WO2016123806A1 - 一种反应性抗菌防污化合物及其制备方法 - Google Patents

一种反应性抗菌防污化合物及其制备方法 Download PDF

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Publication number
WO2016123806A1
WO2016123806A1 PCT/CN2015/072439 CN2015072439W WO2016123806A1 WO 2016123806 A1 WO2016123806 A1 WO 2016123806A1 CN 2015072439 W CN2015072439 W CN 2015072439W WO 2016123806 A1 WO2016123806 A1 WO 2016123806A1
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Prior art keywords
group
diisocyanate
integer
tertiary amine
compound according
Prior art date
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PCT/CN2015/072439
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English (en)
French (fr)
Inventor
陈仕国
朱兴利
陈予想
陈少军
戈早川
杨海朋
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Shenzhen University
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Shenzhen University
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Priority to PCT/CN2015/072439 priority Critical patent/WO2016123806A1/zh
Priority to US15/549,162 priority patent/US10368544B2/en
Priority to CN201580001140.3A priority patent/CN105531258B/zh
Priority to PCT/CN2015/090059 priority patent/WO2016123987A1/zh
Publication of WO2016123806A1 publication Critical patent/WO2016123806A1/zh
Anticipated expiration legal-status Critical
Priority to US16/232,392 priority patent/US10609927B2/en
Priority to US16/804,100 priority patent/US11044908B2/en
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
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    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
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    • C07C271/06—Esters of carbamic acids
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    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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Definitions

  • the invention belongs to the technical field of organic synthesis, in particular to a reactive antibacterial antifouling compound and a preparation method thereof
  • Bacterial or fungal infections have become a worldwide problem that threatens human health and is of global health concern. It is one of the important means to solve bacterial or fungal infections by imparting antibacterial properties to the surface of materials or products to prevent bacteria or fungi from growing or reproducing on their surface, or even killing bacteria or fungi on the surface.
  • international antibacterial materials can be divided into four categories: (1) inorganic antibacterial agents, such as nano titanium dioxide, nano silver, nano copper, and their ions.
  • antibacterial agents such as quaternary ammonium salts, thiazoles, etc.
  • polymeric antibacterial agents such as high molecular quaternary ammonium salts
  • natural and modified antibacterial agents such as chitosan, sorbic acid.
  • antibacterial agents such as nanosilver, nanocopper and their ions or other antibacterial agents
  • a coating containing antibacterial agents such as nanosilver, nanocopper and their ions or other antibacterial agents
  • antibacterial agents such as nanosilver, nanocopper and their ions or other antibacterial agents
  • heavy metal ions relying on it to slowly release metal ions into the surrounding environment for antibacterial or bactericidal purposes, however, as the use time prolongs, its antibacterial activity gradually decreases until it eventually loses its antibacterial activity, and may also induce microbial variation. Increase the probability of developing resistance.
  • the harmfulness of nanomaterials has gradually been recognized and paid attention by humans.
  • Organic antibacterial agents and natural antibacterial agents have poor heat resistance and often limit their use.
  • the polymer quaternary ammonium salt antibacterial agent can overcome the shortcomings of small molecule antibacterial agent such as volatilization, difficult processing, poor chemical stability, and the like, and has excellent antibacterial activity and is not easy to penetrate into human skin, and thus has attracted people's attention.
  • small molecule antibacterial agent such as volatilization, difficult processing, poor chemical stability, and the like
  • methacrylate polymer quaternary ammonium salt antibacterial agents have been prepared by Revo & functional polymers (2007, 67: 355-366), and the MIC is 1.56-20 mg/mL.
  • Polymer antibacterial agents are mainly polymer quaternary ammonium salts and polymer halides.
  • Amine antibacterial agents are not ideal for thermal stability, and in order to obtain good antibacterial agents, antibacterial agents are generally required to be water-soluble, and these unimmobilized polymeric antibacterial agents are also lost, resulting in lack of durability of antibacterial activity. It will also put some pressure on the surrounding environment.
  • Lowe et al. J. Appl. Polym. Sci., 2006, 101: 1036-1041] prepared a series of polymer betaine antibacterial agents with a minimum inhibitory concentration (MIC) of 1125-2000 ug/mL, which is antibacterial.
  • MIC minimum inhibitory concentration
  • the release of the antibacterial agent has at least two disadvantages: (1) the implanted antibacterial agent has a time-release effect, lacks long-lasting antibacterial activity; and (2) the released antibacterial agent puts pressure on the environment. These factors cannot be ignored, and the development and preparation of green non-release antibacterial agents is the general trend. Fixing the antibacterially active group with a chemical bond to the surface of the material or article imparts long-lasting antibacterial activity to the material or article without causing environmental pollution.
