CN103193903A - Sterilization polymer containing quaternary ammonium salt and halamine or halamine precursor functional group as well as preparation method and application of sterilization polymer - Google Patents
Sterilization polymer containing quaternary ammonium salt and halamine or halamine precursor functional group as well as preparation method and application of sterilization polymer Download PDFInfo
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Abstract
The invention relates to a sterilization polymer containing a quaternary ammonium salt and halamine or a halamine precursor functional group as well as a preparation method and application of the sterilization polymer. The preparation method comprises the following steps of: generating a high-molecular polymer containing the quaternary ammonium salt and the halamine precursor functional group through the reaction among a halo-methylated high-molecular polymer serving as a carrier, tertiary amine and a halamine precursor; and generating the sterilization high-molecular polymer containing the quaternary ammonium salt and the halamine precursor functional group through halogenating reaction. The sterilization high-molecular polymer has a quick, efficient and broad-spectrum sterilization effect, can be extensively applied to sterilization treatment of various water bodies and air as well as the control of harmful smelly gas. The sterilization high-molecular polymer also can be mixed with other materials to obtain various sanitary and anti-bacterial products such as an anti-bacterial mattress cover, an anti-bacterial blanket, an anti-bacterial diaper.
Description
Technical field
The present invention relates to the synthetic and application of the new and effective reproducible high molecular polymer sterilant of a class, be specifically related to a class and contain bactericidal polymer of quaternary ammonium salt and halogen amine or halogen amine forebody functional group and its preparation method and application.
Background technology
Effectively the utilization of antibiotic and sterilizing material and technology is that the blocking-up harmful microorganism is propagated and popular important means.Because water-soluble sterilant has toxicity and more greatly, easily causes shortcomings such as pollution, insoluble Polymer Bactericides, the particularly development of water-insoluble resin sterilant more and more cause people's interest.US Patent No. 4349646 discloses the method that a kind of polystyrene resin by chloromethylation or polychlorostyrene methacrylate resin and tertiary amine or two uncles base diamine reactant prepare water-insoluble polyquaternium type sterilization resin.US4826924 discloses a kind of polystyrene resin or polystyrene-divinylbenzene resin and N-alkyl-4 by chloromethylation, 4 '-bipyridine salt, N-alkyl-2,2 '-the quaternary ammonium salt prepared in reaction of bipyridine salt and band tertiary amine groups contains the method for the sterilization resin of double amidopyridine salt and bi-quaternary ammonium salt structure.Chinese patent CN1062714C disclose gel-type that a kind of polystyrene resin by chloromethylation or vinylbenzene and divinylbenzene copolymerization obtain or macroporous ion-exchange resin and amino season phosphonium salt prepared in reaction water do not contain intermingle with the method for season phosphonium salt type sterilization resin.Though more than the prepared insoluble quaternary of water, pyridine salt type or the season phosphonium salt type sterilization resin of these patented methods can effectively kill unwanted bacteria in the water, need relatively long duration of contact.Containing harmful microbe water with flow velocity faster during by water strainer, its sterilization and disinfection effect is difficult to meet the demands.
