group a branched alkane, including isopropane 'secondary butyl, isobutyl, tert-butyl, isoprene and eight similar bases. The no-filament filament contains between the adjacent carbon atoms to = three bonds, ( ί is not referred to as a dilute or a block base. The term "a yene" in this context is used to describe the saturated carbon chain of different bonds between two groups, such as methylation of its silk fissure r_rHPR, " The base bond (-〇, ethylidene chain 2 2 . low carbon alkylene chain) contains, for example, z' A 4, 5, or 6 carbon atoms. 12 201000010 "Cycloalkyl" as used herein Refers to a broadly defined cycloalkyl group, which is broadly referred to and generally used by those skilled in the art (not limited to a particular definition), and, in the non-limiting interpretation, includes alkyl-based oximes, including mono-, and Or a poly-homocyclic alkyl ring system. A cyclic alkyl molecular moiety (also referred to as a "cycloalkyl group" or a "cyclic group of a homocyclic ring" includes, for example, cyclopropane, cyclobutyl, and ring. a pentyl, cyclohexyl, -ch2-cyclopropane, -CH2-cyclobutyl, -CH2-cyclopentyl, -CH2-cyclohexyl, cyclopentenyl, and cyclohexenyl molecular moiety. In a preferred embodiment, a linear alkyl halide is used. Lower alkyl halides are also particularly preferred (e.g., η = 1 to 6). However, alkyl halides having a monohalogen substituent are particularly preferred. Preferably, in a particular embodiment, it is acceptable or even necessary to incorporate two or more il substituents (the same substituent or a different substituent). Particularly preferred alkyl halides include 1 - chloroprene, 1-bromoheptane, 1-bromooctane, and alkyl chloride. Although alkyl halides are preferred, other hydrogen-based divalent carbon-based halides such as aryl halides, aralkyl iodides and alkylaryl halides can also be used. The term "aryl" as used herein is used broadly and is generally used by those skilled in the art (not limited to a particular definition) and, by way of non-limiting explanation, refers to a moiety comprising an aromatic carbocyclic molecule, such as phenyl. Or naphthyl, including mono-, di- and poly-homocyclic aromatic ring systems (eg, C6-18 aryl). As used herein, "aryl burnt" is used broadly and is generally used by those skilled in the art (not limited to a particular definition) and, by way of non-limiting interpretation, means having at least one hydrogen atom 201000010 basal-sub-heart knives (eg, stupid aralkyl groups including c-substituted alkyl groups), -CH2-(stupyl H2'(11-yl), pheno-a) and)'~(CH2)2m, H2' (2~naphthalene, and its t group)2. As used herein; i(Ql2)3, (unclear definition), and generally known to the skilled person, the 'user' is a generalized-institutional molecule::: the lower finger contains the jin:; the father An aromatic aryl group substituted with an aromatic aryl group. Subbenzene. Including gasified benzene' gasification methyl stupid: chlorohaloalkyl decane chlorohydrin (Alk-〇-) 3Si (Hai) ^ Lijia has a chemical group; Hal is selected from 匕^, where Alk is the same Or a different alkyl group, which is also a group of ci, which is particularly composed of Br' f 1 , is good for the season. Alk is preferably selected from the group consisting of lower alkyl groups, oxime, and methyl groups. E is preferably a C 2 m hydrogen-based divalent carbon-based linking group, such as an alkyl chain, or a hydrogen-based divalent carbon group having a phenyl ring linking the broth to the rest of the polymer, as in the chemical formula a group of -CH2_ph-CH2_CH2- (where Ph is a phenyl group). Particularly preferred are those having a methoxy group, such as a positive propane having three methoxy groups and one terminal atom attached to a terminal C1 substituent (e.g., γ-chloropropane trimethoxy decane). In a particular embodiment, the haloalkyl decane may not be used in the reaction mixture to provide a PVP 4 2010 201010 grade salt as an antibacterial functional reactant: sputum-free. Polyethylene (polyvinyl hydride) can be any one having a suitable bond length or molecular weight. Poly (4-ethylene ° ratio) has 2 pyridinium units up to more than about 1500 pyridinium units, preferably from about 100, 200, 300, 400, or 500 pyridinium units up to Approximately 600, 700, 800, 900, or 1000 pyridinium units. Particularly preferred is poly(4-vinylpyridine) having about 190 pyridinium units (equivalent to 20,000 MW). Such poly(4-vinylpyridine) may be a commercially available product such as REILLINETM 410 manufactured by Reilly Indus Tries of Indianapolis Corporation. In particular embodiments, higher molecular weights, such as poly(4-vinylpyrene) of up to about 160,000 MW or higher, can be used. The fourth-order antibacterial functional reagent ❹ As described above, in a specific embodiment, the haloalkyl decane may not be used in the reaction mixture to obtain a PVP quaternary salt as an antibacterial functional reactant: no sinter, for example: 15 201000010 •ch2- -ch2- -ch2-