  • the betaine-type antibacterial and antifouling compound containing a terminal isocyanate group provided by the invention has the general formula I or II:
  • R1 represents OCN-L-NHCOO-R' or represents OCN-L-NHCONH-R';
  • L is a residue remaining after the reaction of the diisocyanate compound (Reactant B) with an amino group or a hydroxyl group;
  • R' -( CH 2 ) m , wherein m is a positive integer greater than or equal to 1, m is preferably 1, 2, 3, 4, 5 or 6; or
  • R' -(CH 2 ) n O(CH 2 ) y wherein n is greater than Or a positive integer equal to 1, n is preferably 1, 2, 3, 4, 5 or 6; y is a positive integer greater than or equal to 1, n is preferably 1, 2, 3, 4, 5 or 6; or
  • R 4 represents -(CH 2 ) q , wherein q is a positive integer greater than or equal to 1, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17;
  • R 5 represents a substituent on the pyridine ring, preferably a group such as -CH 3 , -CH 2 CH 3 , -F, -Cl, -Br, -OMe, -CN, -NO 2 or the like, and may also be one of a combination of multiple groups;
  • A represents -COO or -SO 3 .
  • Another object of the present invention is to provide a method for preparing the above antibacterial antifouling compound, which has simple synthesis process, easy control of conditions, high yield, and easy industrial production.
  • the object is achieved by a method for preparing an antibacterial antifouling compound, the steps of which are:
  • the above white precipitated substance is filtered or centrifuged to obtain a terminal isocyanate-based betaine-type antibacterial antifouling compound, that is, the target product is obtained.
  • the above reactant A is one selected from the group consisting of propane sultone, butyrolactone, ⁇ -propionolactone, X(CH 2 ) v SO 3 - , or X(CH 2 ) v CO 2 -
  • R 4 represents -(CH 2 ) q , wherein q is a positive integer greater than or equal to 1, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17;
  • A represents -COO, or -SO 3 .
  • a typical synthetic route map for the above preparation method is:
  • the preparation method of the intermediate product containing the hydroxyl terminated betaine is as follows: the tertiary hydroxyl group-containing tertiary amine and the reactant A are stirred at a temperature of 10 to 80 ° C. The reaction is continued for 1 to 48 hours in the environment to obtain a white precipitated substance;
  • the above white precipitate is filtered or centrifuged to obtain an intermediate product containing a hydroxyl group-containing betaine compound.
  • the hydroxy-containing betaine prepared above and the reactant B are continuously reacted in the presence of a stirring and a catalyst C at a temperature of 10 to 80 ° C for 1 to 48 hours to obtain a white precipitated substance;
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, that is, a target product is obtained.
  • the tertiary amine containing a terminal isocyanate group is prepared by taking the reactant B, adding a tertiary hydroxyl group-terminated amine under stirring, and performing an addition reaction at a temperature of 10 to 90 ° C and the presence of the catalyst C.
  • the reaction time is 0.5 to 48 hours, that is, a tertiary amine having a terminal isocyanate group is obtained.
  • the reaction time is preferably 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 24 h, 48 h.
  • the tertiary isocyanate group-containing tertiary amine and the reactant A are continuously reacted for 1 to 48 hours under stirring at a temperature of 10 to 80 ° C to obtain a white precipitated substance, preferably a reaction time of 1 h, 2 h, 3 h, 4 h, 6 h. , 10h, 24h, 48h.
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, thereby obtaining a target product;
  • the above reactant A is selected from the group consisting of propane sultone, butyrolactone, ⁇ a propionic acid lactone, X(CH 2 ) v SO 3 - , or X(CH 2 ) v CO 2 - wherein X is Br, Cl or I, and v is a positive integer greater than or equal to 1.
  • the tertiary amine containing a terminal isocyanate group is prepared by taking the reactant B and adding a tertiary amino group-terminated amine under stirring, and performing an addition reaction at a temperature of 10 to 90 ° C for a reaction time of 0.5. ⁇ 48h, a tertiary amine containing a terminal isocyanate group is obtained.
  • the reaction time is preferably 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 24 h, 48 h.
  • the tertiary isocyanate group-containing tertiary amine and the reactant A are stirred at a temperature of 10 to 80 ° C.
  • the reaction in the environment is continued for 1 to 48 hours, and a white precipitated substance is obtained.
  • the reaction time is preferably 1 h, 2 h, 3 h, 4 h, 6 h, 10 h, 24 h, 48 h.
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, thereby obtaining a target product;
  • the above reactant A is selected from the group consisting of propane sultone, butyrolactone, ⁇ a propionic acid lactone, X(CH 2 ) v SO 3 - , or X(CH 2 ) v CO 2 - wherein X is Br, Cl or I, and v is a positive integer greater than or equal to 1.