The N-halamine compounds is the newer antibiotic and sterilizing compound of a class, owing to broad spectrum, high efficiency and the renewable application that obtains more and more widely of its antibiotic and sterilizing.By relevant technologies the N-halamine molecule is grafted on the macromolecular material, can prepares water-insoluble N-halamine high-molecular anti-bacteria pasteurization material.US Patent No. 5490983 adopts polystyrene to make raw material, react by the Fu Ke (Friedel-Crafts) with Acetyl Chloride 98Min., then with the annulation of volatile salt and potassium cyanide, halogenating reaction last and oxidation state halogen such as chlorine or clorox etc. obtains water-insoluble N-halamine macromolecular compound, poly-[1,3-, two chloro-5-methyl-5-(4 '-ethenylphenyl) glycolylurea].This polymkeric substance can effectively be killed unwanted bacteria and other harmful microorganism that comprises streptococcus aureus and intestinal bacteria in the extremely short time.But problem is the Friedel-Crafts reaction of this polymer manufacture the first step uses the dithiocarbonic anhydride that is very easy to volatilization to make solvent and use a large amount of aluminum trichloride (anhydrous)s to make catalyzer, reaction needs after finishing the very high hydrochloric acid soln of working concentration to come aluminum chloride in the hydrolysis reaction mixture, thereby produces a large amount of aluminic acid wastewaters that contain; Second step used excessive highly toxic product potassium cyanide or sodium cyanide and needed to use autoclave, thereby produced a large amount of high density cyanide wastewaters that contain.Simultaneously, because this polymkeric substance is to exist with pulverous form, water is passed through with flow velocity faster.US Patent No. 561162 adopts the macroporous cross-linked polystyrene resin to make raw material on the basis of US5490983 patent, obtain poly-[1 of macro porous crosslinking by Friedel-Crafts reaction, annulation and halogenating reaction, 3-two chloro-5-methyl-5-(4 '-ethenylphenyl) glycolylurea] and poly-[1,3-, two bromo-5-methyl-5-(4 '-ethenylphenyl) glycolylurea] spherical resin and their single halogenated alkali metal salt and protonated derivative.Although such sterilization and disinfection spherical resin is highly suitable for the sterilization application of water strainer; but in their preparation process, can produce a large amount of organic liquid wastes and cyanide wastewater equally; this just makes that the production cost of such sterilization and disinfection resin is very high, and large-scale production is faced with very big environmental protection pressure.Consider after these unfavorable factors, US Patent No. 7687072B2 adopts the macroporous cross-linked polystyrene resin of chloromethylation to make raw material, by in dimethyl formamide (DMF) solvent and 5, halogen amine forebody prepared in reaction halogen amine polymer forebody such as 5-dimethyl hydantion, pass through then and halide reagent prepared in reaction water-insoluble N-halamine polymer sterilization and disinfection resin material such as 1-chloro-5 such as clorox and sodium hypobromite, 5-dimethyl-3-(to the vinyl benzene methylene) glycolylurea polymkeric substance and 1-bromo-5,5-dimethyl-3-(to the vinyl benzene methylene) glycolylurea polymkeric substance.The synthetic route of this series products is simple, the product convenient post-treatment, but its available chlorine or effective bromine content are significantly less than available chlorine or effective bromine content of the sterilization and disinfection spherical resin that adopts US Patent No. 561162 described methods preparations.In addition, chemical structure and space structure from polymkeric substance, adopt the prepared 1-chloro-5 of US Patent No. 7687072B2 technology, 5-dimethyl-3-(to the vinyl benzene methylene) glycolylurea polymkeric substance and 1-bromo-5, the surface hydrophilicity of 5-dimethyl-3-(to the vinyl benzene methylene) glycolylurea fluoropolymer resin is relatively poor, swelling is limited in water, the diameter in its inner duct is usually between several nanometers to tens nanometer, and the size of microorganisms such as bacterium generally reaches micron order, and this is killed with regard to making bacterium can not enter the duct, inside of resin.Simultaneously, oxidation state halogen on its outer surface is because of after sterilization is consumed, oxidation state halogen on the interior surface thereof is difficult to be arrived outside surface as early as possible in the mode by the migration of inner duct and replenishes the oxidation state halogen that is consumed, and this just makes that the utilization ratio of whole effective halogen of sterilization resin may be lower.Take all factors into consideration some shortcomings that existing various sterilization and disinfection macromolecule polymer material up till now exists, we think that exploitation can avoid the disinfecting sterilization macromolecule polymer material of these shortcomings necessary as far as possible.
Summary of the invention
The objective of the invention is to overcome some shortcomings that existing sterilization and disinfection macromolecule polymer material and technology thereof exist, provide that a class chemical structure novelty, sterilization and disinfection high-efficiency broad spectrum, disinfection function are renewable, the simple sterilization and disinfection macromolecule polymer material of synthetic route and technology thereof.
Design of the present invention is such: quaternary ammonium salt functional group has positive charge, has good hydrophilicity; Halogen amine is a class sterilization high-efficiency broad spectrum, the reproducible novel oxidative bactericide of disinfection function.If pass through unique preparation process, make and contain quaternary ammonium salt functional group and halogen amine functional group on the high molecular polymer structure, take full advantage of their unique physico-chemical property and antimicrobial characteristic and possible antibiotic synergistic effects between the two separately, just might synthesize the high molecular polymer bactericidal disinfectant material of new generation that the sterilization and disinfection effect is more powerful, performance is more good.