CnH2n+l CnH2n+I

Alternatively, a haloalkyl decane can be used in the reaction product to produce a cerium-burning quaternary salt such as: CH2--CH2--CH2--CH2

CnH2n+i CnH2n I Si(OCH3)3 The degree of quaternization reaction can be varied by adjusting the amount of alkyl halide (or other hydrogen-based divalent carbon-based halide) in the reaction mixture. In the above two polymer structures, the degree of quaternization reaction was 50%. The degree of ruthenium oxidation in the second structure is 25%. It may also be advantageous to utilize a lower degree of quaternization reaction, favoring less than 50%, such as 5% - 45% of the quaternary oxime reaction; however, it is generally preferred to maximize the quaternization reaction' eg More than 50% of the four-level reaction, such as up to 60%, 16 201000010 70%, 80%, battle 95 team or 1_. The degree of oxidation of the ceramsite can be controlled by the degree of secondary reaction, but it is advantageous to maximize the oxidization, especially in applications where extreme speed is required. ~ A single-type repeating unit can be used, or a mixed chemical repeating unit can be obtained by using a suitable mixture of reactants and different molecular moieties. ❹ ❹ The advantage of the above-mentioned secondary reaction is that the reaction step is reduced by two steps than the conventional method of using 3-aminopropyl propyl dimethoxy; The resulting functionalized product (formylated PVP quaternary salt) also has the advantage that it is soluble in water and/or an organic solvent such as methanol, so that it is further processed and made into (iv). This processing step may include performing coating techniques known in the art on the surface of the substrate, such as dipping, dipping, spraying, aerosolizing, spraying, brushing, curtain coating, rolling, silk~ , yellow light process, inkjet and similar technical materials (such as broken glass) = UrT base side group (such as trimethoxy) as a base group; alcohol group formation is very durable and not easy to remove ( For example, being washed off the substrate may be applied by any method. Preferably, the layer of bis::- ί is coated on the surface including the co-bonded to the antibacterial agent in the antibiotic agent. Alternatively, the antibacterial agent can be coated on the surface with %H' and then transferred to the surface to obtain an antibacterial effect. Anti-can be used as a polishing agent, table "_ 201000010 (cau 1 ks ), adhesive, Tail paint (fin), paint, and sacrificial composition (including phenolic resin, anthrone polymer, chlorinated rubber, coal tar and epoxy composition, epoxy resin, polyamide resin, vinyl resin, Elastomers, acrylate polymers, fluoropolymers, polyesters and polyurethanes, latex), It is delivered to the surface for which an antibacterial effect is to be obtained, and continuous or intermittent coating may be used; the entire surface or part of the surface of the substrate may also be treated. β Application of the coffin may be applied by any appropriate method. Preferably, the antibacterial agent is applied. Applying the antibacterial agent as a coating to a surface comprising a functional group covalently bonded to the corresponding group in the antibacterial agent. Alternatively, the antibacterial agent may be coated on a suitable substrate and then the substrate Transfer to the surface to obtain antibacterial effect. Antibacterial agent can be incorporated into polishing agent, surface cleaner, caulking agent, adhesive, tail paint, paint, wax polymerizable composition (including phenolic resin, • anthrone polymer) , chlorinated rubber, coal tar and epoxy composition, epoxy resin, polyamide resin, vinyl resin, elastomer, acrylate polymer, fluoropolymer, polyester and polyethyl phthalate, latex), It can be transferred to the surface to obtain anti-S effect. It can be used for continuous or inter-four (four) cloth. The entire surface or part can be treated. Preferred embodiment (4) Anti-g functionalization reagent can be used for various purposes, avoiding or inhibiting Bacterial growth. Reagents are particularly effective in inhibiting Gram_ positive and Gram-negative bacterial growth; however, it is also possible to avoid or 18 201000010 to inhibit the growth of other microorganisms and fine organic organisms such as molds, viruses, and protozoa. Positive bacteria have peptido glycans (giyCan) and polysaccharides and/or teichoic acid as their

一 A part of the cell wall structure' and characterized by a blue-violet color reaction in the Gram-staining procedure. Representative Gram-positive bacteria include, but are not limited to, Jci/zzo/zz/ces1, Bacillus anthracis, Bifidobacterium spp., Clostridium botulinum, Clostridium perfringens, Clostridium spp., Clostridium tetani,

