CN107162981B - Antibacterial polymerizable monomer containing halogenated imidazole salt structure and preparation method and application thereof - Google Patents

Antibacterial polymerizable monomer containing halogenated imidazole salt structure and preparation method and application thereof Download PDF

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CN107162981B
CN107162981B CN201710370647.7A CN201710370647A CN107162981B CN 107162981 B CN107162981 B CN 107162981B CN 201710370647 A CN201710370647 A CN 201710370647A CN 107162981 B CN107162981 B CN 107162981B
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bone cement
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何经纬
刘芳
朱文彬
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/288—Halogen containing polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides

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Abstract

The invention discloses an antibacterial polymerizable monomer containing a halogenated imidazolium salt structure, and a preparation method and application thereof. The antibacterial polymerizable monomer containing the halogenated imidazolium salt structure is prepared, and can be used as an antibacterial additive of acrylate bone cement. The monomer is characterized in that the acrylate bone cement has strong antibacterial performance, the curing time of the self-setting acrylate bone cement is less influenced, the dough time of the bone cement can be obviously shortened, and the mechanical property of the bone cement containing the monomer is good.

Description

Antibacterial polymerizable monomer containing halogenated imidazole salt structure and preparation method and application thereof
Technical Field
The invention relates to a series of polymerizable monomers capable of being used as acrylate bone cement additives, in particular to an antibacterial polymerizable monomer containing a halogenated imidazole salt structure, and a preparation method and application thereof.
Background
China is currently moving to an aging society, and orthopedic degenerative diseases related to the elderly population are increasing. And the incidence of bone defects caused by industrial accidents, traffic accidents, orthopedic diseases and the like is maintained at a high level for a long time. Therefore, it is necessary to perform bone repair using artificial materials.
The acrylate bone cement is a bone repair material which is widely applied in clinical application and is used for orthopedic surgery, and the main component of the acrylate bone cement is polymethyl methacrylate (PMMA) which has biological inertia. The acrylate bone cement is prepared with two parts, powder and liquid, and through mixing in certain proportion at room temperature, setting in the position needing joint replacement or filling, and polymerizing reaction for certain time before curing, so as to realize artificial joint fixing or bone defect repair.
Some patients may develop bacterial infections in the joint prosthesis, bone cement prosthesis, and in the surrounding bone and soft tissue due to incomplete surgical sterilization, contamination of instruments, or the presence of an original infection focus in the patient. Serious problems such as prosthesis loosening, osteolysis and the like are easily caused by infection, and revision surgery is needed after infection, so that the pain and burden of a patient are greatly increased.
Acrylate bone cements lack antibacterial activity. At present, antibiotics are mainly added into acrylate bone cement to prevent infection, and an antibacterial bone cement formula containing gentamicin, as disclosed in a patent US4059684, is widely used clinically. However, the bone cement containing antibiotics has the problems of reduced mechanical properties, lack of long-acting antibacterial property and easy generation of drug resistance. In order to find an alternative to antibiotics, silver-containing substances or other organic antibacterial agents are introduced into bone cement to prepare antibacterial bone cement, and for example, patent CN102380126 and patent CN102218158 disclose antibacterial bone cement formulations containing silver and chitosan quaternary ammonium salt, respectively. However, silver-containing implants have proved to possibly cause nervous system diseases, and migratory organic antibacterial agents such as chitosan quaternary ammonium salt and the like cannot endow the bone cement with long-term antibacterial property. Therefore, the development of novel acrylate bone cement antibacterial additives has attracted increasing attention.