For this reason, the present invention adopt can halomethylation high molecular polymer be carrier, generate the high molecular polymer that contains quaternary ammonium salt and halogen amine forebody functional group by the reaction with tertiary amine and halogen amine forebody, generate the sterilization high molecular polymer that contains quaternary ammonium salt and halogen amine functional group by halogenating reaction at last, such sterilization and disinfection high molecular polymer is made up of high molecular polymer carrier and quaternary ammonium salt functional group and halogen amine or halogen amine forebody, and its structural formula is as follows:
The structural formula of high molecular polymer carrier part is:
Wherein P be can halomethylation high molecular polymer, be preferably gel-type or macroporous ion-exchange resin that polystyrene, polystyrene resin, vinylbenzene and divinylbenzene copolymerization obtain; The degree of crosslinking of gel type resin can 1～20%, preferred 1～6%; The degree of crosslinking of macroporous ion-exchange resin can be 1～20%, preferred 1～8%; Y is Cl, Br, I or OH, and k is the mmole number (mmol/g) of the hydroxymethyl that do not generate with monochloromethyl and the hydrolysis thereof of tertiary amine and halogen amine forebody reaction in every gram bactericidal polymer, is 0～3.2mmol/g, is generally 0.3～1.5mmol/g.
R is halogen amine or halogen amine forebody group, and n is the mmole number (mmol/g) of halogen amine functional group or halogen amine forebody in every gram bactericidal polymer, is 0.2～3.2 (mmol/g), is preferably 1.0～2.4 (mmol/g).
The structural formula of quaternary ammonium moiety is:
R
1, R
2, R
3Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl, perhaps R
1, R
2Unite and be C
3-C
7Cycloalkyl or cycloolefin group; X
-aComprise F
-, Cl
-, Br
-, I
-, OH
-, CO
3 2-, SO
3 2-, SO
4 2-, NO
3 -, ClO
-, BrO
-, I
3 -, ClO
3 -, ClO
4 -, HCOO
-, CH
3COO
-, a is the valency of X; M is the mmole number (mmol/g) of quaternary ammonium salt functional group in every gram bactericidal polymer, is 0.2～3.2 (mmol/g), is preferably 0.5～1.9 (mmol/g).
Described halogen amine or halogen amine forebody radicals R can for:
R wherein
1' and R
2' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl, halogen; Perhaps R
1' and R
2' unite and constitute C
3-C
7Cycloalkyl or cycloolefin group; X
1' and X
2' be hydrogen or halogen.
Described halogen amine or halogen amine forebody radicals R can also be for having the group of following structure:
Wherein, R
3', R
4', R
5', R
6' and R
7' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl or halogen, perhaps R
3' and R
4' associating and R
5' and R
6' unite and be C
3-C
7Cycloalkyl or cycloolefin group, X
3' and X
4' be hydrogen or halogen.
Described halogen amine or halogen amine forebody group include, but are not limited to above-mentioned group.
The present invention generates the high molecular polymer that contains quaternary ammonium salt and halogen amine forebody functional group by the reaction of the high molecular polymer of tertiary amine and halogen amine forebody and halomethylation, generate the sterilization high molecular polymer that contains quaternary ammonium salt and halogen amine functional group by halogenating reaction at last, specifically comprise:
1) contain the preparation of the polymkeric substance of quaternary ammonium salt and halogen amine forebody functional group:
Tertiary amine, halogen amine forebody, alkali are joined the polymer P-CH that contains halomethylation in 10:1～100:1～100 in molar ratio
2In the organic solvent or water of Y (Y=Cl, Br, I), 10 ℃～150 ℃ reactions 2 to 48 hours, obtain to contain the polymkeric substance of quaternary ammonium salt and halogen amine forebody functional group behind the filtration washing, oven dry below 100 ℃;
Organic solvent is C
1～C
6The mixture of alcohol, acetone, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF) or their several solvents is preferably C
1～C
4Alcohol, dimethyl formamide, reaction solvent is C
1～C
4During alcohol, temperature of reaction is preferably 30 ℃～80 ℃, and when reaction solvent was water or dimethyl formamide, temperature of reaction was preferably 40 ℃～90 ℃; Reaction times is preferably 8～16 hours.
2) contain the preparation of the polymkeric substance of quaternary ammonium salt and halogen amine functional group:
The polymkeric substance that will contain quaternary ammonium salt and halogen amine forebody functional group joins in the solution of oxidation state halogen that concentration is 0.10wt%～10.00wt%, preferred 0.50wt%～3.00wt%; Regulator solution pH value between 2-13, preferred 6～8;-15 ℃～30 ℃ reactions 10 minutes to 10 hours, preferred-5 ℃～10 ℃ of temperature of reaction, preferred 1-3 of reaction times hour, acquisition contained the polymkeric substance of quaternary ammonium salt and halogen amine functional group behind the filtration washing, oven dry below 50 ℃.
The above-mentioned preparation method who contains the polymkeric substance of quaternary ammonium salt and halogen amine forebody functional group, the chemical structure of said halogen amine forebody are as following shown in each:
Wherein, R
1', R
2', R
3', R
4', R
5', R
6' and R
7' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl or halogen, perhaps R
1' and R
2', R
3' and R
4' and R
5' and R
6' unite and be C
3-C
7Cycloalkyl or cycloolefin group.
The chemical structural formula of said tertiary amine is as follows:
R
1, R
2, R
3Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl, perhaps R
1, R
2Unite and be C
3-C
7Cycloalkyl or cycloolefin group.
Said alkali comprises sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium ethylate and potassium ethylate; Be preferably yellow soda ash and sodium hydroxide.
The above-mentioned preparation method who contains the polymkeric substance of quaternary ammonium salt and halogen amine functional group, said oxidation state halogen comprises Cl
2, Br
2, NaClO, NaBrO, KClO or KBrO; Be preferably NaClO, Cl
2, Br
2
Such sterilization high molecular polymer contains halogen amine sterilization functional group and quaternary ammonium salt bactericide functional group simultaneously, has biocidal efficacies quick, efficient, wide spectrum, can be widely used in the sterilization processing of various water bodys and air and the control of harmful unpleasant gas.Such sterilization and disinfection high molecular polymer also can make various sanitary antimicrobial products such as antibiotic bed mattress cover, antibacterial carpet, antibiotic diaper etc. through certain combination treatment with other material.
The present invention's beneficial effect compared with prior art:
The bactericidal polymer that contains quaternary ammonium salt and halogen amine functional group that the present invention is prepared has brand-new molecular structure, its synthesis technique environmental protection.Introducing by quaternary ammonium salt functional group, make an alkali metal salt of the good halogen amine of wetting ability forebody to generate the bactericidal polymer resin that contains quaternary ammonium salt and halogen amine functional group with the polymkeric substance of halomethylation such as the chloromethylated polystyrene resin generation chemical reaction of macro porous crosslinking than being easier to, thereby simplified preparation technology, reduced production cost.In addition, by the antibiotic functional group of halogen amine and hydrophilic quaternary ammonium salt functional groups on identical high molecular polymer chain, thereby make the surface hydrophilicity of prepared anti-biotic material strengthen greatly, this is with regard to making anti-biotic material be easy to contact with harmful microorganism and strengthened its antibiotic effect greatly.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA3) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 3:1.
Take by weighing 5,5-T10 1.77 grams and yellow soda ash 1.47 grams join in 250 milliliters of round-bottomed flasks, and with the dissolving of 20 milliliters of Virahols, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 0.91 gram down, 60 ℃ of following stirring reactions 12 hours.Reaction finishes the macro porous crosslinking resin PSHTA3 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 3.67 grams.Ultimate analysis test value: C, 66.67; H, 7.876; N, 7.16.IR：3741，3428，3022，2929，1768，1708，1614，1512，1488，1472，1445，1415，1343，1272，1221，1129，1021，976，914，889，828，778，709，603cm
-1。
Embodiment 2
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA3-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA3 macro porous crosslinking resin 1.45 grams of embodiment 1 preparation and place 50 milliliters beaker, add 14 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 6.81 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHTA3-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 5.76%.Ultimate analysis test value: C, 62.62; H, 6.980; N, 6.32.IR：3416，3024，2929，1785，1720，1612，1512，1438，1407，1383，1339，?1223，1178，1135，975，929，889，828，762，735，677，626，451cm
-1。
Embodiment 3
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA3-Br) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA3 macro porous crosslinking resin 1.46 grams of embodiment 1 preparation and place 50 milliliters beaker, add 14 ml deionized water and 1.12 gram Potassium Bromides, place ice bath to stir, slowly the chlorine bleach liquor 6.89 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, dropwise back stirring reaction 2 hours in ice bath.Reaction finishes the macro porous crosslinking resin PSHTA3-Br that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state bromine (Br on the iodometric determination resin
+) content be 12.77%.Ultimate analysis test value: C, 50.54; H, 5.619; N, 5.01.IR：3850，3393，3021，2926，1770，1709，1611，1512，1440，1408，1338，1220，1130，1019，974，920，886，827，763，708，675，629，449cm
-1。
Embodiment 4
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA2) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 1:1.
Take by weighing 5,5-T10 1.18 grams and yellow soda ash 0.98 gram join in 250 milliliters of round-bottomed flasks, and with the dissolving of 20 milliliters of Virahols, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 1.82 grams down, 60 ℃ of following stirring reactions 12 hours.Reaction finishes the macro porous crosslinking resin PSHTA2 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 3.71 grams.Ultimate analysis test value: C, 67.42; H, 7.867; N, 6.21.
Embodiment 5
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA2-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA2 macro porous crosslinking resin 1.54 grams of embodiment 4 preparations and place 50 milliliters beaker, add 15 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 5.06 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHTA2-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 3.07%.
Embodiment 6
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA2-Br) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA2 macro porous crosslinking resin 1.45 grams of embodiment 4 preparations and place 50 milliliters beaker, add 14 ml deionized water and 0.77 gram Potassium Bromide, place ice bath to stir, slowly the chlorine bleach liquor 4.74 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, dropwise back stirring reaction 2 hours in ice bath.Reaction finishes the macro porous crosslinking resin PSHTA2-Br that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state bromine (Br on the iodometric determination resin
+) content be 10.13%.
Embodiment 7
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA1) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 1:3.
Take by weighing 5,5-T10 0.59 gram and yellow soda ash 0.49 gram join in 250 milliliters of round-bottomed flasks, and with the dissolving of 20 milliliters of Virahols, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 2.73 grams down, 60 ℃ of following stirring reactions 12 hours.Reaction finishes the macro porous crosslinking resin PSHTA1 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 3.84 grams.Ultimate analysis test value: C, 65.07; H, 8.625; N, 6.04.
Embodiment 8
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA1-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA1 macro porous crosslinking resin 1.44 grams of embodiment 7 preparations and place 50 milliliters beaker, add 14 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 2.47 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHTA1-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 2.08%.
Embodiment 9
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA1-Br) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHTA1 macro porous crosslinking resin 1.44 grams of embodiment 7 preparations and place 50 milliliters beaker, add 14 ml deionized water and 0.40 gram Potassium Bromide, place ice bath to stir, slowly the chlorine bleach liquor 2.47 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, dropwise back stirring reaction 2 hours in ice bath.Reaction finishes the macro porous crosslinking resin PSHTA1-Br that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state bromine (Br on the iodometric determination resin
+) content be 7.55%.
Embodiment 10
Present embodiment is the preparation that contains (PSHBA) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5,5-T10 and N, and the mol ratio of N-dimethyl butylamine is 1:1.
Take by weighing 5,5-T10 1.18 grams and yellow soda ash 0.98 gram join in 250 milliliters of round-bottomed flasks, and dissolve with 20 ml methanol, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir the N of dropping 98% down, N-dimethyl butyrate amine aqueous solution 0.96 gram was 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHBA that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 4.03 grams.
Embodiment 11
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHBA-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHBA macro porous crosslinking resin 1.99 grams of embodiment 10 preparations and place 50 milliliters beaker, add 20 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 5.94 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHBA-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 3.44%.
Embodiment 12
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHOA) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5,5-T10 and N, and the mol ratio of N-dimethyl octylame is 1:1.
Take by weighing 5,5-T10 1.18 grams and yellow soda ash 0.98 gram join in 250 milliliters of round-bottomed flasks, and dissolve with 20 ml methanol, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir the N of dropping 95% down, N-dimethyl-octa amine aqueous solution 1.53 gram was 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHOA that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 4.47 grams.
Embodiment 13
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHOA-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHOA macro porous crosslinking resin 1.92 grams of embodiment 12 preparations and place 50 milliliters beaker, add 20 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 5.12 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHOA-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 3.55%.
Embodiment 14
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHHA) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5,5-T10 and N, and the mol ratio of N-dimethyl cetylamine is 1:1.
Take by weighing 5,5-T10 1.18 grams and yellow soda ash 0.98 gram join in 250 milliliters of round-bottomed flasks, and dissolve with 20 ml methanol, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir the N of dropping 99% down, N-dimethyl cetylamine solution 2.51 gram was 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHHA that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃, gets product 5.33 grams.
