CN106478711A - The preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC - Google Patents
The preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC Download PDFInfo
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- CN106478711A CN106478711A CN201610882293.XA CN201610882293A CN106478711A CN 106478711 A CN106478711 A CN 106478711A CN 201610882293 A CN201610882293 A CN 201610882293A CN 106478711 A CN106478711 A CN 106478711A
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- quaternary ammonium
- ammonium salt
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- silicone
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 34
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004599 antimicrobial Substances 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- 230000007062 hydrolysis Effects 0.000 claims abstract description 34
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002148 esters Chemical group 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 4
- 150000003077 polyols Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- -1 silane quaternary ammonium salt Chemical class 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PFKRTWCFCOUBHS-UHFFFAOYSA-N dimethyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)C PFKRTWCFCOUBHS-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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
- 239000004094 surface-active agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a kind of preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC, it is with 3 trimethoxy silicon propyl group long chain alkyl ammonium salts as raw material, with high boiling polyol and its alcohol ether as solvent, through hydrolysis, ester exchange reaction generates the safe organosilicon quaternary ammonium salt of low VOC of no methanol release.
Description
Technical field
The invention belongs to organosilicon special surfactant technical field, it is related to a kind of safe organosilicone quaternary ammonium of low VOC
The preparation method of salt antibacterial.
Background technology
The washable antibacterial of fabric durable that 3 trimethoxy silicon propyl group long chain alkyl ammonium salts are universally acknowledged, it has
The Durable antibacterial of wide spectrum, it is to gram positive bacteria, negative bacterium；To various funguses；Virus has stronger bacteria resistance.But
Be, it have the shortcomings that one very big, that is, three methoxyl groups on its molecule, use when, hydrolysis release three methanol divide
Son, methanol is poisonous, and people absorbs 10 milliliters and just causes to lose the sight of both eyes, and absorbs 30 milliliters with regard to causing death.Many people are because containing methanol
Industrial alcohol is sold causing death and is sentenced when edible ethanol.And methanol low boiling point, flash-point is 12 DEG C, easily mix with air and
Become explosive mixture, so when carrying out antibiotic finish with quaternary ammonium silicone to fabric, operator must wear
Mask, or even wear a gas mask and protective clothing, pad working solution pads the isolation of groove air-suction cover, and strengthens aerofluxuss,
Methanol enters air also contaminated air, simply rushes dilute.For this reason, this quaternary ammonium silicone antibacterial is in Medical treatment device
Tool, Personal hygiene protection, on home appliances sterilization application be just restricted although triethoxysilane quaternary ammonium salt no
This toxicity, but preparation is more difficult, and reactivity is low.
Content of the invention
In order to overcome the disadvantages mentioned above of prior art, the present invention provides a kind of safe organosilicon quaternary ammonium salt antibacterial of low VOC
The preparation method of agent, it is more safer than nanometer silver, has no harmful methanol release, low volatilization, safer, the features such as more environmentally friendly.
The technical solution adopted for the present invention to solve the technical problems is：A kind of safe organosilicon quaternary ammonium salt of low VOC resists
The preparation method of microbial inoculum, it with 3 trimethoxy silicon propyl group long chain alkyl ammonium salts as raw material, with high boiling polyol and its alcohol
Ether is solvent, and through hydrolysis, ester exchange reaction generates the safe organosilicon quaternary ammonium salt of low VOC of no methanol release；
Wherein quaternary ammonium silicone refers to the silane quaternary ammonium salt containing three methoxyl groups in molecule, and general molecular formula is
CH3O 3Si (CH2) 3N+R1R2R3X-In formula, R1 is the alkyl of C12～C18, and R2 is the alkyl of C1～C12, and R3 is C1
The alkyl of～C6, X-Include CI for halogen-、Br-.
Quaternary ammonium silicone because of the methoxyl group containing three active facile hydrolysiss, in the steam running in the air or and water
Meet, just hydrolysis generates three silicone hydroxyl, discharges three methanol, hydrolysis equation is as follows simultaneously：
The three silicone hydroxyl silane quaternary ammonium salt generating are very active, and being susceptible to crosslinked polycondensation is 3 D stereo net so as to no longer
It is dissolved in water；
Polyhydric alcohol and polyol ethers include ethylene glycol, Polyethylene Glycol and its ether, propylene glycol, polypropylene glycol and its ether.They are with three
The reaction equation that silicone hydroxyl silane quaternary ammonium salt is esterified is as follows（Polyhydric alcohol is taking dihydroxylic alcohols as a example）：
In formula
R4 is (CH2) n n=2～5
R5 is CH3, C2H5, C4H9, H
Hydrolysis and esterification used catalyst adopt acids such as sulphuric acid, sulfonic acid, alkyl benzene sulphonate etc., and the consumption of acid is reactant
Best PH≤3 in 1～3%, PH≤5 of material total amount.