Corynebacteri um di ph theriae, Corynebacter ium jeikeium, Enterococcus faecal is, Enterococcus faecium, Erysipelo thrix rhusi opa thi ae,

Eubacterium spp. , Gardnerella vaginalis,

Gemella morbi 1 lonm, Leuconostoc spp., Mycobacterium abcessus, Mycobacterium avium complex, Mycobacterium chelonae, Mycobacterium fortuitwn, Mycobacterium haemophi 1 ium, Mycobacterium kansasii, Mycobacterium leprae, Mycobacterium marinum, Mycobacterium scrofulaceum, Mycoba cterium smegma tis, Mycobacterium terrae, Mvcobacterium tuberculosis, Mycobacterium ulcerans, Mocardia 19 201000010 spp., Pep tococcus n iger, Pep tos trep toco ecus spp., Proprionibacterium spp., Staphylococcus aureus, Staphylococcus auricularis, Staphylococcus capitis, Staphylococcus cohnii, Staphylococcus epidermidis, Staphylococcus haemolyticus, Staphylococcus hominis, Staphylococcus lugdanensis, Staphylococcus ❹ saccharolyticus, Staphylococcus saprophyticus, Staphylococcus schlei feri, Staphylococcus si mi Ians, Staphylococcus ivarneri,

Staphylococcus xylosus, (B streptococcus), Streptococcus bo vis, Streptococcus equi, Streptococcus mi ti or, Streptococcus pneumoniae

Streptococcus agalactiae Streptococcus anginosus, Streptococcus can is, Streptococcus mi lleri, Streptococcus mu tans, Streptococcus pyogenes

Str ethnic group A streptococcus), Streptococcus salivarius, and SYrep. Gram - Negative bacteria are characterized by each bacterial cell surrounded by a double membrane. Representative Gram-negative bacteria include, but are not limited to, calcoaceticus, Actinobaci 1 lus act inomyce temcomi tans, Aeromonas hydrophi la,

Alcal igenes xylosoxidans, Bacteroides, 20 201000010 Ο ❹

Bacteroides fragi 1 is, Bartonella bacilliformis, Bordetella spp., Borrelia burgdorferi, Branhawella catarrhalis, Brucella spp., Campylobacter spp., Chalmydia pneumoniae, Chlamydia psi ttaci, Chlamydia trachomatis, Chromobacterium violaceum, Citrobacter spp., Eikenella corrodens, Enterobacter aerogenes, Escherichia Coli, Flavobacterium meningosepticum, Fusobacterium spp., Haemophilus influenzae, Haemophilus spp., Helicobacter pylori, Klebsiella spp., Legionella spp., Leptospira spp., Moraxella catarrhal is, Morganel la morganii, pneumoniae, Neisseria gonorrhoeae, eningi tides, Pasteurel la Pies I omonas shigel loides, Prevotel la spp. Proteus spp., Providencia rettgeri Pseudomonas aeruginosa, Pseudomonas spp. Rickettsia prowazekii, Rickettsia rickettsii Rochalimaea spp. , Salmonella spp. , Salmonella typhi, Serratia marcescens, Shigella spp., Treponema car a teum, Treponema Pallidum, pallidum endemicum,