  • a typical synthetic route map for the above preparation method is:
  • the preparation method of the intermediate product containing the hydroxyl terminated betaine is as follows: the tertiary hydroxyl group-containing tertiary amine and the reactant A are stirred at a temperature of 10 to 80 ° C. The reaction is continued for 1 to 48 hours in the environment to obtain a white precipitated substance;
  • the above white precipitate is filtered or centrifuged to obtain an intermediate product containing a hydroxyl group-containing betaine compound.
  • the hydroxy-containing betaine prepared above and the reactant B are continuously reacted in the presence of a stirring and a catalyst C at a temperature of 10 to 80 ° C for 1 to 48 hours to obtain a white precipitated substance;
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, that is, a target product is obtained.
  • the tertiary amine containing a terminal isocyanate group is prepared by taking the reactant B, adding a tertiary hydroxyl group-terminated amine under stirring, and performing an addition reaction at a temperature of 10 to 90 ° C and the presence of the catalyst C.
  • the reaction time is 0.5 to 48 hours, that is, a tertiary amine having a terminal isocyanate group is obtained.
  • the reaction time is preferably 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 24 h, 48 h.
  • the tertiary isocyanate group-containing tertiary amine and the reactant A are stirred at a temperature of 10 to 80 ° C.
  • the reaction in the environment is continued for 1 to 48 hours, and a white precipitated substance is obtained.
  • the reaction time is preferably 1 h, 2 h, 3 h, 4 h, 6 h, 10 h, 24 h, 48 h.
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, thereby obtaining a target product;
  • the above reactant A is selected from the group consisting of propane sultone, butyrolactone, ⁇ a propionic acid lactone, X(CH 2 ) v SO 3 - , or X(CH 2 ) v CO 2 - wherein X is Br, Cl or I, and v is a positive integer greater than or equal to 1.
  • the tertiary amine containing a terminal isocyanate group is prepared by taking the reactant B and adding a tertiary amino group-terminated amine under stirring, and performing an addition reaction at a temperature of 10 to 90 ° C for a reaction time of 0.5. ⁇ 48h, a tertiary amine containing a terminal isocyanate group is obtained.
  • the reaction time is preferably 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, 24 h, 48 h.
  • the tertiary isocyanate group-containing tertiary amine and the reactant A are continuously reacted for 1 to 48 hours under stirring at a temperature of 10 to 80 ° C to obtain a white precipitated substance, preferably a reaction time of 1 h, 2 h, 3 h, 4 h, 6 h. , 10h, 24h, 48h.
  • the above white precipitated substance is filtered or purified by centrifugation to obtain a betaine antibacterial antifouling compound containing a terminal isocyanate group, thereby obtaining a target product;
  • the above reactant A is selected from the group consisting of propane sultone, butyrolactone, ⁇ a propionic acid lactone, X(CH 2 ) v SO 3 - , or X(CH 2 ) v CO 2 - wherein X is Br, Cl or I, and v is a positive integer greater than or equal to 1.
  • the antibacterial compound has a reactive functional group, isocyanate, which can chemically bond with various material interfaces, thereby imparting long-lasting antibacterial activity to the material or product treated by the antibacterial compound and is strong. Hydrophilicity.
  • the preparation method has simple synthesis process, easy control of conditions, and easy industrialization, and provides convenience for its use in a wide range.
  • the antibacterial compound has the unique advantages of being resistant to acids, alkalis, salts, etc., especially low toxicity, chemical stability and thermal stability, and the surface of the product treated by the antibacterial compound can withstand various common disinfection techniques. Processing.
  • 1,3-PS 48.8g (dissolved in 400mL anhydrous THF), after the completion of the addition, the reaction is continued for 1h to obtain a white precipitate, which is purified by centrifugation several times to obtain a disulfonate type beet with isocyanate end groups.
  • Alkali antibacterial antifouling compound 48.8g (dissolved in 400mL anhydrous THF), after the completion of the addition, the reaction is continued for 1h to obtain a white precipitate, which is purified by centrifugation several times to obtain a disulfonate type beet with isocyanate end groups. Alkali antibacterial antifouling compound.
  • 1,3-PS 24.4g (dissolved in 400mL of anhydrous THF), after the completion of the addition, the reaction is continued for 1 hour to obtain a white precipitate, which is purified by centrifugation several times to obtain a pyridine carboxylic acid type having an isocyanate end group.
  • Betaine antibacterial antifouling compound dissolved in 400mL of anhydrous THF
  • the minimum inhibitory concentration (MIC) of the products of the above examples is shown in Table 1:
  • E. coli ATCC 25922
  • Staphylococcus aureus S. aureues, ATCC 6538
  • the product obtained in the above example was treated with a clean glass surface, and its antibacterial activity and long-lasting antibacterial activity were tested by colony counting method. The results are shown in Table 2.