Water used by hydrolysis is deionized water it is desirable to electrical conductivity of water≤5μS/cm. deionized water in hydrolysis
Consumption be less than 3 times of silane quaternary ammonium salt molal quantity, the consumption of water is big, and the amount generating three silicone hydroxyl is just many, generation polycondensation friendship
The risk of connection is just big, does not add water, and just no hydrolysis occur, and is purely ester exchange reaction；Ester exchange reaction formula is as follows：
When deionized water consumption and silicon quaternary ammonium salt equimolar number, one mole of methoxyl group occurs hydrolysis to generate a mole, of methanol,
Other two mole of methoxy generate two mole, of methanol by ester exchange, and the methanol total amount of release is constant.Reaction equation is as follows：
This law hydrolysis esterification reaction temperature is 30～100 DEG C, and preferably in 50～90 DEG C of scopes, the response time is 0.5～6 hour,
Reaction temperature is higher, and the response time is shorter.The judgement of reaction end, to be determined with the amount of the methanol steaming that reduces pressure.
The positive effect of the present invention is：The three silicone hydroxyl silane that the present invention generates after can making quaternary ammonium silicone hydrolysis
Quaternary ammonium salt is esterified with high boiling polyhydric alcohol or polyol ethers, or directly carries out ester exchange reaction；Product is exactly that storage is stable, and
And in water the also stable safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low volatility, it is more safer than nanometer silver, has no harmful first
Alcohol release, low volatilization, safer, the features such as more environmentally friendly.
Specific embodiment
With reference to embodiment, the present invention is further described.
A kind of preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC, it is with 3 trimethoxy silicon propyl group long-chains
Alkyl quaternary ammonium saltss are raw material, and with high boiling polyol and its alcohol ether as solvent, through hydrolysis, ester exchange reaction generates no methanol release
The safe organosilicon quaternary ammonium salt of low VOC；
Wherein quaternary ammonium silicone refers to the silane quaternary ammonium salt containing three methoxyl groups in molecule, and general molecular formula is
CH3O 3Si (CH2) 3N+R1R2R3X-In formula, R1 is the alkyl of C12～C18, and R2 is the alkyl of C1～C12, and R3 is C1
The alkyl of～C6, X-Include CI for halogen-、Br-.
Quaternary ammonium silicone because of the methoxyl group containing three active facile hydrolysiss, in the steam running in the air or and water
Meet, just hydrolysis generates three silicone hydroxyl, discharges three methanol, hydrolysis equation is as follows simultaneously：
The three silicone hydroxyl silane quaternary ammonium salt generating are very active, and being susceptible to crosslinked polycondensation is 3 D stereo net so as to no longer
It is dissolved in water；
Polyhydric alcohol and polyol ethers include ethylene glycol, Polyethylene Glycol and its ether, propylene glycol, polypropylene glycol and its ether.They are with three
The reaction equation that silicone hydroxyl silane quaternary ammonium salt is esterified is as follows（Polyhydric alcohol is taking dihydroxylic alcohols as a example）：
In formula, R4 is (CH2) n n=2～5
R5 is CH3, C2H5, C4H9, H
Hydrolysis and esterification used catalyst adopt acids such as sulphuric acid, sulfonic acid, alkyl benzene sulphonate etc., and the consumption of acid is reactant
Best PH≤3 in 1～3%, PH≤5 of material total amount.
Water used by hydrolysis is deionized water it is desirable to electrical conductivity of water≤5μS/cm. deionized water in hydrolysis
Consumption be less than 3 times of silane quaternary ammonium salt molal quantity, the consumption of water is big, and the amount generating three silicone hydroxyl is just many, generation polycondensation friendship
The risk of connection is just big, does not add water, and just no hydrolysis occur, and is purely ester exchange reaction；Ester exchange reaction formula is as follows：
When deionized water consumption and silicon quaternary ammonium salt equimolar number, one mole of methoxyl group occurs hydrolysis to generate a mole, of methanol,
Other two mole of methoxy generate two mole, of methanol by ester exchange, and the methanol total amount of release is constant.Reaction equation is as follows：
This law hydrolysis esterification reaction temperature is 30～100 DEG C, and preferably in 50～90 DEG C of scopes, the response time is 0.5～6 hour,
Reaction temperature is higher, and the response time is shorter.The judgement of reaction end, to be determined with the amount of the methanol steaming that reduces pressure.
Embodiment 1., in 500 milliliters of three mouthfuls of round-bottomed flasks of attached motor stirrer and temperature automatically controlled equipment, adds front three
248 grams of oxygen silicon base propyl group octadecyldimethyl ammonium chloride（Content 80%）And 80 grams of propylene glycol, add DBSA
3.3 grams, it is warming up to 80 DEG C, Deca deionized water（Electrical conductivity 3μs/cm）7.2 grams, after reaction 5 hours, it is decompressed to -0.05～-
0.08Mpa, at 50～60 DEG C, steams 43 grams of first alcohol and water, obtains light yellow product, neutralize → filter → must be produced with sodium bicarbonate
320 grams of product, containing free methanol 0.3%, silane-containing quaternary ammonium salt（It is converted to quaternary ammonium silicone）60.3% .