Mycoplasma Neisseria mu 1 toeida

Treponema

Treponema 21 201000010 pertenue, Veillonella spp., Vibrio cho 1 erae, Vibrio vulnificus, Yersinia enterocolitica, and Yersinia pestis. The reagents of the preferred embodiments can be applied to a wide variety of surfaces to provide an antibacterial and odor eliminating effect. Reagents can be used to treat fabrics (woven or non-woven) or fibers, such as collagen, used in clothing, bed and bathroom linen, upholstery and other home accessories (pads, curtains, wallpaper, carpeting). (leather, suede fabric), 纤维素 cellulose (cotton, linen) and horny (wool, silk) materials; synthetic fiber and fiber (polyester, nylon, silicone rubber, latex, plastic, polyanhydride, poly-origin (ortho) ester, polydecylamine, polyacrylonitrile, polyaminodecanoate, polyethylene 'polytetrafluoroacetic acid, polyphazenes and p-benzoquinone t-ethyl, natural-synthetic fiber mixture (eg polyg/cotton 65:35 'DACRON®/cotton, nylon/cotton, and other cotton blends); fiber or fiber for medical use (paper towels, facial tissue, hygiene products, toilet paper' stationery ); glass surface, polymer surface (eg kitchen interior and exterior 'floor and wallpaper, table top, furniture, storage cabinet, personal care products, collection box' utensils, medical devices, vinyl products, latex products, disposable gloves Electronic supplies, computers, keyboards, mobile phones, portable pagers, personal digital assistants, telephone 'computers, handheld electronics, etc.): paints and pigments; ceramic or composite surfaces (eg sinks, bathtubs, showers, toilets, medical Equipment or implants; wood (floor furniture, door and window trim, fine furniture, other building materials 22 201000010 materials); synthetic or natural rock (mixed soil, floor, table top, monument, building) Materials such as stone building materials or grouts; metal (kitchen solitary, medical equipment, cooking surfaces, door handles, table tops, public health industrial machinery, food, cosmetics or medical equipment, water storage tanks, piping And other similar items. The above antibacterial agents are particularly suitable for use in medical industry instruments or devices, whether disposable or reusable, such as scalpels, needles, scissors and other supplies for invasive surgery, treatment or diagnostic procedures. Implantable ❹ medical devices, including artificial blood vessels, catheters, and others to remove or transport fluids to Human equipment, artificial heart, artificial kidney, plastic surgery needle, sheet and implant; catheter and other types of tubes (including urinary and bile ducts, endotracheal tubes, insertable central venous tubes, catheters, washes) Renal catheter, long-term central venous catheter, peripheral venous catheter, short-term central venous catheter, arterial catheter, pulmonary tube, Swan-Ganz catheter, urinary catheter, peritoneal catheter) urinary equipment (including long-term urinary instruments, urinary instruments, Artificial urethral sphincter, urethral dilator), shunt (including ventricular or arterial venous shunt); prosthesis (including breast, artificial penis, artificial grafted blood vessel, heart valve, artificial joint, artificial throat, ear implant Infusion), blood catheter section, bypass catheter, cerebral edema shunt, pacemaker and implantable electric shock, medical equipment, medical gear worn or carried by personnel or set by the medical system, tubes used for respiratory therapy and Jars (including oxygen, dissolved drugs in the sprayer, anesthetic), gloves, work skirts and masks, medical or Equipment for the hand or with a cable, 23201000010 heart valves, hip implants, dentures, crowns, fixture, dental implants, and dental drill equipment. Reagents can also be used in the food processing industry (eg canning equipment for milk, cheese and meat processing equipment), packaging equipment, plastic curtains, conveyor belt materials, visceral equipment, and stainless steel surfaces. Water treatment uses include water cooling towers, water heaters, water delivery pipes, public water storage towers, private wells, and drip irrigation systems. The reagents can also be used for air filtration and treatment, such as air conditioning systems, air purifiers, air ducts, heating units, etc. General Procedure The decylated PVP quaternary salt was prepared according to the following procedure. The materials used included poly(4-vinylpyridine) (42% methanol-based solution, REILLINETM 410, MW 20,000, manufactured by Rei 1 ly Indus, Inc., Annapur, India); 3-chloropropane Burned trioxane zebra (CAS 2530-87-2, KBM-703, manufactured by Shin-Etsu Chemical Co., Ltd., Tokyo, Japan); 1-chlorobutane (CAS 109-69-3, by Acros, Belgium)

Made by Organics); propylene chloride (CAS 107-05-1, manufactured by Ferak Chemical Company, Berlin, Germany); 1-bromooctane (CAS 118-83-1, manufactured by Acros Organics); 1-bromo (CAS 629-04-9, manufactured by Acros Organics); gasified benzene (CAS 100-44-7); ethylbenzene chloride (CAS 26968-58-1), including a ratio of 70:30 And adjacent foods; and methanol (anhydrous). 24 201000010 Poly (4 bite) diluted with methanol to reduce viscosity, making it easy to handle. The amount of molecules is dehydrated to remove residual traces of water. The solid of pvp is rounded up to . It should be noted that the dish linetmi 〇 ( (4 口 疋 疋 疋 疋 疋 疋 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造It is to make the water as little as possible. The dehydrated poly (4-ethylene π ratio bite) (4 〇 millimol of ethylene t monomer repeating unit), 3 〇 -36 胄 Mohr (four) (C4_ c〇 And Η Mix a mixture of mMmol and OM-m 3-chloro(tetra)-oxypropan. Pour into a 5ml-WheatQn glass clear bottle, seal with rubber stopper and cover, then heat at 95-lG (TG hot oil) 12 hours. The reaction mixture changed from two phases to a homogeneous solution during the reaction, and the far infrared (ir) peak was shifted from 1600 cm-ι (pyridine ring C=N elongation bond) to 164 〇(10)-1 (in four stages). After the reaction, % is the completion of the reaction. The obtained product was immediately dissolved in water to form an amber clear solution. 实施 Example Dehydrated REILLINETM 410 poly(4-vinylpyridine) (21.0 g, 40 mmol), 1 - gas butane (32 g, 33 〇 mM), KBM-703 3-propane propane trimethoxy decane (1.2 g, 6.0 mmol) and 9.0 g of sterol The mixture was poured into a 5 ml ml clear glass bottle, sealed and allowed to react at 95 C for 12 hours. The reaction mixture was initially a two phase liquid, but then became homogeneously mixed 25 201000010 upon completion of the reaction. The quaternary polymer is characterized by an IR spectrometer using KBr pellets, showing that the wave temple is moved from 1598 cm_1 (π to ° ring ON) to 1641 cm-1 (after the quaternization reaction). The product is immediately soluble in water. A light orange clear solution is formed. Examples 2 to 10

