CN102391299A - Preparation method for organosilicon quaternary ammonium salt composite and application thereof - Google Patents
Preparation method for organosilicon quaternary ammonium salt composite and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method for organosilicon quaternary ammonium salt composite and application thereof. The preparation method is characterized by comprising the following steps: by means of taking single long chain alkyl dimethyl tertiary amine, r-allyl chloride trimethoxy silane and mixed solvent as raw materials at the molar ratio of 1.0:(1.03-1.05):(7.0-8.0), preparing the single long chain alkyl dimethyl organosilicon quaternary ammonium salt, wherein the mixed solvent comprises carbinol and ethylene glycol; combining a plurality of single long chain alkyl dimethyl organosilicon quaternary ammonium salt monomers at a ratio; and adding a quaternary ammonium salt microcapsule at a certain ratio to prepare the organosilicon quaternary ammonium salt composite. The organosilicon quaternary ammonium salt composite simultaneously performs three actions in the specific application: firstly, the organosilicon quaternary ammonium salt sterilizes and kills pathogenic bacteria on the surface to carry out hazard-free treatment on the pathogenic bacteria; secondly, after the surface coating is dried, the organosilicon quaternary ammonium salt can generate permanent self-cleaning bactriostasis action; and thirdly, the quaternary ammonium salt microcapsule in the composite is slowly released to perform the action of actively sterilizing.
Description
Technical field
The present invention relates to the preparation method and the application thereof of a kind of different carbon chain optimization screening combination, two property, High-Efficient Organic silicon quaternary ammonium salt, belong to surperficial epidemic prevention technology and public health field.
Background technology
Technical characterictic and difference with the prior art for explanation the present invention " organosilicon quaternary ammonium salt optimum combination thing "; At first need clarify two professional technology and concept problems of obscuring easily: (one) non-stripping property antimicrobial surface technology has typical chemically bonded characteristic and self-cleaning antibacterial, but does not possess initiatively sterilization or epidemic prevention function.(2) technological evaluation method and the standard that is adopted of non-stripping property antibacterial surface is " AATCC flask concussion method "; The non-stripping contact germicidal action that promptly under laboratory flask concussion condition, produces; And in practical application, can't not possess " concussion " condition; So non-stripping property antibacterial surface product is difficult to reach the sterilization effect of reality.The argent ionic " safe disinfection plate " that the DC-5700 octadecyl list long-chain organosilicon quaternary ammonium salt that typical case's typical example is produced for Dow corning company, U.S. money base safeguard system company produce is 97197592.2 " senior surface disinfection agent " etc. with the patent No. of French Curie husband institute invention, and it is technological all to belong to simple non-stripping property antibacterial surface.
Organosilicon quaternary ammonium salt optimum combination thing of the present invention is to be combined by the different carbon chain quaternary ammonium salt, and is added with the slow-release type microcapsule quaternary ammonium salt.Therefore, have the dual nature of non-stripping and slowly-releasing, have clean surfaces and efficient initiatively germ-resistant function simultaneously, this is the essential distinction of the present invention and prior art.
In addition; The present invention's's " organosilicon quaternary ammonium salt optimum combination thing " surface disinfection evaluation of effect method is also different with simple non-stripping property antimicrobial surface; Except that adopting flask foam stability method, also adopt simultaneously " carrier immersion quantitative disinfecting test method 2.1.1.7.5 " among the P104 " suspension quantitative disinfecting test method 2.1.10.2.3 " and P33 in ministry of Health of China 2002 version " disinfection technology standard ".Also have, it is also different with DC-5700 organosilicon quaternary ammonium salt and other non-stripping property antibacterial surface technology to be tried bacterial classification, is tried bacterial classification except that selecting for use bacterial reproduction external, also comprises withered grass black bacillus gemma (ATCC9372) and SARS virus.
Look into newly according to computingmachine, do not see two organic silicon quaternary ammonium salt surface disinfection agent that different carbon chain combination of the present invention is arranged at present both at home and abroad as yet.
As everyone knows, the single long-chain octadecyl of commodity DC-5700 by name organosilicon quaternary ammonium salt ([(CH
30)
3Si (CH
2)
3N (CH
3)
2(C
18H
37)]
+Cl
-) the earliest by Dow corning company (DOW Corning) development and production, belong to typical non-stripping property clean surfaces antimicrobial technology.(annotating: do not possess initiatively epidemic prevention and sterilizing function)
Because the DC-5700 product has unique chemical structure, non-dissolution characteristic and excellent surface self-cleaning anti-microbial effect, simultaneously, the security of use is very good.Early eighties, the DC-5700 product is comprised antibiotic clothes, deodorization footwear or socks, medical sheet etc. by the exploitation that Japan is widely used in self-cleaning health textiles.
After outburst " SARS virus " and 2008 outburst " bird flu of H1N1 type " epidemic situations in 2003, the applied research of DC-5700 organosilicon quaternary ammonium salt has reached new climax.
By in June, 2011, synthetic (Chinese) document of visible organosilicon quaternary ammonium salt is about 46 pieces on the internet, a piece of writing surplus the applied research document 80,1 piece of Chinese invention patent.But; If anatomize and to find from the angle of professional technique; Most investigators fail really to understand the surperficial antibiosis characteristic of organosilicon quaternary ammonium salt, have ignored the single long-chain octadecyl of DC-5700 organosilicon quaternary ammonium salt not have the active germicidal action under " non-concussion contact " condition problem and reason.So not seeing so far has pair organosilicon quaternary ammonium salt to carry out the invention technology of substantial improvements, most researchs are repeatability or the research that does not have practical significance.With Chinese invention patent 200510045294.0 organosilicon quaternary ammonium salts is example; Its invention core is to have substituted methyl alcohol with absolute ethyl alcohol; The character of ultimate aim thing and product, usefulness, purposes etc. all do not have substantial improvement, are still single long-chain octadecyl organosilicon quaternary ammonium salt.
2003 the outburst " SARS virus " epidemic situations after, once had enterprise declare " DC-5700 organosilicon quaternary ammonium salt and argent ion surface to virus and gemma the epidemic prevention effect is arranged, be the heavy duty detergent sterilant ....We once adopted " the carrier immersion quantitative disinfecting test method 2.1.1.7.5 " among the P104 " suspension quantitative disinfecting test method 2.1.10.2.3 " and P33 in 2002 version " disinfection technology standard ".DC-5700 organosilicon quaternary ammonium salt compsn and made carrier have been carried out experimental verification; The result shows; No matter be DC-5700 organosilicon quaternary ammonium salt (methanol solvate); Or Chinese invention patent 200510045294.0 organosilicon quaternary ammonium salts (alcohol solvent), or " senior surface disinfection agent " No. 97197592.2 patents of French Curie husband institute invention, and U.S. money base company " silver is sterilizing board " of producing; They only have the surface self-cleaning anti-microbial effect, and so-called germicidal action depends on " flask concussion " subsidiary conditions in the laboratory more.In addition, even under the subsidiary conditions of laboratory " flask concussion ", withered grass black bacillus gemma (ATCC9372) (like anthrax bacillus) that simple antibacterial surface technical antagonism property is stronger and virus is not effect also.
In addition, many memoirs or Chinese invention patent 200510045294.0 documents, all describing has the potassiumiodide of employing to make organosilicon quaternary ammonium salt synthetic catalyzer.But, find that in production application potassiumiodide is also not obvious to the catalyzed reaction effect of organosilicon quaternary ammonium salt, the reaction times that adds potassiumiodide still is not less than 100h.Also find in addition, adopt potassiumiodide catalysis synthetic organosilicon quaternary ammonium salt when treatment of textiles, cause the textiles flavescence easily.
According to China. the Ministry of Health 2002 version " disinfection technology standard " is to chemostefilant usefulness evaluation criteria and terminological interpretation: " chemostefilant that only bacterial propagule is had a killing action is the poor efficiency series products; The product that withered grass black bacillus gemma (ATCC9372) is had killing action can be decided to be the heavy duty detergent series products.”。And the like, non-stripping antibacterial surface technology and effects such as DC-5700 organosilicon quaternary ammonium salt to withered grass black bacillus gemma (ATCC9372) and not effect of virus, do not possess the technical requirements of efficient and Antiepidemic sterilizing.Thus, should belong to self-cleaning sanitary product class.
The contriver is through lot of experiments; And the comparison world and domestic relevant chemical disinfection, sterilization, anti-(pressing down) bacterium technological standard and requirement; The real technological deficiency of the antibacterial surface product technology that discovery DC-5700 organosilicon quaternary ammonium salt etc. are simple is: (1) single non-dissolution characteristic has determined its single clean surfaces sexual function; (2) single organosilicon quaternary ammonium salt carbon-chain structure has determined the low and application limit of its antibiosis usefulness.
Summary of the invention
The objective of the invention is that No. 97197592.2 " senior surface disinfection agent " of " silver is the safe disinfection plate " of producing to existing DC-5700 organosilicon list long chain quaternary, U.S. money base safeguard system company, the invention of French Institut Curie and chemical structure that Chinese 200510045294.0 patents of invention exist are single, single property, effect is single, antibiosis usefulness is low, generated time is long, production cost is high, purposes is limited, the textiles after handling is prone to technological deficiencies such as flavescence; A kind of optimum combination and preparation method of organosilicon quaternary ammonium salt different carbon chain are provided, have comprised the method that adopts mixed solvent reaction and optimum combination to use.
The present invention has not only changed the single carbon-chain structure of existing organosilicon quaternary ammonium salt; Change the optimum combination of many carbochains into by single long-chain, changed the single character of existing organosilicon quaternary ammonium salt simultaneously, change into two property by simple non-stripping property; Promptly have non-dissolution characteristic, have certain slow-releasing again.Thus; Not only has surface of good self-cleaning hygienic function; And increased effect and surperficial epidemic prevention function to withered grass black bacillus gemma (ATCC9372) and virus, and really changed structure, character and the antibiosis usefulness of existing organosilicon quaternary ammonium salt, widened its scope of application.
In addition, the present invention adopts mixed solvent to substitute potassium iodide catalyst, makes the reaction times of organosilicon quaternary ammonium salt foreshorten to 50-70h by original 110h.
The present invention comprises three partial contents altogether, the one, and the monomeric compound method of organosilicon quaternary ammonium salt; The 2nd, the monomeric Combination application of organosilicon quaternary ammonium salt; The 3rd, the application of product is done respectively with narration below.
One, the monomeric compound method of organosilicon quaternary ammonium salt
The present invention adopts mixed solvent and one-step technology; Synthetic respectively 12,14 and the organosilicon quaternary ammonium salt monomer of three different carbon chains such as octadecyl; Then the organosilicon quaternary ammonium salt monomer is optimized combination; Add a certain proportion of slow-release type microcapsule quaternary ammonium salt again, can realize the purpose of organosilicon quaternary ammonium salt optimum combination thing of the present invention.Concrete grammar is following.
(1) the monomeric synthetic and preparation process of dodecyl organosilicon quaternary ammonium salt:
1, calculate the add-on of each reaction mass in molar ratio, wherein, dodecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent=1.0:1.03-1.05:7.0-8.0.Raw materials used is technical grade, and said mixed solvent is methyl alcohol and terepthaloyl moietie, and wherein methyl alcohol accounts for solvent total amount 80-90%, and terepthaloyl moietie is 10-20%.
2, r-chloropropyl triethoxysilane that measures and mixed solvent are joined earlier in the reaction kettle of band condensation and reflux, airtight, open reaction kettle and heat up stirring velocity 50-70 rev/min.When being warming up to 40 ℃, begin to drip the dodecyl dimethyl tertiary amine, the dropping time is 2-3 hour.Be warming up to 60-70 ℃, keep constant temperature, reaction is 50-70 hour under airtight and mixed solvent reflux state, with potentiometric determination [Cl
-] content and calculate reaction process, be benchmark with the dodecyl dimethyl tertiary amine, reaction is to 90% being terminal point.Generally, drip tertiary amine afterreaction 50-70h certainly, can react completely, obtain dodecyl organosilicon quaternary ammonium salt monomer.
3, reduce to normal temperature after, with the PH to 5.5-6.5 of dodecyl organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still, homogeneous stirs 10min; Then with the decolouring of 800# diatomite filtration, removal impurity; It is canned to go out still, promptly gets dodecyl organosilicon quaternary ammonium salt monomer finished product, subsequent use.Its molecular formula is: [(CH
3O)
3Si-(CH
2)
3-N (CH
3)
2-C
12H
25]
+Cl
-Molecular weight is: 412.13.
(2) the monomeric synthetic and preparation process of tetradecyl organosilicon quaternary ammonium salt:
1, calculate the add-on of each reaction mass in molar ratio, wherein, tetradecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent (methyl alcohol and terepthaloyl moietie)=1.0:1.03-1.05:7.0-8.0.Raw materials used is technical grade, and said mixed solvent is methyl alcohol and terepthaloyl moietie, and wherein methyl alcohol accounts for the 80-90% of solvent total amount, and terepthaloyl moietie is 10-20%.
2, r-chloropropyl triethoxysilane that measures and mixed solvent are added earlier in the reaction kettle, airtight, open reaction kettle and heat up stirring velocity 50-70 rev/min.When being warming up to 50 ℃, begin to drip the tetradecyl dimethyl tertiary amine, the dropping time is 2-3 hour.Be warming up to 60-75 ℃, keep constant temperature, reaction is 50-70 hour under airtight and methanol mixed solvent refluxing state, with potentiometric determination [Cl
-] content and calculate reaction process, be benchmark with the tetradecyl dimethyl tertiary amine, reaction is fully to 90%.Generally, drip tertiary amine afterreaction 50-70h, can react completely.
3, be reacted to terminal point, after reaction kettle is reduced to normal temperature, with the PH to 5.5-6.0 of organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still; Homogeneous stirs 10min, and with the decolouring of 800# diatomite filtration, removal impurity, it is canned to go out still then; Promptly get tetradecyl organosilicon quaternary ammonium salt monomer finished product, subsequent use.Its molecular formula is: [(CH
3O)
3Si-(CH
2)
3-N (CH
3)
2-C
14H
29]
+Cl
-Molecular weight is: 440.18.
(3) the monomeric synthetic and preparation process of octadecyl organosilicon quaternary ammonium salt:
1, calculate the add-on of each reaction mass in molar ratio, wherein, octadecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent (methyl alcohol and terepthaloyl moietie)=1.0:1.03-1.05:7.0-8.0.Raw materials used is technical grade, and said mixed solvent is methyl alcohol and terepthaloyl moietie, and wherein methyl alcohol accounts for the 80-90% of solvent total amount, and terepthaloyl moietie is 10-20%.
2, r-chloropropyl triethoxysilane that measures and mixed solvent are added earlier in the reaction kettle, airtight, open reaction kettle and heat up stirring velocity 50-70 rev/min.When being warming up to 50 ℃, begin to drip the octadecyl dimethyl tertiary amine, the dropping time is 1-3 hour.Be warming up to 60-75 ℃, keep constant temperature, reaction is 50-75 hour under airtight and methanol mixed solvent refluxing state, with potentiometric determination [Cl
-] content and material reaction process, be benchmark with the octadecyl dimethyl tertiary amine, reaction is complete to 90%.Generally, dripping tertiary amine afterreaction 50-75h gets final product.
3, question response is reduced to normal temperature after fully, and with the PH to 5.5-6.5 of organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still, homogeneous stirs 10min; Then with the decolouring of 800# diatomite filtration, removal impurity; It is canned to go out still, promptly gets octadecyl organosilicon quaternary ammonium salt monomer finished product, subsequent use.Its molecular formula is: [(CH
3O)
3Si-(CH
2)
3-N (CH
3)
2-C
18H
37]
+Cl
-Molecular weight is: 496.29.
Two, the monomeric optimum combination of organosilicon quaternary ammonium salt is used
With above-mentioned synthetic dodecyl organosilicon quaternary ammonium salt monomer, tetradecyl organosilicon quaternary ammonium salt monomer, octadecyl organosilicon quaternary ammonium salt monomer; Make up by following weight percent; And put into reaction kettle one by one, and mix and stir 10-20min, measure [Cl with the current potential titration method then
-] content, using methyl alcohol adjustment quaternary ammonium salt content is 40%, is organosilicon quaternary ammonium salt optimum combination thing finished product of the present invention.Each composition proportion ratio of optimum combination thing of the present invention is following:
Dodecyl organosilicon quaternary ammonium salt monomer 5-20%
Tetradecyl organosilicon quaternary ammonium salt monomer 5-20%
Octadecyl organosilicon quaternary ammonium salt monomer 50-70%
Hundred shields, 1210 quaternary ammonium salt microcapsule 10-30%
By the organosilicon quaternary ammonium salt after the above-mentioned optimum combination; Have surperficial slowly-releasing and non-stripping double properties simultaneously; And having efficient active epidemic prevention and self-cleaning dual usefulness, withered grass black bacillus gemma (ATCC9372) and virus that antagonism is stronger have reliable inhibition or killing action.
Organosilicon quaternary ammonium salt compsn of the present invention can produce three effects simultaneously in concrete application, and the one, diluted liquid is applied to object (article) surface, can play the sterilization killing action to the already present pathogenic bacterium in this surface, make it innoxious; The 2nd, treat the top coat drying after, can produce nonvolatil self-cleaning bacteriostatic action; The 3rd, the microcapsule quaternary ammonium salt in the compsn slowly discharges, and plays initiatively germ-resistant effect.
First effect can be killed test method determination through ministry of Health of China version " disinfection technology standard " in 2002 bacteria quantified; Second effect can be passed through JIS Z 2801:2000 " antibiotic fabricated product bacterinertness TP and antibacterial effect " and measure; The 3rd effect can be measured through Chinese GB15979-2002 appendix C " product bactericidal property, bacteriostasis property and stability test method ".
Hundred shields, 1210 quaternary ammonium salt microcapsule of the present invention are the commodity by Shanxi crust shield environmental protection technology Research Institute and production.
Embodiment
One, the monomeric synthetic embodiment of organosilicon quaternary ammonium salt
Synthetic embodiment 1: the monomeric preparation of dodecyl organosilicon quaternary ammonium salt
1,, calculates the add-on of each reaction mass in molar ratio with capacity 300L and have condensation and the reaction kettle of reflux is an example.Wherein, dodecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent (methyl alcohol and terepthaloyl moietie)=1.0:1.03:7.0.
Charging capacity is by 201.94Kg: dodecyl dimethyl tertiary amine add-on is 66.03 Kg; R-r-chloropropyl trimethoxyl silane add-on is 64.57 Kg; The mixed solvent add-on is 69.40 Kg.Said mixed solvent is methyl alcohol and terepthaloyl moietie (wherein the weight proportion of methyl alcohol and terepthaloyl moietie is 85:15, and promptly 80% is methyl alcohol, and 15% is terepthaloyl moietie).Raw materials used is technical grade, purity >=98%.
2, r-chloropropyl triethoxysilane and mixed solvent are added earlier in the reaction kettle, airtight, open reaction kettle and heat up 60 rev/mins of stirring velocitys.When being warming up to 50 ℃, begin to drip the dodecyl dimethyl tertiary amine, dropwised in 2 hours.Continue to be warming up to 66 ℃, keep constant temperature, reaction is to 58 hours, with potentiometric determination [Cl under airtight and mixed solvent reflux state
-] content is 55%, reach 90% of theoretical value and be terminal point.
3, shut down, reduce to normal temperature after, with the PH to 6.0 of organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still; Homogeneous stirred 10 minutes, and with decolouring of 800# diatomite filtration and removal impurity, it is canned to go out still then; Promptly get dodecyl organosilicon quaternary ammonium salt monomer finished product of the present invention, subsequent use.
Synthetic embodiment 2: the monomeric preparation of tetradecyl organosilicon quaternary ammonium salt
1,, calculates the add-on of each reaction mass in molar ratio with capacity 300L and have condensation and the enamel reaction still of reflux is an example.Wherein, tetradecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent (methyl alcohol and terepthaloyl moietie)=1.0:1.03:7.0.
By the 201.94Kg that always feeds intake: tetradecyl dimethyl tertiary amine add-on is 66.03 Kg; R-r-chloropropyl trimethoxyl silane add-on is 64.57 Kg; The mixed solvent add-on is that (methyl alcohol is 56Kg to 69.40 Kg; Terepthaloyl moietie is 6.9Kg).Raw materials used is technical grade, purity >=98%.
2, r-chloropropyl triethoxysilane and mixed solvent are added earlier in the reaction kettle, airtight, open reaction kettle and heat up 60 rev/mins of stirring velocitys.When being warming up to 50 ℃, begin to drip the tetradecyl dimethyl tertiary amine, dropwise in 2 hours.Continue to be warming up to 70 ℃, keep constant temperature, reaction is to 58 hours, with potentiometric determination [Cl under airtight and mixed solvent reflux state
-] content is 55%, reaction is to terminal.
3, shut down, reduce to normal temperature after, with the PH to 6.0 of organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still; Homogeneous stirred 10 minutes, and with decolouring of 800# diatomite filtration and removal impurity, it is canned to go out still then; Promptly get tetradecyl organosilicon quaternary ammonium salt monomer finished product of the present invention, subsequent use.
Synthetic embodiment 3: the monomeric preparation of octadecyl organosilicon quaternary ammonium salt
1,, calculates the add-on of each reaction mass in molar ratio with capacity 300L and have condensation and the enamel reaction still of reflux is an example.
Total charging capacity is calculated the add-on of each reaction mass in molar ratio by 101.62Kg.Wherein, octadecyl dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent (methyl alcohol and terepthaloyl moietie)=1.0:1.03:7.0, that is: octadecyl dimethyl tertiary amine add-on is 40.73 Kg; R-r-chloropropyl trimethoxyl silane add-on is 28.55 Kg; The mixed solvent add-on is 30.71 Kg (wherein the weight proportion of methyl alcohol and terepthaloyl moietie is 80:20, and promptly 80% is methyl alcohol, and 20% is terepthaloyl moietie), and raw materials used all is technical grade.
2, r-chloropropyl triethoxysilane and mixed solvent are added earlier in the reaction kettle, airtight, open reaction kettle and heat up 70 rev/mins of stirring velocitys.When being warming up to 50 ℃, begin to drip the octadecyl dimethyl tertiary amine, dropwise in 2 hours.Continue to be warming up to 70 ℃, keep constant temperature, reaction is to 65 hours, with potentiometric determination [Cl under airtight and mixed solvent reflux state
-] content is 54%, is reacted to terminal point.
3, shut down, reduce to normal temperature after, with the PH to 6.0 of organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still; Homogeneous stirred 10 minutes, and with decolouring of 800# diatomite filtration and removal impurity, it is canned to go out still then; Promptly get octadecyl organosilicon quaternary ammonium salt monomer finished product of the present invention, subsequent use.
The octadecyl organosilicon quaternary ammonium salt monomer sample of the present invention's preparation and the DC-5700 performance comparison test of Dow corning company:
(1) carrier: Φ 5mm China filter paper
(2) used antibiotic drop
(1) the octadecyl organosilicon quaternary ammonium salt monomer made from present embodiment, adjusting its concentration is 0.42%, with this concentration formulations prepared from solutions carrier sample.
(2) with the formulations prepared from solutions examination carrier appearance of DC-5700 0.42% concentration of Dow corning company, as control group.
(3) specimen preparation
Earlier the filter paper of sterilising treatment is put into diameter 90mm plate, the test filter paper that to put into 4 diameters in each plate be 5mm, and 1 blank, inhaling 20 μ l antiseptic solutions with micropipet then drips on 4 filter papers, and middle 1 is blank,
Be placed in 37 ℃ of constant incubators dry then.
(4) experimental strain
Streptococcus aureus (ATCC 6539) the 10th generation nutrient agar inclined-plane fresh culture thing
Candida albicans (ATCC 10231) the 6th Dai Shabaoluoshi nutrient agar inclined-plane fresh culture thing
(5) experimental basis
The Ministry of Health's anti-(pressing down) bacterium experimental technique of " disinfection technology standard " P88 in 2002, experimental result is seen table 1, table 2
Antibacterial ring qualitative test is table 1 as a result
Antibacterial ring qualitative test is table 2 as a result
Experiment conclusion:
According to the Ministry of Health's anti-(pressing down) bacterium experimental technique of " disinfection technology standard " P88 in 2002, inhibition zone diameter can be judged as bacteriostatic action greater than 7mm.The inhibition zone diameter of table 1 and table 2 shows, concentration is about the big 2mm of antibacterial ring of the made carrier sample of antibacterial chain rate DC-5700 of 0.42% the made carrier sample of octadecyl organosilicon quaternary ammonium salt monomer solution of the present invention.
Above-mentioned same preparation method can also produce hexadecyl organosilicon quaternary ammonium salt monomer.
Two, organosilicon quaternary ammonium salt combination of monomers application implementation example
Application implementation example 1:
By weight percentage, take by weighing dodecyl organosilicon quaternary ammonium salt monomer 10 Kg; 14 mixed alkyl organosilicon quaternary ammonium salt monomers, 30 Kg; Octadecyl organosilicon quaternary ammonium salt list 50 Kg; Hundred shields, 1210 quaternary ammonium salt microcapsule commodity, 10 Kg form 100 Kg and contain 12,14,18 organosilicon quaternary ammonium salt optimum combination things, put into reaction kettle then one by one, and homogeneous stirs 10min, measure [Cl with the current potential titration method
-] content, using methyl alcohol adjustment quaternary ammonium salt content is 42%, is organosilicon quaternary ammonium salt optimum combination thing finished product of the present invention.
According to the ministry of Health of China antibacterial ring qualitative test of version " disinfection technology standard " in 2002 method; Detect the made carrier of organosilicon quaternary ammonium salt compsn of the present invention of 300 times of dilutions; Being tried bacterial classification is withered grass black bacillus gemma (ATCC9372), intestinal bacteria, streptococcus aureus, Candida albicans, and test-results shows: (1) the present invention has sustained release performance; (2) inhibition zone diameter average out to 9.5mm, showing is had obvious inhibition effect to trying bacterial classification.
Except, adopt ministry of Health of China version " disinfection technology standard " in 2002 P382.1.1.10 " inactivation of virus test method(s) " test, 300 times of material dilutions of the present invention, effect 20min reaches 100% to the SARS virus inactivation ratio.
Adopt same specimen method and tried bacterial classification, DC-5700 organosilicon quaternary ammonium salt and Chinese invention patent 200510045294.0 organosilicon quaternary ammonium salts, to withered grass black bacillus gemma (ATCC9372) and SARS virus all less than acting on.
Application implementation example 2:
By weight percentage, suitably adjust organosilicon quaternary ammonium salt monomer and hundred shield quaternary ammonium salt microcapsule proportioning ratios, can not change flesh and blood of the present invention, can reach equally than the single long-chain organosilicon quaternary ammonium salt of DC-5700 progressive effect.Be exemplified below:
Take by weighing dodecyl organosilicon quaternary ammonium salt monomer 5Kg of the present invention; Tetradecyl organosilicon quaternary ammonium salt monomer 40Kg; Octadecyl organosilicon quaternary ammonium salt list 30 Kg; Hundred shields, 1210 quaternary ammonium salt microcapsule commodity 25Kg form 100 Kg and contain 12,14,18 organosilicon quaternary ammonium salt optimum combination things, put into reaction kettle one by one, mix and stir 8min, measure [Cl with the current potential titration method then
-] content, using methyl alcohol adjustment quaternary ammonium salt content is 42%, is organosilicon quaternary ammonium salt optimum combination thing finished product of the present invention.
According to antibacterial ring carrier qualitative test method(s); Organosilicon quaternary ammonium salt preparation of compositions 5mm filter paper carrier with 300 times of dilutions; Tried bacterial classification and comprise withered grass black bacillus gemma (ATCC9372), intestinal bacteria, streptococcus aureus, Candida albicans bacterium, antibacterial ring mean diameter is 9mm, and test-results shows; Material of the present invention has slowly-releasing and non-stripping dual nature, and the stronger bacterial spore of antagonism shows good inhibition effect.
Adopt AATCC " flask foam stability method " test; Method is earlier with handling on the Chinese filter paper of organosilicon quaternary ammonium salt dip treating of the present invention and through 110 ℃ of dry solidifications; Again through ultrasonic elution test carrier; Through concussion shaking table concussion 10min, being tried bacterial classification is withered grass black bacillus gemma (ATCC9372) then.The result shows: effect 10min can reach 90% to the antibiotic rate of withered grass black bacillus gemma (ATCC9372).This test-results shows that simultaneously organosilicon quaternary ammonium salt compsn of the present invention has non-stripping character.
Adopt same specimen method, tried bacterial classification, action time, DC-5700 organosilicon quaternary ammonium salt and Chinese invention patent 200510045294.0 organosilicon quaternary ammonium salts are to not effect of withered grass black bacillus gemma (ATCC9372).
Application implementation example 3:
Suitably each composition components of plus-minus does not lose main body of the present invention and application.With the mildew-resistant technical application is example:
By weight percentage, take by weighing tetradecyl organosilicon quaternary ammonium salt monomer 50Kg of the present invention; Octadecyl organosilicon quaternary ammonium salt monomer 50 Kg put into reaction kettle then one by one, evenly stir 10min, measure [Cl with the current potential titration method then
-] content; Using methyl alcohol adjustment quaternary ammonium salt content is 42%; Be the mildew-resistant compsn that does not contain dodecyl organosilicon quaternary ammonium salt monomer and hundred shield slow-release microcapsule quaternary ammonium salt compositions; Can reach the application result of the mould proof better effects if of the single long-chain organosilicon quaternary ammonium salt of DC-5700 of producing than Dow corning company, fungicidal properties meets mensuration ASTM G21-96 (2002) standard of U.S.'s synthetic polymeric material mildew resistance.
According to Chinese GB/T 1741-2007 " the anti-mould assay method of paint film "; Test the mildew-resistant compsn that 200 times of distilled water dilutings do not contain dodecyl organosilicon quaternary ammonium salt monomer and hundred shield slow-release microcapsule quaternary ammonium salt compositions, and use carrier with this diluent preparation test.Adopt and use the same method; With 200 times of DC-5700 organosilicon quaternary ammonium salt dilutions and prepare Sample carrier; Find through simultaneous test; Two kinds of organosilicon quaternary ammonium salt compsns of tetradecyl of the present invention and octadecyl are obviously better than the antifungal effect of the single long-chain organosilicon quaternary ammonium salt of DC5700, and the organosilicon quaternary ammonium salt of 14 and 18 combinations all can reach best 0 grade to the anti-mould grade of 8 standard mould bacterial classifications, and DC577 only reaches best 0 grade to 6 mould bacterial classifications.
Except, should be applied to the odorless & perfumed finish of footwear material liner polyster fibre with the described compsn of embodiment, received equally better than DC5700, sooner, more stable and tangible odor-resistant result.
Three, product application embodiment
1, the application of " surface epidemic prevention coating "
Get the present invention's's " application implementation example 1 " organosilicon quaternary ammonium salt optimum combination thing 1Kg, add deionized water or zero(ppm) water 99Kg, process effective content and be 0.4% composition solution.Then; Available spraying or brushing method are coated with and impose on indoor wall, ground, article, hospital door objects such as handrail, elevator button (article) surface, with hair dryer, ir lamp heat drying 1-3min; Can obtain surface epidemic prevention coating, effectively suppress and initiatively kill surperficial unwanted bacteria.
Through antibacterial ring method and flask concussion method test proof; This surface has non-dissolution characteristic and slowly-releasing stripping dual nature; Pathogenic microorganisms such as intestinal bacteria, streptococcus aureus, withered grass black bacillus gemma (ATCC9372), virus there is the effect that initiatively presses down; The favourable PE hygienic quality that improves infects probability with the control transmissible disease; Be particularly useful for the infection control in hospital outpatient, Operation theatre, ward, be applicable to the environment epidemic prevention of complicated public place simultaneously, like frequent places of flow of personnel such as civil aviaton's terminal, train waiting room, railway car, aircraft passenger compartment, Saunas.
2, the application of anti-infective textiles
Get the present invention's's " application implementation example 2 " organosilicon quaternary ammonium salt optimum combination thing 1Kg, add deionized water or zero(ppm) water 99Kg, can be made into effective content and be 0.4% the anti-infective dressing liquid of textiles.Then, available dipping or two soaks two and rolls dyeing and printing process textiles is carried out the processing of anti-infective finishing functions, and drying temperature is 60 ℃, and crosslinking temperature is 120 ℃, 3min.
Through test, the textile surface after the processing can produce efficient, active epidemic prevention anti bactericide effect.So, can realize that organosilicon quaternary ammonium salt optimum combination thing of the present invention prepares the application target of anti-infective textiles.
Adopt the textiles after the organosilicon quaternary ammonium salt compositions-treated of the present invention; The difference maximum with present domestic and international market existing " antibacterial fabric " is: this textiles is except that having general self-cleaning antibacterial; Its surface has more unique slowly-releasing (initiatively) sterilization and epidemic prevention function; Be particularly useful for staff's under army's anti-biological warfare and the high-risk infection environment epidemic prevention, comprise the occupational protection of high-risk work such as hospital, Experiment on Microbiology, CDC.
3, the mildew-resistant of silo grain depot is used
Get the present invention's's " application implementation example 3 " organosilicon quaternary ammonium salt optimum combination thing 1Kg, add deionized water or zero(ppm) water 99Kg, process effective content and be 0.4% fungus resistant coating.Then, with spraying or brushing method, be coated with and impose on silo grain depot article, object, surface, wall ground; Seasoning can form the environment of a no mould-growth and breeding at grain depot, and coating itself is nonpoisonous and tasteless; The safe storage of favourable grain reduces the loss that causes because of going mouldy.
Detect grain depot environmental surfaces effect according to Chinese GB/T 1741-2007 " the anti-mould assay method of paint film " experiment; Adopt the made fungus resistant coating of the present invention to spread the grain depot environmental surfaces; 8 kinds of mould bacterial classifications are all had restraining effect, and the lasting period can reach 3 years, and is harmless pollution-free to grain; Can reduce the medication of storage environment mould, improve grain storage safe coefficient.
4, the application of the fungus-proof antisepsis on food wrapper and carton surface
Get the present invention's's " application implementation example 3 " organosilicon quaternary ammonium salt optimum combination thing 1Kg, add deionized water or zero(ppm) water 99Kg, process effective content and be 0.4% fungus resistant coating working fluid.Then, with the method for spraying, be coated with and impose on that food wrapper is opened or the carton surface, 80 ℃ of dryings can make the surface produce the fungus-proof antisepsis effect of holding effect.Use this mildew-resistant paper or packed in cases fruit, vegetables, food, can reduce the generation of bacterial contamination food accident, can prevent the mouldy and putrid and deteriorated of food, prolong effective period of food quality.
Detect paper and packed in cases mildew-resistant effect according to Chinese GB/T 1741-2007 " the anti-mould assay method of paint film " experiment; This fungus resistant coating surface is all held common 8 kinds of moulds and is imitated and reliable restraining effect, meets the technical requirements of GBT 4768-1995 mouldproof packaging.
In sum, product of the present invention and technology are except that the laboratory obtains experimental verification; Also, prove and to invent technology maturation that technology is advanced through the application verification of industriallization trial production; Scientific formulation, than prior art reaction times shortening 30-50h, the antibiosis usefulness of product significantly improves; Production cost descends about 40%, except that having surperficial non-stripping self-cleaning, has surperficial slowly-releasing sterilization and the initiatively effect of epidemic prevention simultaneously.In fields such as industry, agricultural, plantation, breed, health care, public health security, health textiles, food mould-proof corrosion-proof packings, has broad application prospect.
Claims (10)
1. monomeric compound method of organosilicon quaternary ammonium salt, it is characterized in that: the mole proportioning of the raw material in the said monomeric compound method is: different carbon chain (alkyl) dimethyl tertiary amine: r-r-chloropropyl trimethoxyl silane: mixed solvent=1.0:1.03-1.05:7.0-8.0;
Said mixed solvent is methyl alcohol and terepthaloyl moietie, and wherein methyl alcohol accounts for solvent gross weight 80-90%, and terepthaloyl moietie is 10-20%.
2. the monomeric compound method of a kind of organosilicon quaternary ammonium salt according to claim 1 is characterized in that: said different carbon chain (alkyl) dimethyl tertiary amine is dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine or octadecyl dimethyl tertiary amine.
3. the monomeric compound method of a kind of organosilicon quaternary ammonium salt according to claim 1 and 2, it is characterized in that: said method comprises the steps:
Step 1, calculate the add-on of each reaction mass in molar ratio, and measure;
Step 2, the r-chloropropyl triethoxysilane that measures and mixed solvent are joined earlier in the reaction kettle of band condensation and reflux; Airtight; The unlatching reaction kettle heats up, and stirring velocity 50-70 rev/min, when being warming up to 40-50 ℃; Begin to drip different carbon chain (alkyl) dimethyl tertiary amine, the dropping time is 2-3 hour; Be warming up to 60-75 ℃, keep constant temperature, reaction is 50-70 hour under airtight and mixed solvent reflux state, with potentiometric determination [Cl
-] content and calculate reaction process, be benchmark with different carbon chain (alkyl) dimethyl tertiary amine, reaction drips tertiary amine afterreaction 50-70h certainly to 90% being terminal point, can react completely, and obtains different carbon chain (alkyl) organosilicon quaternary ammonium salt monomer;
Step 3, reduce to normal temperature after; PH to 5.5-6.5 with different carbon chain (alkyl) organosilicon quaternary ammonium salt in the glacial acetic acid adjustment still; Homogeneous stirs 5-10min; With the decolouring of 600-800 order diatomite filtration, removal impurity, it is canned to go out still, promptly gets different carbon chain (alkyl) organosilicon quaternary ammonium salt monomer finished product then.
4. organosilicon quaternary ammonium salt monomer combination; It is characterized in that: will adopt claim 3 method synthetic dodecyl organosilicon quaternary ammonium salt monomer, tetradecyl organosilicon quaternary ammonium salt monomer, octadecyl organosilicon quaternary ammonium salt monomer; Make up by following weight percent; And add a certain proportion of quaternary ammonium salt microcapsule, wherein:
Dodecyl organosilicon quaternary ammonium salt monomer 5-20%
Tetradecyl organosilicon quaternary ammonium salt monomer 5-20%
Octadecyl organosilicon quaternary ammonium salt monomer 50-70%
Hundred shields, 1210 quaternary ammonium salt microcapsule 10-30%,
Put into reaction kettle then one by one, homogeneous stirs, and measures [Cl with the current potential titration method
-] content, with methyl alcohol adjustment quaternary ammonium salt content, be organosilicon quaternary ammonium salt compsn finished product of the present invention.
5. the application of an organosilicon quaternary ammonium salt monomer combination as claimed in claim 4 is characterized in that: described organosilicon quaternary ammonium salt monomer combination is applied to do surface epidemic prevention coating.
6. the application of an organosilicon quaternary ammonium salt monomer combination as claimed in claim 4 is characterized in that: described organosilicon quaternary ammonium salt monomer combination is applied to anti-infective textiles.
7. organosilicon quaternary ammonium salt monomer combination; It is characterized in that: get tetradecyl organosilicon quaternary ammonium salt monomer 40-60% by weight percentage, surplus is an octadecyl organosilicon quaternary ammonium salt monomer, puts into reaction kettle; Mix and stir, measure [Cl with the current potential titration method then
-] content, with methyl alcohol adjustment quaternary ammonium salt content, make organosilicon quaternary ammonium salt compsn finished product, wherein, tetradecyl organosilicon quaternary ammonium salt monomer and octadecyl organosilicon quaternary ammonium salt monomer all adopt the method for claim 3 to make.
8. the application of an organosilicon quaternary ammonium salt monomer combination as claimed in claim 7 is characterized in that: described organosilicon quaternary ammonium salt monomer composition is used for mould proof.
9. the application of a kind of organosilicon quaternary ammonium salt monomer combination according to claim 7 is characterized in that: said mould proof mildew-resistant for silo grain depot or food wrapper and carton surface.
10. the application of an organosilicon quaternary ammonium salt monomer combination as claimed in claim 7 is characterized in that: described organosilicon quaternary ammonium salt monomer composition is applied to the deodorization of footwear material liner polyster fibre.
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| CN104798809A (en) * | 2015-03-12 | 2015-07-29 | 江西领行药业有限公司 | Organosilicon quaternary ammonium long-acting antibacterial product and preparation method thereof |
| CN105145562A (en) * | 2014-08-31 | 2015-12-16 | 仙桃市中楚化工有限责任公司 | Novel efficient bactericide |
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