CN101210062B - Antibiotic polymer material - Google Patents
Antibiotic polymer material Download PDFInfo
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- CN101210062B CN101210062B CN200610148043A CN200610148043A CN101210062B CN 101210062 B CN101210062 B CN 101210062B CN 200610148043 A CN200610148043 A CN 200610148043A CN 200610148043 A CN200610148043 A CN 200610148043A CN 101210062 B CN101210062 B CN 101210062B
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Abstract
The invention discloses an antibacterial polymer material which is polymerized by a plurality of components including antibacterial oligomer. The specific components comprise 30-99.5wt percent of unsaturated double bond monomer, 0.01-50wt percent of unsacturated double bond antibacterial oligomer, 0-10wt percent of hydrophilic monomer, 0.01-5.0wt percent of polymerization initiator and 0-80wt percent of fillings. The antibacterial polymer material of the invention is safe to the health of people and has long antibacterial performance and the antibacterial rates of the invention to staphyloccocus aureus rosenbach and escherichia coli are both more than 99percent. The invention is applicable for medical treatment and hygiene industries, including the wound dressing material, dental recovery materials used in dentistry (such as tooth bonder, tooth recovery coating, tooth recovery substrate and tooth filling materials, etc.), surgery seam and materials for daily use, etc.
Description
Technical field
The present invention relates to a kind of polymkeric substance, particularly a kind of antibiotic polymer material with permanent anti-microbial property.
Background technology
Antibiotic polymer material generally can obtain by following two kinds of methods:
1, directly add organic molecule antiseptic-germicide or inorganic antiseptic in polymer materials, this is the simplest a kind of method.What use morely now is with inorganic antiseptic, and the zeolitic material as metal ion (silver ions, cupric ion, zine ion etc.) directly adds in the polymeric matrix, mixes the back with polymeric matrix, directly prepares corresponding devices.In the textile industry field, handle fabric with the organic antibacterial agent of quaternary ammonium salt very early, so that fabric has anti-microbial property.But no matter be to add inorganic antiseptic or add the organic molecule antiseptic-germicide, their common shortcomings are that antiseptic-germicide can break away from polymeric matrix and runs off, and make goods lose anti-microbial property on the one hand, on the other hand, also can produce harm to environment and human body.
2, make material have anti-microbial property by the method for polymeric matrix being carried out chemical modification.Such as methods such as the block reaction of using graft reaction, surface chemical modification, polymkeric substance and monomeric direct copolymerization reactions, the functional group that will have anti-microbial activity, formal bond with chemical bond is incorporated on the substrate molecule chain of polymkeric substance, makes material have anti-microbial property.This is a kind of more advanced method, and it has solved antibiotic polymer material and has caused its anti-microbial property to reduce owing to the prolongation of time and to environment and the unsafe problem of human body.
China patent CN00125768.4 has described a kind of preparation method of polypropylene dedicated material, is reacted on the polypropylene matrix by the oligopolymer that will have anti-microbial activity, obtains having the polypropylene dedicated material of permanent anti-microbial property.It is the preparation of the anti-biotic material of base-material that but this patent is only applicable to the polypropylene.
China patent CN02111048.4 has further described the preparation of other polyolefine antibacterial plastic concentrates, comprise polyolefine materials such as polyethylene, polyvinyl chloride, polystyrene, the use that the method for chemical bonding is prepared antibiotic polymer material is further widened, and makes its Application Areas wider.
U.S. Pat 5408022 has been described the method with copolymerization, and preparation has the polymer materials of permanent anti-microbial property.The antibacterial monomer that uses is the quaternary amines monomer that has two keys, and the number of two keys can form crosslinked structure for one or more.Other used monomers mainly are acrylate or methyl acrylic ester.But employed antibacterial monomer has expensive shortcoming.
U.S. Pat 6326417B1 provides a kind of polymerisable antimicrobial compound.The antiseptic-germicide that uses is Whitfield's ointment, salicylate class, sulfanilamide (SN), or their composition.Monomer mainly is esters of acrylic acid and methyl acrylic ester.The polymkeric substance that the inventor introduces acquisition has permanent germ resistance.