The experimental procedures for each of Examples 2 to 10 were the same as in Example 1, except that 1-chlorobutane (1-C1C4) used in Example 1 was respectively subjected to 1-bromoheptane in Example 2 (1). -BrC?) substituted; Example 3 was replaced by 1-bromooctane (1-BrC〇; Example 4 was replaced by chlorinated benzene (Bz C1); Example 5 was gasified ethylbenzene (E Bz Cl) is substituted; in Example 6, it is substituted by propylene chloride (Ally C1); in Example 7, it is substituted by vaporized nonylbenzene (MBzCl); and in Example 8, it is substituted by 1-chlorobutane and gasified benzene; In Example 9, it was substituted with 1-hexane butane and ethyl chloride; and in Example 10, 1-butane and methylbenzene were substituted. The composition of the reaction mixture in each example is shown in Table 1 a. Show.

Table la. Transacted reactants (mmolol) Example Ally 1-Cl Bz E Bz 1-BrC 1-Br M Bz KBM-70 PVP Cl c4 Cl Cl 8 Ct Cl 3 1 40 — 33 6 2 40 36 — 2 26 201000010

Comparative example

The procedures of the following comparative examples are substantially the same as those of the above examples, except that KBM-703 3~chloropropane tridecyloxydecane is not used, and REILLINETM 410 poly(4-vinylpyridinium) is not directly dehydrated. use. The composition of the reaction mixture in the comparative examples is as described herein. Table lb. Example reactants (mimo) Ally 1-C1 Bz E Bz HBr 1-Br M Bz PVP Cl C4 Cl Cl Cs Ct Cl Example 1 non-decane 40 — 37.4 — — — 27 201000010 Analogs The non-decane analog of Example 2 40 30 - the non-decane analog of Example 3 40 30 - the non-decane analog of Example 4 - 36 - - - - -矽Calc Analog 40 — — 24 — — — — The non-decane analog of Example 6 40 30 The non-decane analog of Example 7 40 37 The non-decane analog of Example 8 — 17.5 17. 5 — — — — The non-decane analog of Example 9 40 — 17.5 — 17.5 — — — The non-decane analog of Example 10 — 17.5 17.5 28 201000010 Antibacterial test for the antibacterial activity of the immobilized antibacterial agent The procedure is based on the japan industrial standard (JIS) Z2801 (antibacterial object, antibacterial measurement ί fruit 'established in December 20, 2000) and the standard test method of activity Antibacterial antibacterial agent, the condition after the J 4 be modular. Test solution ^ In order to ensure the completion of the A" solution, 〇·5g of acetic acid and 2 J of ... are stirred vigorously. The resulting antibacterial solution was drowned. The solution was hydrolyzed under the chamber to form a clear solution which was used to prepare Example 2 to the temple for more than two weeks. A similar method can be used to provide a solution of the fourth grade product. The aqueous solution was added in the form of a solution. The quaternary product liquid obtained in Example 1 was used. 20% by weight, the tongue is not isolated and purified, that is, one water is dissolved in water, and the solution having the concentration of ^ 5 ^ is added to 100 ml of distillation and vigorously stirred to put an antibacterial solution of π^ °. The resulting antibacterial solution was visualized using a microscope test slide, the German Menz mouth (SuperFrost® Microscope surface, manufactured by Microscope Glass Tester), as a solution for testing the tantalum substrate. In the chamber, the peak is rinsed, then immersed in the above, and placed in 100. (:Oven; After setting for 30 minutes, the glass was dried from the solution for 3 minutes. This step was repeated three times. 29 201000010 According to the following JIS L 0217 (Care Labeling 〇f Textile