Embodiment 2., in 500 milliliters of three mouthfuls of round-bottomed flasks of attached motor stirrer and temperature automatically controlled equipment, adds front three
248 grams of oxygen silicon base propyl group octadecyldimethyl ammonium chloride（Content 80%）, 100 grams of butyl glycol ether, add toluenesulfonic acid 3.5
Gram, it is warming up to 80 DEG C, Deca deionized water（Electrical conductivity 3.5μs/cm）14.5 grams, after reacting 6 hours, at 60～65 DEG C, decompression
To -0.08～-0.06Mpa, steam 53 grams of the mixture of first alcohol and water, obtain light turbid solution, be cooled to 30 DEG C → filter →
Obtain 310 grams of shallow yellow transparent solution, containing methanol 0.5%, silane-containing quaternary ammonium salt（It is converted to quaternary ammonium silicone）
61.5% .
Embodiment 3., in 500 milliliters of three mouthfuls of round-bottomed flasks of attached motor stirrer and temperature automatically controlled equipment, adds 80%
248 grams of front three oxygen silicon base propyl group octadecyldimethyl ammonium chloride, adds 150 grams of triethylene glycol butyl ether, 0.8 gram of citric acid, rises
Temperature, to 90 DEG C, is not added with deionization, ester exchange reaction, after 4 hours, at 60～65 DEG C, is decompressed to -0.08～-0.06Mpa, steams first
38 grams of alcohol, obtains 360 grams of shallow yellow transparent solution, containing free methanol 0.2%, silane-containing quaternary ammonium salt（It is converted to trimethoxy silane
Quaternary ammonium salt）55.1% .
Embodiment 4., in 500 milliliters of three mouthfuls of round-bottomed flasks of attached motor stirrer and temperature automatically controlled equipment, adds 80% 3
248 grams of methoxy silane quaternary ammonium salt (ibid), 100 grams of propylene glycol monomethyl ether, 3.0 grams of p-methyl benzenesulfonic acid, it is warming up to 85 DEG C, be not added with
Ion, ester exchange reaction, after 3 hours, at 60～65 DEG C, is decompressed to -0.06～-0.08Mpa, steams 36 grams of methanol, is cooled to 40
DEG C, filter, obtain 312 grams of shallow yellow transparent solution, containing free methanol 0.5%, silane-containing quaternary ammonium salt（It is converted to trimethoxy silicon
Alkane quaternary ammonium salt）63.0% .
Implement 1～4 products obtained therefrom and be all dissolved in water, in the deionized water solution of organosilane quaternary ammonium salt content 1～10%, deposit
More than half a year, for processing fabric, no methanol release substantially, for medical apparatus and instruments；Domestic appliance is sterilized, and meets the relevant mark of country
Accurate.
The three silicone hydroxyl silane quaternary ammonium salt high boiling points that the present invention generates after can making quaternary ammonium silicone hydrolysis
Polyhydric alcohol or polyol ethers esterification, or directly carry out ester exchange reaction；Product is exactly that storage is stable, and also stable in water
The safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low volatility, it is more safer than nanometer silver, have no harmful methanol release, low volatilization,
Safer, the features such as more environmentally friendly.
Claims (3)
1. a kind of preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC, is characterized in that：It is with 3 trimethoxy silicon
Propyl group long chain alkyl ammonium salt is raw material, and with high boiling polyol and its alcohol ether as solvent, through hydrolysis, ester exchange reaction generates no
The safe organosilicon quaternary ammonium salt of low VOC of methanol release；
Wherein quaternary ammonium silicone refers to the silane quaternary ammonium salt containing three methoxyl groups in molecule, and general molecular formula is
CH3O 3Si (CH2) 3N+R1R2R3X-In formula R1 be C12～C18 alkyl, R2 be C1～C12 alkyl, R3 be C1～
The alkyl of C6, X-Include CI for halogen-、Br-.
2. the preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC as claimed in claim 1, is characterized in that：Trimethoxy
Base silane quaternary ammonium salt, because of the methoxyl group containing three active facile hydrolysiss, is met in the steam running in the air or with aqueous phase, just hydrolysis life
Become three silicone hydroxyl, discharge three methanol, hydrolysis equation is as follows simultaneously：
The three silicone hydroxyl silane quaternary ammonium salt generating are very active, and being susceptible to crosslinked polycondensation is 3 D stereo net so as to no longer
It is dissolved in water；
Polyhydric alcohol and polyol ethers include ethylene glycol, Polyethylene Glycol and its ether, propylene glycol, polypropylene glycol and its ether；
The reaction equation that they are esterified with three silicone hydroxyl silane quaternary ammonium salt is as follows（Polyhydric alcohol is taking dihydroxylic alcohols as a example）：
In formula, R4 is (CH2) n n=2～5
R5 is CH3, C2H5, C4H9, H
Hydrolysis and esterification used catalyst adopt acids such as sulphuric acid, sulfonic acid, alkyl benzene sulphonate etc., and the consumption of acid is reaction
Best PH≤3 in 1～3%, PH≤5 of material total amount.
3. the preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC as claimed in claim 1, is characterized in that：Hydrolysis is anti-
Water that should be used is deionized water it is desirable to electrical conductivity of water≤5μS/cm. in hydrolysis, the consumption of deionized water is silane season
Less than 3 times of ammonium salt molal quantity, the consumption of water is big, and the amount generating three silicone hydroxyl is just many, produces the crosslinked risk of polycondensation just big, no
Add water, just no hydrolysis occur, be purely ester exchange reaction；
Ester exchange reaction formula is as follows：
When deionized water consumption and silicon quaternary ammonium salt equimolar number, one mole of methoxyl group occurs hydrolysis to generate a mole, of methanol,
Other two mole of methoxy generate two mole, of methanol by ester exchange, and the methanol total amount of release is constant；Reaction equation is as follows：
This law hydrolysis esterification reaction temperature is 30～100 DEG C, and preferably in 50～90 DEG C of scopes, the response time is 0.5～6 hour,
Reaction temperature is higher, and the response time is shorter；
The judgement of reaction end, to be determined with the amount of the methanol steaming that reduces pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610882293.XA CN106478711A (en) | 2016-10-10 | 2016-10-10 | The preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610882293.XA CN106478711A (en) | 2016-10-10 | 2016-10-10 | The preparation method of the safe silicone Quaternary Ammonium Salt Antimicrobial Agent of low VOC |
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| CN106478711A true CN106478711A (en) | 2017-03-08 |
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Cited By (6)
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| CN107114396A (en) * | 2017-06-07 | 2017-09-01 | 南雄鼎成新材料科技有限公司 | A kind of stabilizer for being used to stablize the trialkoxy silane quaternary ammonium salt antiseptic aqueous solution |
| WO2020082026A1 (en) | 2018-10-18 | 2020-04-23 | Topikos Pharmaceuticals, Inc. | Organosilanes for the treatment of infections |
| CN111235884A (en) * | 2020-02-28 | 2020-06-05 | 稳健医疗（黄冈）有限公司 | Antibacterial finishing agent, antibacterial all-cotton spunlace non-woven fabric and product thereof |
| CN112708135A (en) * | 2020-12-29 | 2021-04-27 | 江西晨光新材料股份有限公司 | Degradable organic silicon elastomer and synthesis method thereof |
| US12006338B2 (en) | 2019-10-18 | 2024-06-11 | Topikos Scientific, Inc. | Antimicrobial organosilanes |
| US12134628B2 (en) | 2022-04-18 | 2024-11-05 | Topikos Scientific, Inc. | Antimicrobial organosilanes |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107114396A (en) * | 2017-06-07 | 2017-09-01 | 南雄鼎成新材料科技有限公司 | A kind of stabilizer for being used to stablize the trialkoxy silane quaternary ammonium salt antiseptic aqueous solution |
| WO2020082026A1 (en) | 2018-10-18 | 2020-04-23 | Topikos Pharmaceuticals, Inc. | Organosilanes for the treatment of infections |
| EP3866601A4 (en) * | 2018-10-18 | 2022-08-17 | Topikos Pharmaceuticals, Inc. | Organosilanes for the treatment of infections |
| US12006338B2 (en) | 2019-10-18 | 2024-06-11 | Topikos Scientific, Inc. | Antimicrobial organosilanes |
| US12024533B2 (en) | 2019-10-18 | 2024-07-02 | Topikos Scientific, Inc. | Antimicrobial organosilanes |
| CN111235884A (en) * | 2020-02-28 | 2020-06-05 | 稳健医疗（黄冈）有限公司 | Antibacterial finishing agent, antibacterial all-cotton spunlace non-woven fabric and product thereof |
| CN112708135A (en) * | 2020-12-29 | 2021-04-27 | 江西晨光新材料股份有限公司 | Degradable organic silicon elastomer and synthesis method thereof |
| CN112708135B (en) * | 2020-12-29 | 2022-10-21 | 江西晨光新材料股份有限公司 | Degradable organic silicon elastomer and synthesis method thereof |
| US12134628B2 (en) | 2022-04-18 | 2024-11-05 | Topikos Scientific, Inc. | Antimicrobial organosilanes |
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