Disclosure of Invention
The invention aims to provide a preparation method and application of a series of antibacterial methacrylate monomers capable of endowing acrylate bone cement with long-acting antibacterial performance against the defects that the conventional bone cement containing antibiotics is reduced in mechanical performance of the bone cement, has non-lasting antibacterial performance and can cause bacteria to generate drug resistance.
The invention also aims to provide the application of the antibacterial methacrylate monomer in acrylate bone cement.
The above object of the present invention is achieved by the following method.
The antibacterial polymerizable monomer containing the halogenated imidazole salt structure has a structural formula shown as a formula (I);
Figure BDA0001302684430000021
in the formula (I), n is any integer of 1-5; in the formula (I), R1Taking any one of a methyl group or a (II);
Figure BDA0001302684430000022
i in the structural formula (II) is any one of values of 0-26;
x in the formula (I) is any one of the formulas (III);
X＝F，Cl，Br,I (Ⅲ)。
a preparation method of an antibacterial polymerizable monomer containing a halogenated imidazolium salt structure comprises the following steps:
adding N-hydroxyalkyl imidazole and a solvent into a reaction vessel, adding isocyano ethyl methacrylate under stirring, reacting for 0.5-12 hours at 5-60 ℃ to ensure that isocyanate groups are completely reacted, then adjusting the reaction temperature to 50-100 ℃, adding alkyl halide, reacting for 5-100 hours to generate a product, and then purifying the reaction product to obtain the antibacterial polymerizable monomer containing the halogenated imidazole salt structure.
In the method, the ratio of the amount of the isocyanoethyl methacrylate to the amount of the N-hydroxyalkyl imidazole is 1:1.0 to 1: 1.5; the ratio of the amount of the alkyl halide to the amount of the N-hydroxyalkyl imidazole is 1:1.0 to 1: 3.0.
In the above method, in the step, the N-hydroxyalkyl imidazole comprises N-hydroxymethyl imidazole, N-hydroxyethyl imidazole, N-hydroxypropyl imidazole, N-hydroxybutyl imidazole or N-hydroxypentyl imidazole; the types of the solvent include acetone, butanone, cyclohexanone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, dichloromethane, or chloroform.
In the above method, in the step, the alkyl halide includes: fluoromethane, 1-fluoroethane, 1-fluoropropane, 1-fluorobutane, 1-fluoropentane, 1-fluorohexane, 1-fluoroheptane, 1-fluorooctane, 1-fluorononane, 1-fluorodecane, 1-fluoroundecane, 1-fluorododecane, 1-fluorotridecane, 1-fluorotetradecane, 1-fluoropentadecane, 1-fluorohexadecane, 1-fluoroheptadecane, 1-fluorooctadecane, 1-fluorononadecane, 1-fluoroeicosane, 1-fluoroheneicosane, 1-fluorodocosane, 1-fluorotricosane, 1-fluorotetracosane, 1-fluoropentacosane, 1-fluorohexacosane, 1-fluoroheptacosane, 1-fluorooctacosane, chloromethane, 1-chloroethane, 1-chloropropane, 1-chlorobutane, 1-chloropentane, 1-chlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, 1-chloroundecane, 1-chlorododecane, 1-chlorotridecane, 1-chlorotetradecane, 1-chloropentadecane, 1-chlorohexadecane, 1-chloroheptadecane, 1-chlorooctadecane, 1-chlorononadecane, 1-chloroeicosane, 1-chloroheneicosane, 1-chlorodocosane, 1-chlorotricosane, 1-chlorotetracosane, 1-chloropentacosane, 1-chlorohexacosane, 1-chloroheptacosane, 1-chlorooctacosane, bromomethane, 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-chlorobutane, chlorodecane, 1-chlorononadecane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-bromopentadecane, 1-bromohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-bromononadecane, 1-bromoeicosane, 1-bromoheneicosane, 1-bromodocosane, 1-bromotricosane, 1-bromotetracosane, 1-bromopentacosane, 1-bromohexacosane, 1-bromoheptacosane, 1-bromooctacosane, iodomethane, 1-iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane, 1-iododecane, 1-iodoundecane, 1-iodododecane, 1-iodotridecane, 1-iodotetradecane, 1-iodopentadecane, 1-iodohexadecane, 1-iodoheptadecane, 1-iodooctadecane, 1-iodononadecane, 1-iodoeicosane, 1-iodoheneicosane, 1-iododocosane, 1-iodotricosane, 1-iodotetracosane, 1-iodopentacosane, 1-iodohexacosane, 1-iodoheptacosane or 1-iodooctacosane.
Taking N-hydroxyethyl imidazole, isocyano ethyl methacrylate and bromohexadecane as raw materials as an example, the chemical equation of the reaction is as follows:
Figure BDA0001302684430000031
the polymerization product of the polymerizable monomer has broad-spectrum efficient antibacterial property, and can partially replace methyl methacrylate in acrylate bone cement to prepare the antibacterial acrylate bone cement when being applied specifically.
Compared with the prior art, the invention has the following beneficial effects:
the antibacterial polymerizable monomer containing the halogenated imidazolium salt structure has the remarkable advantages of broad-spectrum and efficient antibacterial property, can participate in the curing process of acrylate bone cement, and endows the bone cement with a long-acting infection prevention function. Therefore, the antibacterial polymerizable monomer containing the halogenated imidazolium salt structure has the potential of being developed into an antibacterial additive of acrylate bone cement.
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FIG. 1 shows example A2BnF is a comparison graph of antibacterial performance of bone cement prepared by partially substituting methyl methacrylate in acrylate bone cement by a mass fraction of 5%.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to limit the present invention in any way.
The antibacterial polymerizable monomer containing the halogenated imidazolium salt structure has a structural formula shown as a formula (I);
Figure BDA0001302684430000041
in the formula (I), n is any integer of 1-5; in the formula (I), R1Taking any one of a methyl group or a (II);
Figure BDA0001302684430000042
i in the structural formula (II) is any one of values of 0-26;
x in the formula (I) is any one of the formulas (III);
Figure BDA0001302684430000043
example 1
This example preparation A2B12F monomer, the main steps are as follows:
charging 1 into the reaction vessel12g of N-hydroxyethylimidazole and 50mL of tetrahydrofuran, 1.55g of isocyanoethyl methacrylate was added dropwise at a rate of 20 drops per minute with stirring, the reaction was carried out at 45 ℃ for 12 hours to complete the reaction of the isocyanate groups, then 2.49g of bromododecane was added thereto at a reaction temperature of 65 ℃ for 72 hours to give a product, which was then subjected to purification treatment to give A2B12The F type monomer, the product is characterized by nuclear magnetic resonance hydrogen spectrum:
1H-NMR(DMSO-d6，600MHz)：δ0.85[3H，t]，1.24[18H，s]，1.79[2H，m]，1.87[3H，s]，3.24[2H，q]，4.07[2H，t]，4.20[2H，t]，4.32[2H，t]，4.45[2H，t]，5.68[1H，s]，6.05[1H，s]，7.52[1H，t]，7.80[1H，s]，7.85[1H，s]，9.29[1H，s]
example 2
This example preparation A2B16F monomer, the main steps are as follows:
adding 1.12g of N-hydroxyethyl imidazole and 50mL of tetrahydrofuran into a reaction container, dropwise adding 1.55g of isocyano ethyl methacrylate at the speed of 20 drops per minute under the stirring state, reacting for 12 hours at 45 ℃ to completely react isocyanate groups, adjusting the reaction temperature to 65 ℃, adding 3.05g of bromohexadecane, reacting for 72 hours to generate a product, and purifying to obtain A2B16The F type monomer, the product is characterized by nuclear magnetic resonance hydrogen spectrum:
1H-NMR(DMSO-d6，600MHz)：δ0.85[3H，t]，1.23[26H，s]，1.77[2H，m]，1.87[3H，s]，3.24[2H，q]，4.07[2H，t]，4.19[2H，t]，4.32[2H，t]，4.44[2H，t]，5.68[1H，s]，6.04[1H，s]，7.49[1H，t]，7.79[1H，s]，7.84[1H，s]，9.26[1H，s]
example 3
This example preparation A2B18F monomer, the main steps are as follows:
1.12g of N-hydroxyethylimidazole and 50mL of tetrahydrofuran were charged into a reaction vessel, 1.55g of isocyanoethyl methacrylate was added dropwise at a rate of 20 drops per minute with stirring, and the reaction was carried out at 45 ℃ for 12 hours to complete the reaction of the isocyanate group, followed by adjustment of the reactionAdding 3.33g bromododecane at 65 ℃, reacting for 72 hours to generate a product, and then purifying to obtain A2B18The F type monomer, the product is characterized by nuclear magnetic resonance hydrogen spectrum:
1H-NMR(DMSO-d6，600MHz)：δ0.85[3H，t]，1.24[30H，s]，1.79[2H，m]，1.87[3H，s]，3.25[2H，q]，4.07[2H，t]，4.20[2H，t]，4.32[2H，t]，4.45[2H，t]，5.68[1H，s]，6.05[1H，s]，7.51[1H，t]，7.80[1H，s]，7.85[1H，s]，9.30[1H，s]
example 4
A2B12F、A2B16F and A2B18And F accounts for 5 percent of the operation, curing property and mechanical property of the acrylate bone cement.
This example uses A in an amount of 5% by mass of the acrylate bone cement prepared2B12F、A2B16F and A2B18F, respectively partially replacing methyl methacrylate in the acrylate bone cement liquid, and researching the operation, curing characteristics and mechanical properties of the prepared bone cement, wherein the formula is as follows:
bone cement liquid: methyl methacrylate: a. the2BnF: n, N-dimethyl-p-toluidine: hydroquinone 27.58: 5: 0.67: 0.05(n ═ 12, 16, 18); bone cement powder: polymethyl methacrylate particles: zirconium dioxide: benzoyl peroxide 55.37: 10: 1.33; the bone cement liquid and the bone cement powder are mixed according to the proportion of 1: 2 to prepare a sample. The results of the handling characteristics and curing characteristics are shown in Table 1. The mechanical properties are shown in Table 2.
As is clear from tables 1 and 2, the compound contains A2BnThe time of the bone cement dough of F is reduced, the highest temperature is reduced, the setting time meets the use requirement, and the operation performance is optimized on the whole. As can be seen from Table 2, the compound contains A2BnThe bone cement of F has good mechanical properties.
Table 1 contains 5% by mass of A2BnDough time, setting time and maximum temperature of bone cement of F
Figure BDA0001302684430000061
Table 2 contains 5% by mass of A2BnFlexural modulus, flexural strength and compressive strength of the bone cement of F
Figure BDA0001302684430000062
Example 5A2B12F、A2B16F and A2B18Antibacterial property of acrylate bone cement with mass fraction of F being 5%
This example uses A in an amount of 5% by mass of the acrylate bone cement prepared2B12F、A2B16F and A2B18F, respectively partially substituting methyl methacrylate in the acrylate bone cement liquid, and researching the antibacterial property of the prepared bone cement, wherein the formula is as follows:
bone cement liquid: methyl methacrylate: a. the2BnF: n, N-dimethyl-p-toluidine: hydroquinone 27.58: 5: 0.67: 0.05(n ═ 12, 16, 18); bone cement powder: polymethyl methacrylate particles: zirconium dioxide: benzoyl peroxide 55.37: 10: 1.33; the bone cement liquid and the bone cement powder are mixed according to the proportion of 1: 2 to prepare a sample. To contain no A2BnThe bone cement of F is used as a control and contains 5 percent of A by mass2BnThe antibacterial ratio of the bone cement of F is shown in fig. 1.
As can be seen from FIG. 1, A2BnThe addition of F improves the antibacterial performance of the bone cement. Containing 5% of A2B12The bone cement of F has relatively good antibacterial effect on Escherichia coli. For Staphylococcus aureus, 5% A2B12F、A2B16F、A2B18The bone cement of F has good antibacterial performance.

Claims (1)

1. The application of the antibacterial polymerizable monomer containing the halogenated imidazole salt structure in preparing the polymerizable antibacterial additive serving as acrylate bone cement is characterized in that the structural formula is shown as the formula (I);
Figure FDA0002387560260000011
in the formula (I), n is any integer of 1-5; in the formula (I), R1Taking any one of methyl or formula (II);
Figure FDA0002387560260000012
i in the structural formula (II) is any one of values of 0-26;
x in the formula (I) is any one of the formulas (III);
X＝F，Cl，Br，I (Ⅲ)。
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CN108484487B (en) * 2018-03-23 2021-10-22 华南理工大学 Antibacterial (methyl) acrylate monomer containing quaternary pyridinium salt and carbamate structure and preparation method and application thereof
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