Goods) Standard procedure for preparing fabrics. The fabric used was 1% woven (undyed) knitted natural white cotton cloth sterilized with 〇·1% Tween-20 solution and autoclave before microbial cultivation. After the test specification was tested in JIS L 1902 (antibacterial activity and efficacy on fabric products), the test results were compared with the control group, and the percentage of bacterial flora reduction was used as the fourth-grade product obtained in Example 1-1. Quantification of the surface antibacterial activity of beta. In the step, the concentration of 1 〇 microliter of the bacteria is adjusted to 1-5 X 105 cells/ml (according to JIS l 1902, step 8.1.2), the inoculum is sterilized using a micropipette that has been sterilized. Already / Xiao Wei's "glass on the glass. The test piece was lightly covered with the already sterilized thin glass piece and cultured at 37 ° C for 18 hours. According to step 10.1.3 of jis L 1902, the number of bacterial flora was counted after each test piece was washed with 2 ml of ice physiological saline. When the growth value F is greater than 丨.5, the test is judged to be valid. If the growth value is less than 1.5, the result is discarded and the new process is repeated. The bacterial strains tested included aureus (ATCC 29737) and Escherichia coli (ATCC 10536). The antibacterial activity of the treated microscopy glass after the flushing cycles 1, 2 and 3 (the anti-test results are shown in Table 2. As shown by the data, the quaternary products exhibit good antibacterial activity and durability, chlorinated benzene The derivative exhibits particularly high antibacterial activity and durability. 30 201000010 Table 2. Reduction of the experimental bacterium cluster (%) on the glass surface Cleaning cycle 1 Cleaning cycle 2 Cleaning cycle 3 Example 1 (1-C1C4) 97.25 96.91 71.78 Non-decane of Example 1 94.3 54.5 - Example 2 (1-BrO) 80.9 73.74 78. 1 Non-methane derivative of Example 2 98.7 14.3 ___ Example 3 (l-BrCs) 82.9 63.8 70.16 Example 3 Non-decane analog 92.5 6.0 ___ Example 4 (Bz C1) 99.45 97.42 91.29 Non-decane analog of Example 4 90.75 58 ___ Example 5 (E Bz C1) 98.75 92 - Example 5 is similar to non-decane 95.5 74.5 ___ Example 6 (Ally C1) 99.3 97.96 — 31 201000010 Non-decane analog of Example 6 99.85 75.77 ___ Example 8 (1-C1C4 + Bz Cl) 99.7 80.44 ___ Example 8 is similar to non-methane 99.85 30.07 ___ Example 9 (1-C1C4 + E Bz Cl) 99.99 94. 6 ___ Non-decane analog of Example 9 89.19 28.76