Summary of the invention
The object of the present invention is to provide a kind of to human body safety and antibiotic polymer material with long-term antibacterial.
The object of the present invention is achieved like this:
A kind of antibiotic polymer material is polymerized by the various ingredients that comprises antibiotic oligopolymer, and component comprises:
The monomer 30%-99.5% (weight) of band unsaturated double-bond;
The antibiotic oligopolymer 0.01%-50% (weight) of band unsaturated double-bond;
Hydrophilic monomer 0-10% (weight);
Polymerization starter 0.01%-5.0% (weight);
Filler 0-80% and greater than 0 (weight).
The reaction monomers of described band unsaturated double-bond is selected from esters of acrylic acid, methyl acrylic ester, methacryloyl amine, vinyl carboxylates class or vinylbenzene, and its add-on is 30%-99.5%.Add-on is lower than the mechanical property that 30% meeting influence material, if add-on greater than 99.5%, then influences the add-on of other material, is difficult to reach the required over-all properties requirement of material.
The reaction monomers of band unsaturated double-bond of the present invention can be the monomer that contains single pair of key, also can be the monomer that contains two two keys, can also be the monomer that contains a plurality of pairs of keys.
A, contain the monomer of single pair of key, as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) ethyl acrylate, vinylbenzene, cinnamic derivative etc.
B, contain the monomer of two two keys, as: two-(methyl) vinylformic acid glycol esters, two-(methyl) vinylformic acid propylene glycol esters, two-(methyl) vinylformic acid butanediol esters, two-(methyl) vinylformic acid pentadiol esters, two-(methyl) vinylformic acid hexylene glycol esters, two-(methyl) vinylformic acid ethohexadiol esters etc.
Perhaps as more following materials: two-(methyl) vinylformic acid glycol ether esters, two-(methyl) vinylformic acid Triethylene Glycols, two-(methyl) vinylformic acid tetraethylene-glycol esters, two-(methyl) the vinylformic acid four five ethylene glycol ester that contracts, and two-(methyl) vinylformic acid dipropylene glycol esters, two-(methyl) vinylformic acid diacrylate, two-(methyl) vinylformic acid three four propylene glycol esters that contract.
Perhaps as more following materials: the reaction product of two-(methyl) vinylformic acid glycerine esters, dihydroxyphenyl propane dimethyl allene acid glycidyl ester (" two-GMA "), dihydroxyphenyl propane diacrylate glycidyl ester (" two-GA "), two-(methyl) vinylformic acid dihydroxyphenyl propane esters or (methyl) vinylformic acid and isocyanic ester.
C, contain the monomer of a plurality of pairs of keys, as: three-(methyl) vinylformic acid glyceryl ester, four-(methyl) vinylformic acid-pentaerythritol esters.
The antibiotic oligopolymer of band unsaturated double-bond of the present invention, its molecular weight have following feature structure between 300-50000:
Wherein, n is the integer of 2-20, and m is the integer of 4-200, and Y is a negatively charged ion, comprises Cl
-, NO
3 -, HCO
3 -Or H
2PO
4 -, X is acyl class or the ester class group that contains 1-5 active unsaturated double-bond, as acryloyl, methacryloyl, maleoyl, fumaryl, clothing health acyl, undecylene acyl, ethyl propenoate, propyl acrylate or methacrylic acid hydroxyl propyl ester, Z is hydrogen or X.The add-on of antibiotic oligopolymer is 0.01%-50%.If its add-on is lower than 0.01%, then be difficult to play the antimicrobial effect; If add-on greater than 50%, then can influence the mechanical property of material.
The said hydrophilic monomer of the present invention refers to the monomer that some contain carboxyl, phosphoryl, alkylsulfonyl, hydroxyl or amides.As: methacrylic acid, toxilic acid, maleic anhydride, reaction product, acrylamide, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc. to vinyl benzoic acid, (methyl) vinylformic acid and phosphoric acid.Its add-on is 0-10%.Can not add hydrophilic monomer, but if necessary, also can add, add-on is decided as required, generally 10% with interior for well.
The filler that the present invention adopts, add-on are 0-80% and greater than 0, also can add more filler, change the performance of material, also can reduce cost simultaneously.Filler can be silicon-dioxide, talcum powder, strontium glass, barium glass, lithium aluminosilicate, silica powder, lime carbonate, oxide powder and zinc etc., can also be polymer powder, comprises powder, polystyrene powder or other polymer powders of polymethylmethacrylate.Use the field in dentistry, filler is silicon-dioxide, talcum powder, strontium glass, barium glass, lithium aluminosilicate preferably, and its particulate size between the 4 μ m, 400nm more than is divided into two classes at 40nm with interior and granular size with granular size at 10nm.Wherein, 40nm accounts for the 60%-95% of filler gross weight with the consumption of interior filler, and the above filler of 400nm accounts for the 5%-40% of filler gross weight, and preferably 10% to 20%.The filler of this collocation, the anti-biotic material of acquisition have good aesthetic property and polishing performance if be used in the dental material aspect.
The mineral filler that the present invention adopts will be handled through silane coupling agent, with the bonding force between reinforcing filler and the polymkeric substance.Silane coupling agent is selected from vinyltriacetoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (beta-methoxy-oxyethyl group) silane, γ-(methacryloxy) propyl trimethoxy silicane, N '-vinyl benzyl-N-Trimethoxy silane propyl group ethylenediamine-hydrochloride.
The initiators for polymerization that the present invention adopts can be a peroxide initiator, also can be redox initiation system, can also be light initiation system.The add-on of initiator is 0.01%-5.0%.The add-on of initiator is lower than 0.01%, can influence the preparation process of material, prolongs the reaction times, reduces reaction efficiency.Add-on then can influence the mechanical property of material greater than 5.0%.Peroxide initiator wherein can be one or more in benzoyl peroxide, dicumyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide, the tert butyl peroxy benzoate.Redox initiation system can be the ferrous system of superoxide-naphthoic acid, the sour cobalt system of superoxide-Xin (naphthalene), superoxide-dimethyl benzene amine system etc.Light initiation system can be cooperation system, camphorquinone-peroxide systems, camphorquinone-aldehyde system or the camphorquinone-mercaptan system of camphorquinone, camphorquinone and tertiary amine.
Can also select other auxiliary agents as required, such as regulate molecular weight, to increase the luminescent properties of material, use uv-absorbing agent to increase the ultra-violet resistance of material with luminous agent with chain-transfer agent.
Antibiotic polymer material of the present invention, to human body safety and have long-term antibacterial, its antibiotic rate to streptococcus aureus＞99% is to antibiotic rate＞99% of colon bacillus.Can be used for medical treatment and health industry, comprise wound coating material, dental prosthetic material (repairing base-material, tooth filling material etc.), operating sutures and materials more used in everyday etc. such as tooth binding agent, tooth reparation, tooth.
Embodiment
The present invention can further specify by some following embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Get methyl methacrylate 95 grams, maleoyl 5 grams of polyethyene diamine Guanidinium carbonate, benzoyl peroxide 1 gram mixes, and can obtain antibiotic polymer material after the polymerization, is designated as 1#.
Embodiment 2
Get dihydroxyphenyl propane dimethyl allene acid glycidyl ester (" two-GMA ") 60 grams, methacryloyl 10 grams of poly-hexanediamine Guanidinium nitrate, 40nm is with interior SiO
218 grams, the SiO that 400nm is above
212 grams, benzoyl peroxide-xylidine 0.8 gram mixes, and can obtain antibiotic polymer material after the polymerization, is designated as 2#.
Embodiment 3
Get four-(methyl) vinylformic acid-pentaerythritol esters, 70 grams, acryloyl 10 grams of polyethyene diamine Guanidinium hydrochloride, 40nm is with interior lime carbonate 10 grams, lime carbonate 10 grams that 400nm is above, camphorquinone 1.0 grams mix, can obtain antibiotic polymer material after the polymerization, be designated as 3#.
Embodiment 4
Get two-methacrylic acid glycol ester, 85 grams, hydrophilic monomer Jia base Bing Xi Suan Hydroxyalkyl ethyl ester 5 grams, fumaryl 10 grams of poly-decamethylene diamine Guanidinium hydrochloride, benzoyl peroxide-cobalt octoate 0.8 gram mixes, and can obtain antibiotic polymer material after the polymerization, is designated as 4#.
Comparative Examples 1
Get methyl methacrylate 100 grams, benzoyl peroxide 1 gram mixes, and polymerization, obtains polymer materials, is designated as 5#.
Comparative Examples 2
Get methyl methacrylate 100 grams, benzoyl peroxide 1 gram, organic antibacterial agent cetalkonium chloride 2 grams mix, and polymerization, obtain polymer materials, are designated as 6#.
Table 1 is the anti-bacteria test result of gained sample (antibiotic rate is 24 hours a antibiotic rate, 1# ', 2# ', 3# ', 4# ', 5# ', 6# ' are that corresponding sample soaks a month later numbering in water):
The anti-bacteria test result of table 1 sample
| Sample | Antibiotic rate to colon bacillus | Antibiotic rate to golden yellow grape ball |
| 1# | ＞99％ | ＞99％ |
| 2# | ＞99％ | ＞99％ |
| 3# | ＞99％ | ＞99％ |
| 4# | ＞99％ | ＞99％ |
| 5# | ＜10％ | ＜10％ |
| 6# | ＞99％ | ＞99％ |
| 1#’ | ＞99％ | ＞99％ |
| 2#’ | ＞99％ | ＞99％ |
| 3#’ | ＞99％ | ＞99％ |
| 4#’ | ＞99％ | ＞99％ |
| 5#’ | ＜10％ | ＜10％ |
| 6#’ | ＜30％ | ＜30％ |
By the test result of table 1 as seen, embodiment 1-4 adopts the antibiotic polymer material of formulation of the present invention, to the antibiotic rate of streptococcus aureus and colon bacillus all greater than 99%; And Comparative Examples 1 is not adopt the polymer materials of formulation of the present invention, to the antibiotic rate of streptococcus aureus and colon bacillus less than 10%; Comparative Examples 2 adopts the organic antibacterial agent cetalkonium chloride, and its antibiotic rate is soaking an also reduction greatly later in month.
Claims (4)
1. an antibiotic polymer material is characterized in that, is polymerized by the various ingredients that comprises antibiotic oligopolymer, and component comprises:
The monomer 30%-99.5% (weight) of band unsaturated double-bond;
The antibiotic oligopolymer 0.01%-50% (weight) of band unsaturated double-bond;
Hydrophilic monomer 0-10% (weight);
Polymerization starter 0.01%-5.0% (weight);
Filler 0-80% and greater than 0 (weight);
The weight percentage sum of above-mentioned each component equals 100%:
The monomer of described band unsaturated double-bond is selected from acrylate, methacrylic ester, Methacrylamide, vinyl carboxylates or vinylbenzene;
The molecular weight of the antibiotic oligopolymer of described band unsaturated double-bond has following feature structure between 300-50000:
Wherein, n is the integer of 2-20, and m is the integer of 4-200, and Y is Cl
-, NO
3 -, HCO
3 -Or H
2PO
4 -, X is acyl class or the ester class group that contains 1-5 active unsaturated double-bond, comprises maleoyl, fumaryl, clothing health acyl or undecylene acyl, Z is hydrogen or X;
Described hydrophilic monomer is selected from the monomer that contains carboxyl, phosphoryl, alkylsulfonyl, hydroxyl or amides, comprising methacrylic acid, toxilic acid, maleic anhydride, reaction product, acrylamide, (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate to vinyl benzoic acid, (methyl) vinylformic acid and phosphoric acid;
To between the 4 μ m, wherein, the amount of filler of particle diameter 10nm-40nm accounts for the 60%-95% of filler gross weight to the particle diameter of described filler at 10nm, and the filler of particle diameter 400nm-4 μ m accounts for the 5%-40% of filler gross weight.
2. antibiotic polymer material according to claim 1, it is characterized in that: described filler is selected from silicon-dioxide, talcum powder, strontium glass, barium glass, lithium aluminosilicate, silica powder, lime carbonate or oxide powder and zinc.
3. antibiotic polymer material according to claim 1, it is characterized in that: the particle diameter of described filler at 10nm between the 4 μ m, wherein, the amount of filler of particle diameter 40nm-10nm accounts for the 80%-90% of filler gross weight, and the filler of particle diameter 400nm-4 μ m accounts for 10% to 20% of filler gross weight.
4. antibiotic polymer material according to claim 1, it is characterized in that: described polymerization starter is selected from peroxide initiator, redox initiation system or light initiation system; Peroxide initiator wherein is selected from one or more in benzoyl peroxide, dicumyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide, the tert butyl peroxy benzoate; Redox initiation system is selected from the ferrous system of superoxide-naphthoic acid, superoxide-cobalt octoate system, superoxide-naphthoic acid cobalt system or superoxide-dimethyl benzene amine system; Light initiation system is selected from cooperation system, camphorquinone-peroxide systems, camphorquinone-aldehyde system or the camphorquinone-mercaptan system of camphorquinone, camphorquinone and tertiary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610148043A CN101210062B (en) | 2006-12-27 | 2006-12-27 | Antibiotic polymer material |
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|---|---|---|---|
| CN200610148043A CN101210062B (en) | 2006-12-27 | 2006-12-27 | Antibiotic polymer material |
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| CN101210062B true CN101210062B (en) | 2010-05-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627126A (en) * | 2012-08-20 | 2014-03-12 | 叶向明 | Antibiosis master batch and application of antibiosis master batch in blended yarn, blended fabric and woven fabric |
| CN104592459B (en) * | 2015-01-21 | 2017-08-04 | 广西大学 | A kind of hud typed long acting antibiotic emulsion and preparation method thereof |
| CN109021220A (en) * | 2018-08-13 | 2018-12-18 | 贾勋 | A kind of long acting antibiotic polymer and its preparation method and application |
| CN110951014A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | Antibacterial polymethacrylate material and preparation method thereof |
| CN109467698B (en) * | 2018-10-10 | 2019-08-30 | 桂林新先立抗菌材料有限公司 | A kind of antibacterial polymer and preparation method thereof |
| CN109208174B (en) * | 2018-10-10 | 2019-09-27 | 桂林新先立抗菌材料有限公司 | A kind of melt spraying non-woven fabrics and preparation method thereof |
| WO2021096230A1 (en) * | 2019-11-13 | 2021-05-20 | 주식회사 엘지화학 | Superabsorbent polymer and preparation method therefor |
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| CN1350022A (en) * | 2000-10-19 | 2002-05-22 | 上海塑杰科技有限公司 | Polyamine-guanidine salt polymer and its prepn |
| CN1351086A (en) * | 2000-10-26 | 2002-05-29 | 上海塑杰科技有限公司 | Functional polypropylene for special purpose and its preparing process and application |
| CN1445270A (en) * | 2002-03-15 | 2003-10-01 | 上海塑杰科技有限公司 | Functional agglomerates of polyolefin as well as its preparing method and application |
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2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350022A (en) * | 2000-10-19 | 2002-05-22 | 上海塑杰科技有限公司 | Polyamine-guanidine salt polymer and its prepn |
| CN1351086A (en) * | 2000-10-26 | 2002-05-29 | 上海塑杰科技有限公司 | Functional polypropylene for special purpose and its preparing process and application |
| CN1445270A (en) * | 2002-03-15 | 2003-10-01 | 上海塑杰科技有限公司 | Functional agglomerates of polyolefin as well as its preparing method and application |
Non-Patent Citations (1)
| Title |
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| JP昭62-230806A 1987.10.09 |
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