CN101628952B - Method for preparing uramine-type macromolecule anti-bacterial agent - Google Patents
Method for preparing uramine-type macromolecule anti-bacterial agent Download PDFInfo
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- CN101628952B CN101628952B CN2009101445603A CN200910144560A CN101628952B CN 101628952 B CN101628952 B CN 101628952B CN 2009101445603 A CN2009101445603 A CN 2009101445603A CN 200910144560 A CN200910144560 A CN 200910144560A CN 101628952 B CN101628952 B CN 101628952B
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 31
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- -1 dope Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000007306 functionalization reaction Methods 0.000 claims description 28
- 238000005303 weighing Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 150000001298 alcohols Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- NNMVCZMTGPUMHP-UHFFFAOYSA-N 1-(n,n'-dimethylcarbamimidoyl)-1,2,3,3-tetramethylguanidine Chemical compound CNC(=NC)N(C)C(=NC)N(C)C NNMVCZMTGPUMHP-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 13
- 239000004033 plastic Substances 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 13
- 229960004198 guanidine Drugs 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229920002413 Polyhexanide Polymers 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000003643 water by type Substances 0.000 description 10
- 230000003115 biocidal effect Effects 0.000 description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 230000002045 lasting effect Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010064696 N,O-diacetylmuramidase Proteins 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ISNICOKBNZOJQG-UHFFFAOYSA-O guanidinium ion Chemical compound C[NH+]=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a method for preparing an uramine-type macromolecule anti-bacterial agent, comprising two steps as follows: A, mixing any one solution of guanidine hcl, Polyhexamethyleneguanidine chloride and polyhexamethylene biguanide hydrochloride with maleic anhydride solution; introducing nitrogen for constant-temperature water bath reaction to obtain functional uramine salt; B, mixing functional uramine salt solution with acrylamide and/or styrene for constant-temperature water bath reaction to obtain ivory-white stringy liquid; depositing soft white solid with solvent for vacuum drying to obtain ivory-white bulk uramine-type copolymer, i.e, uramine-type macromolecule anti-bacterial agent. The uramine-type macromolecule anti-bacterial agent has remarkable effect and simple synthesis process, ensures that the anti-bacterial group is hard to move and the processing thermal stability is excellent through copolymerization on macromolecule long chain. The invention can be widely used in fields of plastic, dope, powder dope, rubber, wood plastic, rubber plastic, spinning, water processing, and the like.
Description
Technical field
The invention belongs to the sterilant technical field, be specifically related to a kind of preparation method of uramine-type macromolecule anti-bacterial agent.
Background technology
Along with the raising of China's living standards of the people, low pollution, healthy macromolecule product are approved by masses.People are by the PP that discovers to environmental microorganism, the bacterium that surface of plastic products such as PS are polluted and grown, and the plastics that use in the communal facility place are because the frequent contact meeting of crowd constitutes certain threat to using with the people's that contact them health.Antibacterial plastic product is in Japan at present, the widespread use of Korea S and American-European countries, more domestic antimicrobial prods exist easy to change, bad dispersibility in base material, antibacterial ion or group easily move, and the reason of poor heat stability has limited the widespread use of antibiotic plastic.
Present of a great variety of antiseptic-germicide, the kind of antiseptic-germicide can be divided into five big classes, inorganic antiseptic, organic antibacterial agent, inorganic and organic composite antibiotic agent, natural antibacterial agent, polymer antibacterial agent.Though domestic antimicrobial prod has been obtained a lot of gratifying breakthroughs at present, even exist some problems: 1, the easy oxidation of silver-series antibacterial agent, light stability is poor, be not easy to tinted material, owing to reason duration of service of oxidation of a specified duration later goods can turn black, and the heavy metal metal ionic that discharges in the use is on the increase, and easily environment is polluted, and cost is relatively more expensive.2, titanium dioxide series antibacterial agent, single use, limitation is too strong, can only could use under light-catalysed condition.3, natural organic antibacterial agent such as chitosan, the poor heat resistance of chitosan and derivative antibacterial agent thereof, antibacterial effect is not lasting, is not suitable for being used in the industry that plastics etc. are had relatively high expectations to thermotolerance.4, quaternary ammonium salt antiseptic-germicide (comprising quaternary ammonium salt polymer antiseptic-germicide), poor heat resistance, antibacterial effect is not lasting, is not suitable for being used in the industry that plastics etc. are had relatively high expectations to thermotolerance, and life-time service can produce certain resistance and use after resistates produce certain toxicity.5, season phosphonium salt class antiseptic-germicide (comprising season phosphonium salt polymer antiseptic-germicide), because synthetic materials is limited, price is higher, and synthesis condition is more harsh with respect to quaternary ammonium salt.
The advantage of polymer antiseptic-germicide is with antibioticization of polymer itself, is with having the function monomer of anti-microbial property specifically, and by grafting, means such as copolymerization are incorporated into the antibacterial group on the polymer long-chain.Number of patent application is a patent report of 4 25154.1979 U.S., contains
Group is kind of a good sterilant, is widely applied in the middle of the farm crop.Number of patent application is a patent report of 3 606 294.1988 Germany, contains
Group is kind of a good antiseptic-germicide.There is poor heat stability in more existing polymer antiseptic-germicides, are applied in to disperse inhomogeneously in the plastics, and antibiotic ion or group be the shortcoming of migration easily.
Summary of the invention
In order to solve existing polymer antiseptic-germicide poor heat stability, to be applied in and to disperse the easily problem of migration of inhomogeneous, antibiotic ion or group in the plastics, the present invention is intended to utilize inexpensive raw material, and a kind of preparation method who has efficient, long-acting, safe, stable, low toxicity, good dispersion, is easy to the uramine-type macromolecule anti-bacterial agent of high temperature process is provided.
Concrete operations step of the present invention is as follows:
The preparation method of uramine-type macromolecule anti-bacterial agent comprises following operation steps:
(1) the first step complex functionality guanidinesalt:
Take by weighing 15 parts of maleic anhydrides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 27.3% maleic anhydride solution;
Take by weighing 20 parts of Guanidinium hydrochlorides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 33.3% guanidine hydrochloride solution;
Take by weighing 30 parts of poly-hexamethyl guanidinesalt hydrochlorates and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 42.9% poly-hexamethyl guanidinesalt acid salt solution;
Take by weighing 40 parts of poly-hexamethyl biguanide hydrochlorides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 50% poly-hexamethyl biguanide hydrochloride solution;
Getting in the guanidine hydrochloride solution of preparation, poly-hexamethyl guanidinesalt acid salt solution, the poly-hexamethyl biguanide hydrochloride solution any one mixes with maleic anhydride solution, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 50～85 ℃ water bath with thermostatic control, continue stirring reaction 5～7h, obtain flaxen functionalization guanidinesalt;
(2) second one-step functional guanidinesalts with can regulate the polar monomer copolymerization:
Take by weighing 45 parts of vinylbenzene and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 37.5% styrene solution;
Take by weighing 50 parts of acrylamides and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 40% acrylamide soln;
Take by weighing 30 parts of functionalization guanidinesalts and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution of preparation is carried out binary with styrene solution and/or acrylamide soln or ternary is mixed; Feed nitrogen, add initiator, add the copolymerization solvent, continue to stir in 70-95 ℃ water bath with thermostatic control and carry out binary or terpolymer, reaction 6-10h obtains ivory-white stringy liquid; Going out white softish white solid with solvent precipitation is the guanidine analog copolymer, and in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains the copolymerization product of white blocky guanidinesalt, i.e. guanidine family macromolecule antiseptic-germicide;
Institute's synthetic guanidine family macromolecule antiseptic-germicide is white blocks of solid, is dissolved in methyl-sulphoxide, and N, N dimethyl formamide are water insoluble, dehydrated alcohol, acetone, toluene, ethyl acetate;
Described copolymerization solvent is any one in dehydrated alcohol, the toluene;
Described initiator is dicumyl peroxide (DCP) or Diisopropyl azodicarboxylate (AIBN), and initiator amount is 2.5 parts.
The solvent of used precipitating guanidinesalt multipolymer be in distilled water, the dehydrated alcohol any one.
The advantage of polymer antiseptic-germicide is with antibioticization of polymer itself, is with having the function monomer of anti-microbial property specifically, and by grafting, means such as copolymerization are incorporated into the antibacterial group on the polymer long-chain.Uramine-type macromolecule anti-bacterial agent of the present invention is owing to be by being incorporated on the polymer long-chain with the means that can regulate the polar monomer copolymerization with the antibacterial group, thereby have efficient, wide spectrum, non-volatile, it is more lasting that antibiotic group is difficult for the migration antibacterial, be easy to high temperature process, plurality of advantages such as favorable dispersity is easy to store, and is cheap, therefore have wide prospect more, the present situation of present domestic polymer antibacterial agent is in the starting stage.
Compared with prior art, the present invention has following excellent effect: (1) uramine-type macromolecule anti-bacterial agent antibacterial effect of the present invention is more remarkable; (2) preparation technology is simple, only needs for two steps can obtain; (3) guanidine family macromolecule antiseptic-germicide of the present invention can reach 369 ℃ through thermogravimetric analyzer (TG) test decomposition temperature, and good thermal stability can satisfy high temperature process, the difficult degraded; (4) antiseptic-germicide of the present invention is obtained by copolymerization by the antibacterial group, makes antibiotic group be difficult for migration, and antibacterial effect is more lasting; (5) be difficult for oxidized and variable color through actual observation with the product of antiseptic-germicide of the present invention institute processing and preparing; (6) uramine-type macromolecule anti-bacterial agent of the present invention's preparation can be widely used in plastics, coating, and powder coating, rubber, wood is moulded, rubber and plastic, weaving, fields such as water treatment.
Antibiotic mechanism is: the hydrate of guanidine is a kind of monoatomic base, and its alkalescence is equivalent to NaOH.Guanidine obtains to form stable positively charged ion behind the proton, guanidinium ion and acid ion are combined into guanidinesalt, organic guanidine compound purposes the most widely is as sterilant, and be many-sided to the influence of mushroom, general by influencing the growth division of bacterium, destroy cell walls, suppress microbial respiratory and reach the antimicrobial purpose.Thereby the negatively charged ion generation electrostatic adhesion on the positively charged ion of Guanidinium hydrochloride and microorganism cells surface has hindered the effect of cell N,O-Diacetylmuramidase, the destroy microorganisms surface structure, thus reached the sterilization purpose.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
The preparation method of uramine-type macromolecule anti-bacterial agent comprises following operation steps:
A, the 15g maleic anhydride added to be made into massfraction in the 40g dehydrated alcohol be 27.3% maleic anhydride solution, with being made into massfraction in the 20g Guanidinium hydrochloride adding 40g dehydrated alcohol is 33.3% guanidine hydrochloride solution, described two kinds of solution are added in the there-necked flask, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 60 ℃ of waters bath with thermostatic control, react 7h, obtain faint yellow functionalization guanidinesalt
B, take by weighing 45g vinylbenzene and be dissolved in that to be made into massfraction in the 75g dehydrated alcohol be 37.5% styrene solution; Take by weighing 30g functionalization guanidinesalt and be dissolved in that to be made into massfraction in the 75g dehydrated alcohol be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution of preparation is mixed with styrene solution and carries out copolymerization, the Diisopropyl azodicarboxylate (AIBN) that adds 2.5g, feed nitrogen, in 95 ℃ of waters bath with thermostatic control, react 6h, obtain white pliable solid with the distilled water precipitating, in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains milky block guanidine analog copolymer and is uramine-type macromolecule anti-bacterial agent.
Embodiment 2
A, the 15g maleic anhydride is added 40g, and to be made into massfraction in the acetone be 27.3% maleic anhydride solution, the poly-hexamethyl guanidinesalt hydrochlorate adding of 30g 40g is made into massfraction in the acetone be 42.9% poly-hexamethyl guanidinesalt acid salt solution, described two kinds of solution are added in the there-necked flask, stir, add spherical condensation tube simultaneously, feed nitrogen 30 minutes, and in 75 ℃ of waters bath with thermostatic control, reacted 6h, obtain flaxen functionalization guanidinesalt;
B, take by weighing 45g vinylbenzene and be dissolved in that to be made into massfraction in the 75g toluene be 37.5% styrene solution, take by weighing 30g functionalization guanidinesalt and be dissolved in that to be made into massfraction in the 75g toluene be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution and the styrene solution of preparation are carried out copolymerization, and adding 2.5g dicumyl peroxide (DCP), feed nitrogen, in 85 ℃ of waters bath with thermostatic control, react 7h, obtain white pliable solid with the dehydrated alcohol precipitating, in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains milky block guanidine analog copolymer and is uramine-type macromolecule anti-bacterial agent.
Embodiment 3
A, the 15g maleic anhydride added to be made into massfraction in the 40g dehydrated alcohol be 27.3% maleic anhydride solution, with being made into massfraction in the 20g Guanidinium hydrochloride adding 40g dehydrated alcohol is 33.3% guanidine hydrochloride solution, two kinds of solution are added in the there-necked flask, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 85 ℃ of waters bath with thermostatic control, react 5h, obtain flaxen functionalization guanidinesalt
B, take by weighing 45g vinylbenzene and be dissolved in that to be made into massfraction in the 75g toluene be 37.5% styrene solution, take by weighing 30g functionalization guanidinesalt and be dissolved in that to be made into massfraction in the 75g toluene be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution of preparation is mixed with styrene solution and carries out copolymerization, add 2.5g Diisopropyl azodicarboxylate (AIBN) again, feed nitrogen, in 70 ℃ of waters bath with thermostatic control, react 9h, obtain white pliable solid with the dehydrated alcohol precipitating, in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains milky block guanidine analog copolymer and is uramine-type macromolecule anti-bacterial agent.
Can prepare antibiotic and fire-retardant economic benefits and social benefits functional master batch according to following prescription.As: polypropylene 100g, talcum powder 15g, POE10g, TDE 24g, antimonous oxide 8g.Add 1.5g respectively therein, 3g, 4.5g, 6g guanidine family macromolecule antiseptic-germicide obtains antibiotic fire-retardant economic benefits and social benefits functional master batch in 170 ℃ of two rod mills or injection moulding machine blend.
Embodiment 4
A, the 15g maleic anhydride is added 40g, and to be made into massfraction in the acetone be 27.3% maleic anhydride solution, the poly-hexamethyl biguanide hydrochloride adding of 40g 40g is made into massfraction in the acetone be 50% poly-hexamethyl biguanide hydrochloride solution, described two kinds of solution are added in the there-necked flask, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 50 ℃ of waters bath with thermostatic control, react 6h, obtain flaxen functionalization guanidinesalt
B, take by weighing 45g vinylbenzene and be dissolved in that to be made into massfraction in the 75g toluene be 37.5% styrene solution; Take by weighing the 50g acrylamide and be dissolved in that to be made into massfraction in the 75g toluene be 40% acrylamide soln; Take by weighing 30g functionalization guanidinesalt and be dissolved in that to be made into massfraction in the 75g toluene be 28.6% functionalization guanidinesalt solution;
Functionalization guanidinesalt solution and styrene solution and the acrylamide soln of preparation are carried out terpolymer, add 2.5g dicumyl peroxide (DCP), feed nitrogen, in 75 ℃ of waters bath with thermostatic control, react 8h, obtain white pliable solid with the dehydrated alcohol precipitating, in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains milky block guanidine analog copolymer and is uramine-type macromolecule anti-bacterial agent.
Embodiment 5
A, the 15g maleic anhydride added to be made into massfraction in the 40g dehydrated alcohol be 27.3% maleic anhydride solution, with being made into massfraction in the 20g Guanidinium hydrochloride adding 40g dehydrated alcohol is 33.3% guanidine hydrochloride solution, described two kinds of solution are added in the there-necked flask, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 70 ℃ of waters bath with thermostatic control, react 7h, obtain flaxen functionalization guanidinesalt
B, take by weighing the 50g acrylamide and be dissolved in that to be made into massfraction in the 75g dehydrated alcohol be 40% acrylamide soln; Take by weighing 30g functionalization guanidinesalt and be dissolved in that to be made into massfraction in the 75g dehydrated alcohol be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution and the acrylamide soln of preparation are carried out copolymerization, the Diisopropyl azodicarboxylate (AIBN) that adds 2.5g, feed nitrogen, in 90 ℃ of waters bath with thermostatic control, react 10h, obtain white pliable solid with the distilled water precipitating, in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains milky block guanidine analog copolymer and is uramine-type macromolecule anti-bacterial agent.
With 3g, 6g, 9g, 12g, uramine-type macromolecule anti-bacterial agent respectively with 300g vibrin, 300g Resins, epoxy, 6g flow agent (E-12) 503, the 3g st-yrax grinds, again with extruding under 110 ℃ of conditions of forcing machine, through pulverizing, after the electrostatic spraying, solidify 20min down at 180 ℃, promptly get antibacterial powder paint.
Claims (2)
1. the preparation method of uramine-type macromolecule anti-bacterial agent is characterized in that comprising following operation steps:
(1) the first step complex functionality guanidinesalt:
Take by weighing 15 parts of maleic anhydrides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 27.3% maleic anhydride solution;
Take by weighing 20 parts of Guanidinium hydrochlorides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 33.3% guanidine hydrochloride solution;
Take by weighing 30 parts of poly-hexamethyl guanidinesalt hydrochlorates and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 42.9% poly-hexamethyl guanidinesalt acid salt solution;
Take by weighing 40 parts of poly-hexamethyl biguanide hydrochlorides and be dissolved in that to be made into massfraction in 40 parts of dehydrated alcohols or the acetone be 50% poly-hexamethyl biguanide hydrochloride solution;
Getting in the guanidine hydrochloride solution of preparation, poly-hexamethyl guanidinesalt acid salt solution, the poly-hexamethyl biguanide hydrochloride solution any one mixes with maleic anhydride solution, stir, add spherical condensation tube simultaneously, fed nitrogen 30 minutes, in 50～85 ℃ water bath with thermostatic control, continue stirring reaction 5～7h, obtain flaxen functionalization guanidinesalt;
(2) second one-step functional guanidinesalts with can regulate the polar monomer copolymerization:
Take by weighing 45 parts of vinylbenzene and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 37.5% styrene solution;
Take by weighing 50 parts of acrylamides and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 40% acrylamide soln;
Take by weighing 30 parts of functionalization guanidinesalts and be dissolved in that to be made into massfraction in 75 parts of dehydrated alcohols or the toluene be 28.6% functionalization guanidinesalt solution;
The functionalization guanidinesalt solution of preparation is carried out binary with styrene solution and/or acrylamide soln or ternary is mixed; Feed nitrogen, add initiator, add the copolymerization solvent, continue to stir in 70-95 ℃ water bath with thermostatic control and carry out binary or terpolymer, reaction 6-10h obtains ivory-white stringy liquid; Going out white softish white solid with solvent precipitation is the guanidine analog copolymer, and in vacuum drying oven 60 ℃, dry 24h under the 0.2MPa obtains the copolymerization product of white blocky guanidinesalt, i.e. uramine-type macromolecule anti-bacterial agent;
Institute's synthetic uramine-type macromolecule anti-bacterial agent is white blocks of solid, is dissolved in methyl-sulphoxide, and N, N dimethyl formamide are water insoluble, dehydrated alcohol, acetone, toluene, ethyl acetate;
Described copolymerization solvent is any one in dehydrated alcohol, the toluene;
Described initiator is dicumyl peroxide (DCP) or Diisopropyl azodicarboxylate (AIBN), and initiator amount is 2.5 parts.
2. the preparation method of uramine-type macromolecule anti-bacterial agent according to claim 1 is characterized in that: the solvent of used precipitating guanidine analog copolymer be in distilled water, the dehydrated alcohol any one.
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