The results of the antibacterial activity test results of the treated cotton fabrics after the washing cycles 1, 2 and 3 are shown in Table 3. As shown by the data, each of the four grades exhibited good antibacterial activity and Q durability. The durability of the antimicrobial coating is quite two even during repeated rinse cycles. ^__3. Experiment 5! Reduction of flora (%) on cotton fabrics 32 201000010 Wash cycle 0 Wash cycle 10 Wash cycle 20 Example 1 (1-C1C4) 96.53 99.8 91.33 Example 1 non-decane analog 99.92 99. 58 98.2 Example 4 (Bz C1) 97.64 99. 5 98.09 Non-decane analog of Example 4 93.85 99.3 97.32 Non-methane derivative of Example 5 99.996 ___ 99. 996 Example 6 is similar to non-decane 99. 978 一 一 99.997 Non-decane analog of Example 7 99.971 ___ 99.997 Non-methane derivative of Example 8 99. 949 ___ 99. 964 Example 10 non-decane analog 99. 947 ___ 99 856 The antibacterial activity of the treated cotton fabric against ^ c σ / i 33 201000010 was also tested after repeated rinse cycles. As shown in the data in Table 4, after the repeated weigh cycle, the product of the fourth grade in the cotton material μ is used. ^Excellent antibacterial activity and resistance on the fabric. 4. Experiment----- E. Col cleaning cycle 0 ~~--- cleaning cycle 10 3) on the cotton cleaning cycle 20 ------ Exhaust cleaning cycle 30 ~----- S less case cleaning cycle 50 Example 1 U-C1C4) Non-methane analog 98.94 99.39 99. 11 98. 09 96. 93 The data in Table 5 shows 'in a single rinse After cycling, the glass surface treated with the selected quaternary product exhibited good antibacterial activity against E coli. Table 5 Reduction of Experimental Footnote Cluster (%) on Glass Surface Cleaning Cycle 1 Example 1 (1-C1C4) 97.7 Non-Methane Analogue 50 of Example 1 Example 4 (Bz C1) 98.8 Example 4 Non-methane is similar to 85.4 34 201000010. Example 5 (E Bz C1) 99.6 Non-decane analog of Example 5 99.6 The above table also provides a non-decane counterpart of the quaternary product of the examples (non-曱) Data for decane analogs). For non-ruthenium use (such as cotton fiber, synthetic fiber or other natural fiber), although not as fast as the decane product, it still exhibits satisfactory antibacterial activity and durability. The polymerizable bacterial composition of the preferred embodiment can be covalently bonded to the surface of the enamel material through a mercaptoalkyl group incorporated into its polymer backbone, or can be firmly attached to natural fibers (such as cotton) and synthetic fibers ( For example, T/C, a synthetic/natural blend of poly(ethylene terephthalate) under the trade name DACRON® and 35/65 in cotton, and long chains without the use of a decyl group Tolerate multiple physical cleanings without losing the physical interaction of antibacterial effects. In contrast, short-chain, monomeric analogs of benzalkonium chloride (Example 8) are not resistant to cleaning. The long-term antibacterial effect of the fungal non-smoldering analogs of the examples on fabrics is one of the most surprising features. For non-decylated PVP quaternary salts for both fabrics including natural and synthetic fibers. Just like the methylated PVP quaternary salt, it can provide the advantages of cost saving and easy to use. PVP quaternary salts of aralkyl compounds, such as chlorinated stupid, vaporized nonylbenzene, and chlorine Chemical Base benzene is an effective antibacterial agent. Both single and mixed forms are effective antibacterial forms. Higher degree of quaternization reaction, the stronger the polarity of PVp quaternary salt, is therefore beneficial to water solubility; however, in fabric use In the case where the PVP quaternary salt is attached to the porous surface of the fiber, its water solubility does not have any negative impact on the washability. Tables 6 and 7 provide information on the non-metallurgical analog used on τ/c. ❹ Anti-Of <h and Z. Service (10)/This data on antimicrobial activity. Tables 8 and 9 provide data on the anti-囷 activity of the non-methane analogs used on cotton fabrics against $ and /. Each of the non-decane analogs tested exhibited excellent anti-folding activity after repeated washing cycles (please refer to the data shown in Table 6, Table 7, and Table 8). Table 9 is based on the test method (European Pharmacopoeia test) Methodology' provides the difference in the number of microbial communities in the treated, untreated, and untreated fibers (control group) at intervals of 6, 24, and 48 hours. Table 6 Experiments £ Flora (%) at T/C Reduction on the cleaning cycle 0 clear Cycle 20 The non-methane of Example 4 is similar to 99. 979 99.982 36 201000010 ❹ Ο Table 7 Experimental K. pneumoniae ATCC 4352 Drop plexus (%) reduction on τ/C Wash cycle 0 Wash cycle 10 Example 1 Formane analog 99.997 99.988 Non-methane analog of Example 4-----------1 99. 998 99. 998 Example 9 Non-decane analog 99.999 99. 74 Chlorination Stupid Ammonium Ammonium - _ 99.999 80.9 Table 8 ~---------- Experimental S. aureus ATCC 29737 flora (%) on cotton fabric reduction L. -------- --* Wash cycle 0 Wash cycle 20 37 201000010 Non-methane analog of Example 4 99.98 99.98 Non-decane analog of Example 8 99.99 - 99-74 Benzolammonium chloride 99. 99 80.9 9 Experimental ATCC 2785 P. aeruginosa 3 囷 (%) reduction on cotton fabric 0 Hour 6 Hour 24 Hour 48 Hour Example 4 96.465 99. 977 99. 997 99.996 Preferred embodiment of the functionalization reagent to Gram - positive bacteria (eg ai/rei/s) and Gram-negative bacteria (eg Escherichia Coli, Pseudomonas aeruginosa, both Antibacterial activity. It is especially suitable for the protection of tantalum materials, cellulosic materials, keratinous materials and collagen materials such as fabrics, leather, wood, glass, ceramics, rock and other building materials. Other types of surfaces, such as metal surfaces, polymeric surfaces and similar surfaces, can also be rendered antimicrobial by coating a suitable intermediate layer or by subjecting the surface to an intermediate functionalization reaction. 38 201000010 The cotton fiber treated with the functionalizing agent of the preferred embodiment exhibits excellent durability regardless of whether it has a carbaryl oxime or not. The treated fibers are able to withstand the washing cycle of the washing machine and can be used as an antibacterial coating for close-fitting clothing such as socks and underwear. References used herein are hereby incorporated by reference. To the extent that the disclosure, patent, or patent application of the present invention is incorporated by reference in its entirety, the present disclosure is intended to waive and/or replace the contradictions. ❹ “Inclusion” as used herein refers to the inclusion, inclusion, or characteristic of synonymy, as an open or blocked interpretation, and does not exclude additional, unmentioned elements or method steps. All quantities indicating the ingredients, reaction conditions, and numbers used in the specification and the scope of the patent application should be understood to extend the interpretation in all instances. Therefore, unless stated to be inconsistent, the numbers stated in the specification and claims are approximations and may vary depending on the characteristics to be obtained in accordance with the invention. At least without deliberately limiting the equivalence of the patent application, each number should be a substantial number of bits and is generally known. The above description discloses some of the methods and materials of the present invention. The present invention allows for equivalent changes to methods and materials, as well as manufacturing methods and equipment. This change will be readily apparent to those skilled in the art from this disclosure. Therefore, the above description is only a preferred embodiment of the present invention, and thus is not intended to limit the scope of the invention. Therefore, the equivalent structural changes of the present invention and the contents of the drawings are the same. It is included in the scope of the present invention and is combined with Chen Ming. [Simple description of the diagram] None [Main component symbol description]