Embodiment 15
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHHA-Cl) of quaternary ammonium salt and halogen amine functional group.
Take by weighing PSHHA macro porous crosslinking resin 1.98 grams of embodiment 14 preparations and place 50 milliliters beaker, add 20 ml deionized water, place ice bath to stir, slowly the chlorine bleach liquor 4.42 of dropping 10% restrains, regulate pH value about 7 with 1N hydrochloric acid simultaneously, drip the back and in ice bath, continued stirring reaction 2 hours.Reaction finishes the macro porous crosslinking resin PSHHA-Cl that after-filtration obtains containing quaternary ammonium salt and halogen amine functional group, and water cleans 6 times, is dried to constant weight then under 45 ℃.By the oxidation state chlorine (Cl on the iodometric determination resin
+) content be 2.10%.
Embodiment 16
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA4) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 1:2.
Take by weighing 5,5-T10 0.71 gram and yellow soda ash 0.59 gram join in 250 milliliters of round-bottomed flasks, and dissolve with 30 ml deionized water, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 2.19 grams down, 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHTA4 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 80 ℃, gets product 3.83 grams.
Embodiment 17
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA5) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 1:1.
Take by weighing 5,5-T10 1.07 grams and yellow soda ash 0.88 gram join in 250 milliliters of round-bottomed flasks, and dissolve with 30 ml deionized water, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 1.64 grams down, 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHTA5 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 80 ℃, gets product 3.75 grams.
Embodiment 18
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA6) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 2:1.
Take by weighing 5,5-T10 1.42 grams and yellow soda ash 1.18 grams join in 250 milliliters of round-bottomed flasks, and dissolve with 30 ml deionized water, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 1.09 grams down, 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHTA6 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 80 ℃, gets product 3.68 grams.
Embodiment 19
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA7) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 3:1.
Take by weighing 5,5-T10 1.60 grams and yellow soda ash 1.33 grams join in 250 milliliters of round-bottomed flasks, and dissolve with 30 ml deionized water, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 0.82 gram down, 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHTA7 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 80 ℃, gets product 3.53 grams.
Embodiment 20
Present embodiment is the preparation that contains the macro porous crosslinking resin (PSHTA8) of quaternary ammonium salt and halogen amine forebody functional group, and wherein reactant 5, and the mol ratio of 5-T10 and Trimethylamine 99 is 5:1.
Take by weighing 5,5-T10 1.78 grams and yellow soda ash 1.47 grams join in 250 milliliters of round-bottomed flasks, and dissolve with 30 ml deionized water, add poly-p-chloromethyl styrene resin 2.82 grams of macro porous crosslinking, stir and to drip 30% trimethylamine aqueous solution 0.55 gram down, 60 ℃ of following stirring reactions 8 hours.Reaction finishes the macro porous crosslinking resin PSHTA8 that after-filtration obtains containing quaternary ammonium salt and halogen amine forebody functional group, and water cleans 6 times, is dried to constant weight then under 80 ℃, gets product 3.42 grams.
Embodiment 21
Present embodiment is the antibiotic effect test that contains the bactericidal polymer of quaternary ammonium salt and halogen amine functional group.
Experiment selects for use intestinal bacteria as bacteria tested, divides following two groups of experiments: blank, raw material p-chloromethyl styrene macroporous polymer cross-linked resin (PS), PSHTA1, PSHTA1-Br, PSHTA2, PSHTA2-Cl, PSHTA2-Br, PSHTA3, PSHTA3-Cl, PSHTA3-Br; Blank, raw material PS, PSHTA2, PSHTA2-Cl, PSHBA-Cl, PSHOA-Cl, PSHHA-Cl.Every group of experiment takes by weighing 0.75 gram sample and puts into 250 milliliters of Erlenmeyer flasks (except the blank group), add 75 milliliters of PBS buffered soln and 0.75 milliliter of bacterium liquid of cultivating 24 hours, place 37 ℃ concussion tank with the concussion of the rotating speed of 200r/min, when 1min, 5min, 10min, get 1 milliliter of supernatant liquor respectively and make gradient dilution, and when diluting for the first time, add an amount of hypo solution in the diluent and reduce the oxidation state halogen that may exist in the supernatant liquor, adopt dull and stereotyped live bacterial count to measure the bacterium colony group number of viable bacteria.The calculation formula of antibiotic rate is:
Antibiotic rate (%)=[(initial bacterium number-one-tenth viable count)/initial bacterium number] * 100%
The antibiotic effect test result sees Table 1 and table 2:
Table 1
Table 2
Claims (14)
1. a class contains the bactericidal polymer of quaternary ammonium salt and halogen amine or halogen amine forebody functional group, it is characterized in that, is made up of high molecular polymer carrier and quaternary ammonium salt functional group and halogen amine or halogen amine forebody, and its structural formula is as follows:
The structural formula of high molecular polymer carrier part is:
Wherein P be can halomethylation high molecular polymer, Y is Cl, Br, I or OH, k be in every gram bactericidal polymer not with the monochloromethyl of tertiary amine and the reaction of halogen amine forebody and the mmole number of the hydroxymethyl that hydrolysis generates thereof, be 0～3.2 (mmol/g);
R is halogen amine or halogen amine forebody group, and n is the mmole number of halogen amine functional group or halogen amine forebody in every gram bactericidal polymer, is 0.2～3.2 (mmol/g).
The structural formula of quaternary ammonium moiety is:
R
1, R
2, R
3Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl, perhaps R
1, R
2Unite and be C
3-C
7Cycloalkyl or cycloolefin group; X
-aComprise F
-, Cl
-, Br
-, I
-, OH
-, CO
3 2-, SO
3 2-, SO
4 2-, NO
3 -, ClO
-, BrO
-, I
3 -, ClO
3 -, ClO
4 -, HCOO
-, CH
3COO
-, a is the valency of X; M is the mmole number of quaternary ammonium salt functional group in every gram bactericidal polymer, is 0.2～3.2 (mmol/g).
2. according to the described bactericidal polymer of claim 1, it is characterized in that described polymer P that can halomethylation comprises gel-type and the macroporous ion-exchange resin that polystyrene, polystyrene resin, vinylbenzene and divinylbenzene copolymerization obtain; The degree of crosslinking of gel type resin is 1～20%; The degree of crosslinking of macroporous ion-exchange resin is 1～20%.
3. according to the described bactericidal polymer of claim 1, it is characterized in that the degree of crosslinking of gel type resin is 1～6%; The degree of crosslinking of macroporous ion-exchange resin is 1～8%.
4. according to the described bactericidal polymer of claim 1, it is characterized in that k is that 0.3～1.5, n is that 1.0～2.4, m is 0.5～1.9.
5. according to the described bactericidal polymer of claim 1, it is characterized in that the substituent chemical structure of described R is suc as formula (I)～formula (VI) shown in each,
R wherein
1' and R
2' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl, halogen; Perhaps R
1' and R
2' unite and constitute C
3-C
7Cycloalkyl or cycloolefin group; X
1' and X
2' be hydrogen or halogen.
6. according to the described bactericidal polymer of claim 1, it is characterized in that the substituent chemical structure of described R is suc as formula (VII)～formula (XII) shown in each,
Wherein, R
3', R
4', R
5', R
6' and R
7' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl or halogen, perhaps R
3' and R
4' associating and R
5' and R
6' unite and be C
3-C
7Cycloalkyl or cycloolefin group, X
3' and X
4' be hydrogen or halogen.
7. the preparation method of any described bactericidal polymer of claim 1～6 is characterized in that, comprises following reactions steps:
1) contain the preparation of the polymkeric substance of quaternary ammonium salt and halogen amine forebody functional group:
Tertiary amine, halogen amine forebody, alkali are joined the polymer P-CH that contains halomethylation in 10:1～100:1～100 in molar ratio
2In the organic solvent or water of Y (Y=Cl, Br, I), 10 ℃～150 ℃ reactions 2 to 48 hours, obtain to contain the polymkeric substance of quaternary ammonium salt and halogen amine forebody functional group behind the filtration washing, oven dry below 100 ℃;
2) contain the preparation of the polymkeric substance of quaternary ammonium salt and halogen amine functional group:
The polymkeric substance that will contain quaternary ammonium salt and halogen amine forebody functional group joins in the solution of oxidation state halogen that concentration is 0.10wt%～10.00wt%, regulator solution pH value is between 2-13,-15 ℃～30 ℃ reactions 10 minutes to 10 hours, obtain to contain the polymkeric substance of quaternary ammonium salt and halogen amine functional group behind the filtration washing, oven dry below 50 ℃.
8. the preparation method of the described bactericidal polymer of claim 7 is characterized in that, organic solvent is C in the step 1)
1～C
6A kind of or any several mixture in alcohol, acetone, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), the dimethyl formamide.
9. the preparation method of the described bactericidal polymer of claim 8 is characterized in that, organic solvent is C1～C4 alcohol in the step 1), and temperature of reaction is 30 ℃～80 ℃, and the reaction times is 8～16 hours; Perhaps, organic solvent is water or dimethyl formamide, and temperature of reaction is 40 ℃～90 ℃, and the reaction times is 8～16 hours.
10. the preparation method of the described bactericidal polymer of claim 7 is characterized in that, the chemical structural formula of tertiary amine described in the step 1) is as follows:
R
1, R
2, R
3Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl, perhaps R
1, R
2Unite and be C
3-C
7Cycloalkyl or cycloolefin group.
11. the preparation method of the described bactericidal polymer of claim 7 is characterized in that, the chemical structural formula of the amine of halogen described in step 1) forebody is as following shown in each:
Wherein, R
1', R
2', R
3', R
4', R
5', R
6' and R
7' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or haloolefin group, C
1-C
8Hydroxyalkyl or aminoalkyl group, phenyl, aryl, hydrogen, hydroxyl or halogen, perhaps R
1' and R
2', R
3' and R
4' and R
5' and R
6' unite and be C
3-C
7Cycloalkyl or cycloolefin group.
12. the preparation method of the described bactericidal polymer of claim 7 is characterized in that, alkali described in the step 1) comprises sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium ethylate and potassium ethylate.
13. the preparation method of the described bactericidal polymer of claim 7 is characterized in that step 2) described in the oxidation state halogen comprise Cl
2, Br
2, NaClO, NaBrO, KClO and KBrO.
14. any described bactericidal polymer of claim 1-6 is used for sterilization.
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| CN103880991A (en) * | 2014-03-11 | 2014-06-25 | 上海师范大学 | High molecular polymer material having anti-bacterial and trace element slow release functions and preparation method thereof |
| CN105601778A (en) * | 2016-01-19 | 2016-05-25 | 江南大学 | Annular halamine type polymeric antibacterial agent containing quaternary ammonium group and preparation method and application of polymeric antibacterial agent |
| CN106359383A (en) * | 2016-08-08 | 2017-02-01 | 山东科技大学 | Bifunctional bactericide containing double bond, quaternary ammonium salt and halamine, and preparation method and application thereof |
| CN114766503A (en) * | 2022-05-06 | 2022-07-22 | 上海循诺环保科技有限公司 | Preparation and application methods of bactericide for reverse osmosis system |
| CN115926297A (en) * | 2023-01-30 | 2023-04-07 | 广东中港印务有限公司 | Antibacterial food packaging film and preparation method thereof |
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| TW200734406A (en) * | 2005-08-11 | 2007-09-16 | Univ Auburn | N-halamine/quaternary ammonium polysiloxane copolymers |
| CN102796214A (en) * | 2012-06-08 | 2012-11-28 | 上海师范大学 | Bactericidal polymer containing quaternary ammonium salt and halogen amine or halogen amine precursor functional group and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880991A (en) * | 2014-03-11 | 2014-06-25 | 上海师范大学 | High molecular polymer material having anti-bacterial and trace element slow release functions and preparation method thereof |
| CN103880991B (en) * | 2014-03-11 | 2016-09-07 | 上海师范大学 | A kind of have antibacterial macromolecule polymer material with trace-element slow-release function and preparation method thereof |
| CN105601778A (en) * | 2016-01-19 | 2016-05-25 | 江南大学 | Annular halamine type polymeric antibacterial agent containing quaternary ammonium group and preparation method and application of polymeric antibacterial agent |
| CN106359383A (en) * | 2016-08-08 | 2017-02-01 | 山东科技大学 | Bifunctional bactericide containing double bond, quaternary ammonium salt and halamine, and preparation method and application thereof |
| CN114766503A (en) * | 2022-05-06 | 2022-07-22 | 上海循诺环保科技有限公司 | Preparation and application methods of bactericide for reverse osmosis system |
| CN115926297A (en) * | 2023-01-30 | 2023-04-07 | 广东中港印务有限公司 | Antibacterial food packaging film and preparation method thereof |
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