  • toluene diisocyanate (TDI, 4-toluene diisocyanate, 2,6-toluene diisocyanate or a mixture of the two), diphenylmethane diisocyanate, may be selected in a substantial amount ( MDI), 1,5-naphthalene diisocyanate (NDI), tetramethyl diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), p-phenyl diisocyanate (PPDI), dimethylene phenyl diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethane diisocyanate (HMDI) in place of isophorone diisocyanate (IPDI); but also in a comparable amount of butane sultone, X (CH 2 ) v SO 3 Na or X(CH 2 ) v CO 2 Na
  • the antibacterial compound provided by the invention has an all-functional functional group - isocyanate, and the reactive group can be chemically bonded to a plurality of material interfaces to impart a long-lasting surface to the material or product treated by the reactive betaine antibacterial antifouling compound. Antibacterial and antifouling properties.
  • the preparation method of the compound is simple in process, easy to control and easy to industrialize, and it is convenient for use in a wide range.

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Abstract

提供一种具有通式(I)或(II)的异氰酸酯甜菜碱型抗菌防污化合物及其制备方法：其中，R 1代表OCN-L-NHCOO-R'或代表OCN-L-NHCONH-R'；L为二异氰酸酯化合物与羟基或氨基反应后留下的残基；R'＝-(CH 2) m，其中m为1-6之间任意一个整数；或R'＝-(CH 2) nO(CH 2) y其中n为1-6之间任意一个整数；y为1-6之间任意一个整数；或R'＝-(CH 2) mAr其中m为1-6之间任意一个整数；或R'＝-(CH 2) nO(CH 2) yAr其中n为1-6之间任意一个整数；y为1-6之间任意一个整数；其中Ar为芳基；R 2代表是-(CH 2) pCH 3，其中p为1-17之间任意一个整数；R 3代表是-(CH 2) pCH 3，其中p为1-17之间任意一个整数；R 4代表是-(CH 2) q，其中q为1-17之间任意一个整数；R 5代表是吡啶环上的取代基；A代表-COO或-SO 3。

Description

一种反应性抗菌防污化合物及其制备方法 技术领域
本发明属于有机合成技术领域，尤其涉及一种反应性抗菌防污化合物及其制备方法
背景技术
细菌或真菌感染已成为威胁人类健康并备受全球医疗卫生事业关注的世界性重要问题。赋予材料或制品表面抗菌性能，以阻止细菌或真菌在其表面生长或繁殖，甚至杀死表面的细菌或真菌，是解决细菌或真菌感染的重要手段之一。目前国际上的抗菌材料可以分为四大类：(1)无机抗菌剂，比如纳米二氧化钛，纳米银、纳米铜，以及它们的离子等。(2)有抗菌剂，例如季铵盐，噻唑类等；(3)高分子抗菌剂，例如高分子季铵盐；(4)天然及其改性抗菌剂：如壳聚糖，山梨酸。
赋予材料或制品表面抗菌性能最常用的是在其表面涂覆一层含抗菌剂(如纳米银、纳米铜及其它们的离子或者其他抗菌剂)的涂层，纳米银、纳米铜以及其他重金属以及重金属离子，依靠其缓慢释放金属离子到周围环境中而达到抑菌或杀菌目的，然而随着使用时间的延长，其抗菌活性逐渐降低，直至最终完全丧失其抗菌活性，同时还可能诱导微生物变异，增加产生耐药性的概率。另外，纳米材料的危害性也逐渐被人类所认识和关注。有机抗菌剂和天然抗菌剂其耐热性差，常常限制了其使用范围。高分子季铵盐抗菌剂可克服小分子抗菌剂的易挥发、难加工、化学稳定性差等缺点，且抗菌活性优良，不易渗透入人体皮肤，因而受到人们的关注。例如符若文课题组[Reactive & functional polymers，2007，67：355-366]制备了一系列甲基丙烯酸酯类高分子季铵盐抗菌剂，MIC为1.56-20mg/mL。聚合物抗菌剂主要还是聚合物季铵盐以及聚合物卤 胺抗菌剂，其热稳定性也不理想，而且，为了获得良好的抗菌剂，一般要求抗菌剂是水溶性的，这些未固定化的高分子抗菌剂也存在流失性而导致抗菌活性缺乏持久性，同样也会给周围环境造成一定的压力。如Lowe等人[J.Appl.Polym.Sci.，2006，101：1036-1041]制备了一系列聚合物甜菜碱抗菌剂，其最低抑菌浓度(MIC)为1125-2000ug/mL，为抗菌剂的开发提出了一种新的思路，但是其没有可以固定化的反应性官能团，避免不了其释放性流失的缺点。
这种释放性的抗菌剂至少有两个方面的不利因素：(1)植入的抗菌剂有释放的时效性，缺乏持久抗菌活性；(2)释放出来的抗菌剂给环境带来压力。这些因素是不容忽视的，开发和制备绿色的非释放性的抗菌剂是大势所趋的。将带有抗菌活性基团以化学键形式固定于材料或制品表面，可赋予材料或制品持久抗菌活性，而且也不致于对环境造成污染。Madkour[Langmuir，2009，25：1060-1067]以含卤硅烷与含羟基的表面反应，进一步采用原子转移自由基聚合的方法制备了快速抗菌的涂层，但是工艺复杂，条件苛刻，难以产业化。Saif[Langmuir，2009，25：377-379]制备了具有持久抗菌活性的有机硅季铵盐抗菌剂，以及早期DOW Coming公司研发的出来的DC-5700都属于这一类，但是季铵盐的抗菌剂的耐热性不好，从而限制了它的使用范围。陈仕国等人采用两步经典的化学反应制备了含有反应性硅氧烷基团的甜菜碱抗菌化合物[US8623843，ZL201010116533，CN201210377540]，并成功用于抗菌整理棉纺织品[ZL 201010106007]。但是反应性硅氧烷易于自缩合反应而丧失其反应活性，致使储存稳定性不佳，需要保存于异丙醇等溶剂中。
如何克服目前抗菌剂领域如以上所述存在的缺点，研究和开发一类新的可固定化的具有长效性的抗菌剂是人类社会发展的新要求。
发明内容
本发明的目的在于提供一种抗菌防污化合物，该化合物可以通过反应性官能团(异氰酸酯)以化学键合方式牢固地与多种材料或产品界面键合，获得持 久的抗菌活性和亲水性。
本发明所提供的含端异氰酸酯基的甜菜碱型抗菌防污化合物，具有通式I或II：
Figure PCTCN2015072439-appb-000001
其中，R1代表OCN-L-NHCOO-R′或代表OCN-L-NHCONH-R′；L为二异氰酸酯化合物(反应物B)与氨基或羟基反应后留下的残基；R′＝-(CH2)m，其中m为大于或等于1的正整数，m优选1，2，3，4，5或6；或R′＝-(CH2)nO(CH2)y其中n为大于或等于1的正整数，n优选1，2，3，4，5或6；y为大于或等于1的正整数，n优选1，2，3，4，5或6；或R′＝-(CH2)mAr，其中m为大于或等于1的正整数，m优选1，2，3，4，5或6；或R′＝-(CH2)nO(CH2)yAr其中n为大于或等于1的正整数，n优选1，2，3，4，5或6；y为大于或等于1的正整数，n优选1，2，3，4，5或6；其中Ar为芳基；
R2代表是-(CH2)pCH3，其中p＝0～17，优选0，1，2，3，4，5，6；
R3代表是-(CH2)pCH3，其中p＝0～17；优选0，1，2，3，4，5，6；
R4代表是-(CH2)q，其中q为大于或等于1的正整数，优选1，2，3，4，5，6，7，8，9，10，11，12，13，14，15，16，17；
R5代表是吡啶环上的取代基，优选-CH3，-CH2CH3，-F，-Cl，-Br，-OMe，-CN，-NO2等基团，也可为其中一个和多个基团的组合；
A代表-COO或-SO3。
上述通式(I)或(II)中，取代基R2与R3是相同的基团或不同的基团。
本发明的另一目的在于提供上述抗菌防污化合物的制备方法，其合成工艺简单，条件易控制，产率高，易于工业化生产。
该目的是这样实现的，一种抗菌防污化合物的制备方法，其步骤为：
制取含端异氰酸酯基的叔胺，并将该端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质；
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基甜菜碱型抗菌防污化合物，即制得目标产物。
上述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl其中，R1代表-(CH2)m，其中m为大于或等于1的正整数，m优选1，2，3，4，5或6；或R1＝(CH2)nO(CH2)y其中n为大于或等于1的正整数，n优选1，2，3，4，5或6；y为大于或等于1的正整数，n优选1，2，3，4，5或6；或R1＝-(CH2)mAr其中m为大于或等于1的正整数，m优选1，2，3，4，5或6；或R1＝(CH2)nO(CH2)yAr其中n为大于或等于1的正整数，n优选1，2，3，4，5或6；y为大于或等于1的正整数，n优选1，2，3，4，5或6；其中Ar为芳基；
R2代表是-(CH2)pCH3，其中p＝0～17，优选0，1，2，3，4，5，6；
R3代表是-(CH2)pCH3，其中p＝0～17；优选0，1，2，3，4，5，6；
R4代表是-(CH2)q，其中q为大于或等于1的正整数，优选1，2，3，4，5，6，7，8，9，10，11，12，13，14，15，16，17；
A代表-COO，或-SO3。
上述制备方法的典型合成路线图为：
Figure PCTCN2015072439-appb-000002
上述制备步骤中所述抗菌防污化合物的制备方法中，其中间产物含端羟基甜菜碱的制备方法步骤为：将含端羟基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质；
将上述白色沉淀物质过滤或离心分离纯化，得中间产物含端羟基的甜菜碱化合物。
将上述制取的含端羟基甜菜碱与反应物B在搅拌和催化剂C存在下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质；
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物。
Figure PCTCN2015072439-appb-000003
上述制备步骤中，其中含端异氰酸酯基的叔胺的制备方法为：取反应物B，并在搅拌下滴加端羟基的叔胺，在温度10～90℃和催化剂C存在下进行加成反应，反应时长0.5～48h，即得含端异氰酸酯基的叔胺。优选反应时间1h，2h，4h，6h，8h，10h，24h，48h。
将上述含端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质，优选反应时间1h，2h，3h，4h，6h，10h，24h，48h。
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物；上述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl或I，v为大于或等于1的正整数。
Figure PCTCN2015072439-appb-000004
上述制备步骤中，其中含端异氰酸酯基的叔胺的制备方法为：取反应物B，并在搅拌下滴加端氨基的叔胺，在温度10～90℃下进行加成反应，反应时长0.5～48h，即得含端异氰酸酯基的叔胺。优选反应时间1h，2h，4h，6h，8h，10h，24h，48h。
将上述含端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的 环境中持续反应1～48h，得白色的沉淀物质，优选反应时间1h，2h，3h，4h，6h，10h，24h，48h。
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物；上述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl或I，v为大于或等于1的正整数。上述制备方法的典型合成路线图为：
Figure PCTCN2015072439-appb-000005
上述制备步骤中所述抗菌防污化合物的制备方法中，其中间产物含端羟基甜菜碱的制备方法步骤为：将含端羟基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质；
将上述白色沉淀物质过滤或离心分离纯化，得中间产物含端羟基的甜菜碱化合物。
将上述制取的含端羟基甜菜碱与反应物B在搅拌和催化剂C存在下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质；
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物。
Figure PCTCN2015072439-appb-000006
上述制备步骤中，其中含端异氰酸酯基的叔胺的制备方法为：取反应物B，并在搅拌下滴加端羟基的叔胺，在温度10～90℃和催化剂C存在下进行加成反应，反应时长0.5～48h，即得含端异氰酸酯基的叔胺。优选反应时间1h，2h，4h，6h，8h，10h，24h，48h。
将上述含端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的 环境中持续反应1～48h，得白色的沉淀物质，优选反应时间1h，2h，3h，4h，6h，10h，24h，48h。
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物；上述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl或I，v为大于或等于1的正整数。
Figure PCTCN2015072439-appb-000007
上述制备步骤中，其中含端异氰酸酯基的叔胺的制备方法为：取反应物B，并在搅拌下滴加端氨基的叔胺，在温度10～90℃下进行加成反应，反应时长0.5～48h，即得含端异氰酸酯基的叔胺。优选反应时间1h，2h，4h，6h，8h，10h，24h，48h。
将上述含端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48h，得白色的沉淀物质，优选反应时间1h，2h，3h，4h，6h，10h，24h，48h。
将上述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物；上述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl或I，v为大于或等于1的正整数。
上述三种技术方案的优点在于：该抗菌化合物，具有反应性官能团——异氰酸酯，其可以与多种材料界面发生化学键合作用，从而赋予由抗菌化合物处理的材料或制品持久的抗菌活性以及很强的亲水性。同时，制备方法的合成工艺简单，条件容易控制，易于产业化，为它在广泛范围内使用提供了方便。另外，该抗菌化合物还具有耐酸、碱、盐等独特优点，尤其是毒性低、化学稳定性和热稳定性好，经该抗菌化合物处理的制品表面可以经受常用的各种消毒技 术处理。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二丁基二月桂酸锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g二甲基乙醇胺【HO CH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000008
以下简称1，3-PS】24.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得得带异氰酸酯端基的甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000009
实施例2
称取44.6g二苯甲烷二异氰酸酯(MDI)【MDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二丁基二月桂酸锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加20.6g二乙基乙醇胺【HO CH2CH2N(CH2CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000010
以下简称1，3-PS】24.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的磺酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000011
实施例3
称取44.6g六亚甲基二异氰酸酯【HDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的辛酸亚锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g N，N-二甲基乙醇胺【HO CH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，并向滤液中滴加93.2氯乙酸钠【ClCH2CO2Na】(溶于400mL无水THF中)，20℃温度下反应24h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的羧酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000012
实施例4
称取44.692，6-甲苯二异氰酸酯【TDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二月桂酸二丁基锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g二甲基乙醇胺【HO CH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，并向滤液中滴加14.4g的β-丙内酯【
Figure PCTCN2015072439-appb-000013
】(溶解于400mL丁酮中)，40℃温度下继续反应6h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的羧酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000014
实施例5
称取44.6g二环己基甲烷二异氰酸酯【HMDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二月桂酸二丁基锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g N，N-二甲基乙二胺【H2NCH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000015
以 下简称1，3-PS】24.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的磺酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000016
实施例6
称取44.6g佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二丁基二月桂酸锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g N，N-二甲基乙二胺【H2NCH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，并向滤液中滴加14.4g的β-丙内酯【
Figure PCTCN2015072439-appb-000017
】(溶解于400mL丁酮中)，40℃温度下继续反应6h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的羧酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000018
实施例7
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二月桂酸二丁基锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加37.4g 3，3′-亚胺基双(N，N-二甲基丙胺)【(CH3CH2)2CH2CH2NHCH2CH2N(CH2CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000019
以下简称1，3-PS】48.8g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的双磺酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000020
实施例8
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二月桂酸二丁基锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加21.8g 4-羟甲基吡啶，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000021
以下简称1，3-PS】24.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得带异氰酸酯端基的吡啶羧酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000022
实施例9
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的辛酸亚锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加24.4g 2，6-二甲基-4-氨基吡啶，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加丙磺酸内酯【
Figure PCTCN2015072439-appb-000023
以下简称1，3-PS】24.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得得带异氰酸酯端基的吡啶羧酸型甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000024
实施例10
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二丁基二月桂酸锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g二甲基乙醇胺【HO CH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加2-溴乙磺酸钠42.2g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得得带异氰酸酯端基的甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000025
实施例11
称取44.6g异佛尔酮二异氰酸酯【IPDI】加入到带有机械搅拌圆底烧瓶里，加入0.2ml的二丁基二月桂酸锡催化剂后，在搅拌和30℃温度下用滴液漏斗缓慢滴加17.8g二甲基乙醇胺【HO CH2CH2N(CH3)2】，滴加完毕后继续反应1h，并在此温度下继续搅拌反应12h，然后滴加4-溴丁酸钠37.4g(溶于400mL无水THF中)，滴加完毕后继续反应1h，得白色的沉淀，离心分离数次纯化，得得带异氰酸酯端基的甜菜碱抗菌防污化合物。
Figure PCTCN2015072439-appb-000026
上述实施例产品的最低抑菌浓度(MIC)如表1所示：
表1、实施例1-11的最低抑菌浓度(MIC，单位：μmol/mL)
Figure PCTCN2015072439-appb-000027
注：大肠杆菌(E.coli，ATCC 25922)和金黄色葡萄球菌(S.aureues，ATCC6538)
将上述实例所得产物处理洁净的玻璃表面，并采用菌落计数法测试其抗菌活性及持久抗菌活性，结果如表2所示。
表2、实施例1-11的抗菌剂改性玻璃表面的持久抗菌活性分析(平板计数法)
Figure PCTCN2015072439-appb-000028
Figure PCTCN2015072439-appb-000029
在本发明其它优选的实施例中，可以选择以相当物质的量的甲苯二异氰酸酯(TDI，含4-甲苯二异氰酸酯，2，6-甲苯二异氰酸酯或二者混合物)，二苯甲烷二异氰酸酯(MDI)、1，5-萘二异氰酸酯(NDI)、四甲基二异氰酸酯(TMXDI)、六亚甲基二异氰酸酯(HDI)、对苯基二异氰酸酯(PPDI)、二亚甲基苯基二异氰酸酯(XDI)，甲基环己基二异氰酸酯(HTDI)、二环己基甲烷二异氰酸酯(HMDI)代替异佛尔酮二异氰酸酯(IPDI)；也可选择以相当物质的量的丁磺酸内酯、X(CH2)vSO3Na或X(CH2)vCO2Na(其中X是Br、Cl或I；v为大于或等于1的正整数)代替丙磺酸内酯、β-丙内酯、ClCH2CO2Na或ClCH2CH2SO3Na代替1，3-PS。
本发明所提供的抗菌化合物，具有应性官能团——异氰酸酯，该反应性基团可以与多种材料界面发生化学键合作用，从而赋予由反应性甜菜碱抗菌防污化合物处理的材料或制品表面持久的抗菌防污性。同时，该化合物的制备方法工艺简单，条件容易控制易于产业化，为它在广泛范围内使用提供了方便。
以上所述的仅是本发明的几种实施方式，其描述较为具体和详细，并不能因此而理解为对本发明专利范围的限制，应当指出，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出其他若干变形和改进，这些都属于本发明的保护范围。

Claims (12)

  1. 一种反应性抗菌防污化合物，其特征在于，其具有通式(I)或(II)的含端异氰酸酯基：
    Figure PCTCN2015072439-appb-100001
    其中，R1代表OCN-L-NHCOO-R′或代表OCN-L-NHCONH-R′；L为二异氰酸酯化合物与羟基或氨基反应后留下的残基；R′＝-(CH2)m，其中m为1-6之间任意一个整数；或R′＝-(CH2)nO(CH2)y其中n为1-6之间任意一个整数；y为1-6之间任意一个整数；或R′＝-(CH2)mAr其中m为1-6之间任意一个整数；或R′＝-(CH2)nO(CH2)yAr其中n为1-6之间任意一个整数；y为1-6之间任意一个整数；其中Ar为芳基；
    R2代表是-(CH2)pCH3，其中p为1-17之间任意一个整数；
    R3代表是-(CH2)pCH3，其中p为1-17之间任意一个整数；
    R4代表是-(CH2)q，其中q为1-17之间任意一个整数；
    R5代表是吡啶环上的取代基，优选-CH3，-CH2CH3，-F，-Cl，-Br，-OMe，-CN，-NO2等基团，也可为其中一个和多个基团的组合；
    A代表-COO或-SO3。
  2. 如权利要求1所述的反应性抗菌防污化合物，其特征在于：所述通式(I)～(II)中，取代基R2与R3是相同的基团或不同的基团。
  3. 如权利要求1所述的反应性抗菌防污化合物，其特征在于：R5选自-CH3、-CH2CH3、-F、-Cl、-Br、-OMe，、-CN、-NO2基团其中一个或多个基团的组合。
  4. 一种如权利要求1至3任意一项所述反应性抗菌防污化合物的制备方法，其特征在于，包括如下步骤：
    制取含端异氰酸酯基的叔胺，并将该端异氰酸酯基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48小时，得白色的沉淀物质；
    将所述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物；所述反应物A是选自丙磺酸内酯、丁磺酸内酯、β-丙酸内酯、X(CH2)vSO3 -、或X(CH2)vCO2 -中的一种，其中X是Br、Cl或I，v为大于或等于1的正整数。
  5. 根据权利要求4所述的反应性抗菌防污化合物的制备方法，其特征在于，所述含端异氰酸酯基的叔胺的制备方法为：取反应物B，并在搅拌下滴加端羟基的叔胺，在温度10～90℃和催化剂C存在下进行加成反应，反应时长0.5～48小时，即得所述含端异氰酸酯基的叔胺；或取反应物B，并在搅拌下滴加端氨基的叔胺，在温度10～90℃和催化剂C存在下进行加成反应，反应时长0.5～48小时，即得所述含端异氰酸酯基的叔胺。
  6. 一种如权利要求1至3任意一项所述反应性抗菌防污化合物的制备方法，其特征在于，包括如下步骤：
    制取含端氨基甜菜碱或端羟基甜菜碱，并将所述端羟基甜菜碱或端氨基甜菜碱与反应物B在搅拌下、在温度10～80℃的环境中持续反应1～48小时，得白色的沉淀物质；
    将所述白色沉淀物质过滤或离心分离纯化，得含端异氰酸酯基的甜菜碱抗菌防污化合物，即制得目标产物。
  7. 根据权利要求4或6所述的反应性抗菌防污化合物的制备方法，其特征在于，中间产物含端氨基甜菜碱或端羟基甜菜碱的制备方法，其步骤为：将含端羟基的叔胺或含端氨基的叔胺与反应物A在搅拌下、在温度10～80℃的环境中持续反应1～48小时，得白色的沉淀物质；
    将上述白色沉淀物质过滤或离心分离纯化，得中间产物含端氨基的甜菜碱化合物或含端羟基的甜菜碱化合物。
  8. 根据权利要求5或7所述的反应性抗菌防污化合物的制备方法，其特征在于， 所述含端羟基的叔胺或含端氨基的叔胺选自N，N-二甲基乙醇胺、N，N-二乙基乙醇胺、N，N-二甲基乙二胺、N，N-二乙基乙二胺、3，3’-亚氨基双(N，N-二甲基丙胺)、3-(二丁氨基)丙胺、3-二乙胺基丙胺、4-羟甲基吡啶、2，6-二甲基-3-氨基吡啶、2，6-二甲基-4-氨基吡啶、3-二甲基氨基-1-丙醇、2-[2-(二甲基氨基)乙氧基]乙醇中的一种。
  9. 根据权利要求5或6所述的反应性抗菌防污化合物的制备方法，其特征在于，所述反应物B是为二异氰酸酯化合物。
  10. 根据权利要求9所述的反应性抗菌防污化合物的制备方法，其特征在于，所述二异氰酸酯化合物选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯甲烷二异氰酸酯、1，5-萘二异氰酸酯、四甲基二异氰酸酯、六亚甲基二异氰酸酯、对苯基二异氰酸酯、二亚甲基苯基二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
  11. 根据权利要求5所述的反应性抗菌防污化合物的制备方法，其特征在于，催化剂C选自二月桂酸二丁基锡、辛酸亚锡、环烷酸金属盐的一种或几种组合物。
  12. 根据权利要求11所述的反应性抗菌防污化合物的制备方法，其特征在于，所述环烷酸金属盐选自环烷酸铜盐、环烷酸锌盐、环烷酸铅盐中的一种或几种。
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