Claims (1)

201000010, the scope of application for patents: 1. A polymeric material with antibacterial effect, including a repeating unit: -D- η Wherein R is a substituted or unsubstituted phenyl group, 1 is a Ci (alkyl chain; D is a Cl-6 alkyl chain; χ is a dentate, and n is at least 2. 2, as in the case of the patent (4) A polymeric material having an antibacterial effect, wherein R is a phenyl group. 3. A polymeric material having an anti-S effect as claimed in claim 1 wherein X is selected from the group consisting of chlorine and bromine. A polymeric material having an anti-g effect according to item 1, wherein A is selected from the group consisting of methylene and ethylene. A polymeric material having an antibacterial effect as claimed in claim 1 Where D is a building. 41 201〇〇0〇lΟ A polymeric material with an antibacterial effect, as in the scope of the patent application, wherein R is replaced by _ (E)m-Si(-〇-Alk)3 a phenyl group, wherein each Aik is a Cl_e alkyl group, and E is a hydrogen-based divalent carbon group (hydrocarbyi) containing m atoms of rabbits, m is from 0 to 12. ',, 7, and as claimed The polymer material having the anti-g effect of the sixth item of the range 'where the - (m(-〇-αιι〇3 is a para-substituent on the phenyl group) ' Each of Aik is a f-group and _(E)p is a lower alkylene chain. 8 . A polymeric material having an antibacterial effect according to item 7 of the claim range, wherein E 4- has The group of the formula _CH2_ph_CH2_CH2- wherein Ph is a phenyl group. ^ 9, as for the material of the material of the 丨 围 具有 具有 具有 其中 其中 其中 其中 其中 其中 η η η η η η η η η η η η η η η η η η η η a method for preparing a polymeric material having an anti-g effect, the method comprising: mixing a hydrogen-based divalent carbon-based chloride with a poly(4-core (4) to form a one-pot, to obtain an antibacterial The nature of the stone is burned to the fourth grade salt. 42 201000010 1. The method of claim 10, which further includes the chlorine base (four) and the hydrogen-based divalent carbon group and poly (4-ethylene t) The first reaction is as follows: 2. For the method of the U, the chlorinated decane is γ-chloropropane trimethoxy decane. 3. The method of claim 1G, wherein the hydrogen The chemical formula of the divalent carbon-based chloride is CnI12n+i_x, where η is i to 18 and X is chlorine or bromine. The method of the first aspect, wherein the hydrogen-based divalent carbon-based vapor is selected from the group consisting of chlorobutane, hydrazine-bromoheptane, bromooctane, chlorinated benzene, ethyl chloride, and propylene. 5. The group of constituents 5. The method of claim 10, wherein the poly(4-vinylpyridine) has a molecular weight of from about 10,000 MW to about 16 Å, and is lagging. 6. As claimed in claim 10 The method wherein the antimicrobial polymeric material is at least 50% quaternized. 7. The method of claim 1, further comprising the step of applying a beta-alkaline salt having an antibacterial property to the surface of an article to thereby impart an antibacterial effect to the surface of the article. 43 8 >^〇1〇〇〇〇l〇 If you apply for the method of item 10 of the patent scope, then from none, the surface of the item is the surface of the cotton fiber. - a surface resistant to bacterial growth' wherein the surface comprises a polymeric material having an antibacterial effect of the repeating unit of formula 1: R formula 1 /, R is a substituted or unsubstituted phenyl group, · A hospital base chain; D A 〇 , , Ci-6 yard base chain; χ is halogen, and n 2 ° 2 〇, as claimed in the scope of the 19th fiber surface. The surface of the item 'where the surface is cotton 201000010 VII. Designated representative figure: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: