CN113582862A - Rosin-based quaternary ammonium salt for preparing efficient environment-friendly multifunctional cooling water biocide, and preparation method and application thereof - Google Patents
Rosin-based quaternary ammonium salt for preparing efficient environment-friendly multifunctional cooling water biocide, and preparation method and application thereof Download PDFInfo
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- CN113582862A CN113582862A CN202111016493.4A CN202111016493A CN113582862A CN 113582862 A CN113582862 A CN 113582862A CN 202111016493 A CN202111016493 A CN 202111016493A CN 113582862 A CN113582862 A CN 113582862A
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- ammonium salt
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 103
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 103
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 69
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 57
- 239000000498 cooling water Substances 0.000 title claims abstract description 42
- 239000003139 biocide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 81
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 239000004094 surface-active agent Substances 0.000 claims description 30
- -1 polyoxyethylene Polymers 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 150000004985 diamines Chemical class 0.000 claims description 10
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Natural products CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 3
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005764 inhibitory process Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 241000195493 Cryptophyta Species 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 210000003097 mucus Anatomy 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- ZMYKITJYWFYRFJ-UHFFFAOYSA-N 4-oxo-4-(2-phenylethylamino)butanoic acid Chemical compound OC(=O)CCC(=O)NCCC1=CC=CC=C1 ZMYKITJYWFYRFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/86—Ring systems containing bridged rings containing four rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a rosin-based quaternary ammonium salt for preparing a high-efficiency environment-friendly multifunctional cooling water biocide, a preparation method and application thereof, wherein the rosin-based quaternary ammonium salt for preparing the high-efficiency environment-friendly multifunctional cooling water biocide has the structural formula:
the invention is used for preparing efficient and environment-friendlyThe rosin-based quaternary ammonium salt of the multifunctional cooling water biocide takes rosin as a raw material, belongs to a bio-based green product, has the characteristics of being renewable and degradable, and accords with a green product; the preparation method is simple and convenient to operate; can be used for preparing the biocidal scale inhibitor; the obtained biocide antisludging agent has broad-spectrum and high-efficiency sterilization and algae removal capability, can effectively control the propagation of bacteria and algae and the growth of slime in water, has good slime stripping effect and certain dispersion and permeation effects, and has excellent antisludging and corrosion inhibition effects; the raw materials are green, environment-friendly and degradable, the application of the rosin is widened, and the consumption of petrochemical resources is reduced.
Description
Technical Field
The invention relates to a rosin-based quaternary ammonium salt for preparing a high-efficiency environment-friendly multifunctional cooling water biocide, a preparation method and application thereof, belonging to the technical field of rosin derivatives.
Background
In a direct-discharge cooling water system and a partial circulating cooling water system, mass propagation of microorganisms and shellfish often occurs, and meanwhile, the microorganisms and the shellfish secrete mucus to form biological slime which is adhered to pipelines and equipment of the system, so that the heat exchange effect of the equipment is reduced, and the energy consumption is increased; meanwhile, the biological slime is adhered to the equipment to form under-deposit corrosion, and the service life of the equipment is shortened.
Although the prior art also reports the biocidal and scale inhibition of cooling water systems, the following defects exist: large toxicity, large pollution and poor degradability; a large consumption of petrochemicals; the product has single function; the dosage is large.
Rosin is a natural and renewable green raw material and is low in price, the recoverable amount and the output of gum rosin resources in China are the first place in the world, and the rosin serving as the raw material is used for developing a cooling water treatment agent to replace part of petrochemical resources, so that the rosin has very important social significance.
Disclosure of Invention
The rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide, the preparation method and the application thereof provided by the invention have the advantages that rosin is used as a raw material, the rosin-based quaternary ammonium salt belongs to a bio-based green product, the product is in accordance with the green product, the preparation method is simple, the operation is convenient, the effect is obvious, and the characteristics of high efficiency, environment friendliness, multiple functions, degradability and the like are realized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a rosin-based quaternary ammonium salt for preparing a high-efficiency environment-friendly multifunctional cooling water biocide has a structural formula as follows:
the preparation method of the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide comprises the following steps:
(1) mixing acrylpimaric acid diamine and epichlorohydrin in an ethanol solvent, reacting for 10-24h at 10-30 ℃, and removing the solvent to obtain a product 1;
(2) and stirring the product 1 and N, N-dimethyl tetradecylamine in an ethanol solvent at 10-35 ℃ for 2-30h, and recrystallizing and drying in a mixed solvent of ethanol and ethyl acetate to obtain the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide.
The preparation of acrylpimaric diamine is carried out according to the prior art, for example according to the protocol disclosed in application No. 201910350644.6.
In order to take account of both the product yield and the reaction efficiency, in the step 1), the molar ratio of the acrylpimaric acid diamine to the epichlorohydrin is (1:4) - (1: 8); the molar ratio of the epichlorohydrin to the ethanol is (1:1) - (1: 20).
In order to give consideration to both the product yield and the reaction efficiency, in the step 2), the molar ratio of the product 1 to the N, N-dimethyl tetradecylamine is (1:4) - (1: 15); the molar ratio of the N, N-dimethyl tetradecane to the ethanol is (1:1) - (1: 5).
In order to further improve the product yield, in the step 2), the volume ratio of ethanol to ethyl acetate in the mixed solvent of ethanol and ethyl acetate is (1:0.5) - (1:25), and more preferably, the volume ratio of ethanol to ethyl acetate is (1:3) - (1: 8).
The rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide can be used for preparing the biocidal antisludging agent of a cooling water system.
A biocidal scale inhibitor comprises 15-20 parts of rosin-based quaternary ammonium salt, 15-20 parts of polyepoxysuccinic acid, 10-15 parts of polymerized rosin quaternary ammonium salt, 3-5 parts of rosin ester alcohol ether type quaternary ammonium salt surfactant, 2-3 parts of rosin-based polyoxyethylene amine type bi-surfactant and 50-80 parts of water, wherein the parts are parts by weight.
The applicant finds that the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide has a good biocidal effect, and particularly after the rosin-based quaternary ammonium salt is compounded with polymerized rosin quaternary ammonium salt, the biocidal effect can be remarkably improved; meanwhile, after the rosin-based quaternary ammonium salt and the polyepoxysuccinic acid which are used for preparing the efficient environment-friendly multifunctional cooling water biocide are compounded for use, the two have obvious mutual promotion and promotion effects on the performance, and very ideal biocidal, scale inhibition and corrosion inhibition effects are obtained; the rosin ester alcohol ether type quaternary ammonium salt surfactant and the rosin-based polyoxyethylene amine type gemini surfactant can effectively promote the dispersion of all components of the biocidal scale inhibitor and promote the biocidal scale inhibition effect to be improved to a certain extent; and all the raw materials have good degradability, and are green and environment-friendly; the biocidal mechanism is that the biocidal agent is adsorbed to the surface of thallus to destroy the cell wall and membrane structure, inhibit enzyme activity, influence cell metabolism and other modes, and the hydrophobic radical and hydrophilic radical of quaternary ammonium salt are penetrated deeply into the lipoid layer and protein layer of cell to result in enzyme deactivation and protein denaturation.
When the biocidal scale inhibitor is prepared, the uniform and stable biocidal scale inhibitor can be obtained only by stirring for 30 +/-5 min at the temperature of 60-70 ℃ and at the speed of 800 +/-50 r/min and cooling, and the preparation method is simple and easy to operate and is easy to industrialize.
The polymerized rosin quaternary ammonium salt is polymerized rosin quaternary ammonium salt
Polymerizing to obtain the product;
the structural formula of the rosin ester alcohol ether type quaternary ammonium salt surfactant is as follows:
the structural formula of the rosinyl polyoxyethylene amine type gemini surfactant is as follows:
wherein MPEG is polyethylene glycol monomethyl ether.
The usage amount of the biocidal scale inhibitor is 15-20 PPM.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide takes rosin as a raw material, belongs to a bio-based green product, has the characteristics of reproducibility and degradability, and accords with a green product; the preparation method is simple and convenient to operate; can be used for preparing the biocidal scale inhibitor; the obtained biocide antisludging agent has broad-spectrum and high-efficiency sterilization and algae removal capability, can effectively control the propagation of bacteria and algae and the growth of slime in water, has good slime stripping effect and certain dispersion and permeation effects, and has excellent antisludging and corrosion inhibition effects; the raw materials are green, environment-friendly and degradable, the application of the rosin is widened, and the consumption of petrochemical resources is reduced.
Drawings
FIG. 1 is an infrared spectrum of i) N, N-dimethyltetradecane, ii) propylenedipimaric acid, iii) rosin-based quaternary ammonium salt for preparing the efficient environmentally-friendly multifunctional cooling water biocide of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a polymerizable quaternary ammonium rosin salt obtained in example 4;
FIG. 3 is an IR spectrum of a rosin ester alcohol ether quaternary ammonium salt surfactant obtained in example 5;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the rosinyl polyoxyethylene amine type gemini surfactant obtained in example 6;
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The preparation of the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide comprises the following steps:
(1) mixing 10g of acrylpimaric acid diamine and 12g of epichlorohydrin in 10ml of ethanol solvent, reacting for 15h at 20 ℃, and removing the solvent to obtain the product 1.
(2) And (3) stirring the product 1(5g) and N, N-dimethyl tetradecylamine (12g) in an ethanol (12ml) solvent at 15 ℃ for 24 hours, recrystallizing in a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:5, and drying to obtain the target product No. 1.
In FIG. 1, i is N, N-dimethyltetradecylamine, ii is propylenedipimaric acid diamine), and iii) is an infrared spectrum of the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide, and it can be seen from the infrared spectrum that a C-N-based characteristic peak of the N, N-dimethyltetradecylamine is at 1461cm < -1 > in the curve of i; and (4) observing a ii curve, wherein the 3294cm-1 part is an amino characteristic peak of the propylenedipimaric acid diamine. Observing the curve iii, the C-N group characteristic peak of tertiary amine at 1461cm-1 is enlarged, and the hydroxyl group characteristic peak of reaction at 3218cm-1 indicates that the rosin-based quaternary ammonium salt for preparing the high-efficiency environment-friendly multifunctional cooling water biocide is successfully synthesized, and the structural formula is as follows:
carbon spectrum characterization of rosin-based quaternary ammonium salt for preparing efficient environment-friendly multifunctional cooling water biocide: 146.75ppm ofChemical shift peak of carbon-carbon double bond of rosin, 64.71ppm has chemical shift peak of C-O, 47.78-18.37ppm has CH in structure2And CH3Chemical shift peak of carbon.
Example 2
The preparation of the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide comprises the following steps:
(1) mixing 9g of acrylpimaric acid diamine and 12g of epichlorohydrin in a solvent of ethanol (16ml), reacting for 24h at 25 ℃, and removing the solvent to obtain a product 1.
(2) The product 1(5g) and N, N-dimethyl tetradecylamine (14g) are stirred and reacted in an ethanol (12ml) solvent at 25 ℃ for 25 hours, then recrystallized and dried in a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:5 to obtain a target product No. 2, and the obtained spectrogram is consistent with that of example 1 and is not provided repeatedly.
Example 3
The preparation of the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide comprises the following steps:
(1) mixing 8g of acrylpimaric acid diamine and 12g of epichlorohydrin in 14ml of ethanol solvent, reacting for 18h at 27 ℃, and removing the solvent to obtain the product 1.
(2) The product 1(5g) and N, N-dimethyl tetradecylamine (16g) are stirred and reacted in ethanol (17ml) solvent at 25 ℃ for 15h, then recrystallized and dried in a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:5 to obtain the target product No. 3, and the obtained spectrogram is consistent with that of example 1 and is not provided repeatedly.
The preparation of the example 1 is amplified by 200 times and used for application tests, and the obtained spectrogram of the rosin-based quaternary ammonium salt used for preparing the efficient environment-friendly multifunctional cooling water biocide is consistent with that of the example 1.
Example 4
Preparation of polymerized rosin quaternary ammonium salt:
100g of rosin and 27.5g of maleic anhydride are respectively weighed and poured into a 1000mL four-neck flask, then 400mL of acetic acid and 0.128g of p-toluenesulfonic acid are added as catalysts, the mixture is heated to 120 ℃, condensed and refluxed, stirred to be fully reacted, and filtered after the reaction for 10 hours to obtain the maleopimaric acid compound. Adding 10g of maleopimaric acid and 250mL of ethanol into a 500mL four-neck flask, heating to 85 ℃, condensing and refluxing, dropwise adding 2.8mL of N, N-dimethyl ethylenediamine, reacting for 5h after dropwise adding, standing for crystallization, and filtering to obtain the maleopimaric acid tertiary amine compound. And then adding 5g of the maleopimaric acid tert-amine compound, 15.5mL of bromoethane and 200mL of tetrahydrofuran into a 500mL single-neck flask, heating to 60 ℃, condensing and refluxing, stirring to fully react, reacting for 30h, and filtering a product to obtain the rosin quaternary ammonium salt compound. Adding 5g of the rosin quaternary ammonium salt compound, 1.21g of glycerol methacrylate, 0.065g of benzyltriethylammonium chloride and 250mL of ethanol into a 500mL single-neck flask, heating to 85 ℃, reacting for 4 hours, and performing rotary evaporation to remove the ethanol to obtain a polymerizable rosin quaternary ammonium salt bactericide, wherein a nuclear magnetic spectrum is shown in FIG. 2;
dissolving 10g of polymerizable rosin quaternary ammonium salt and 5mg of initiator (4,4' -azobis (4-cyanopentanoic acid)) in 150mL of ethanol, adding into a 500mL four-neck flask, heating to 80 ℃, condensing and refluxing, stirring to fully react, and after reacting for 8h, performing rotary evaporation to remove ethanol to obtain the polymerized rosin quaternary ammonium salt. The above preparation was amplified by 50 times and used in application experiments, and the product spectra were consistent with those of the previous example.
Example 5
Preparing the rosin ester alcohol ether type quaternary ammonium salt surfactant:
weighing rosin and polyethylene glycol 600 with a molar ratio of 1:1, pouring the rosin and polyethylene glycol 600 into a 500mL four-neck flask, adding zinc oxide (the mass of the zinc oxide accounts for 0.15% of the mass of the rosin) serving as a catalyst, heating to 240 ℃, allowing the mixture to react sufficiently, and cooling after the acid value is reduced to about 10 mgKOH/g. Taking 0.1mol of the reaction product, putting the reaction product into a 250mL dry three-neck flask, adding 0.1mol of epichlorohydrin, 0.12mol of sodium hydroxide (added by a water solution with the mass concentration of 50%), tetrabutylammonium bromide with the mass of 0.1% of rosin and a dichloromethane solvent, heating to 50 ℃, stirring for reaction for 4h, cooling to room temperature, and carrying out suction filtration. The solid phase is washed twice by dichloromethane, and dichloromethane and a small amount of unreacted epichlorohydrin (about 85 ℃) are removed by distillation to obtain the rosin-based alcohol ether intermediate. A250 mL dry three-necked flask was charged with the intermediate synthesized in the previous step, 0.1mol of triethylamine hydrochloride and50mL of ethanol solvent is stirred and reacted for 3.5h at 78 ℃, ethanol and water are evaporated to obtain the rosin ester alcohol ether type quaternary ammonium salt surfactant, n is 600, R is CH3The IR spectrum is shown in FIG. 3. The above preparation was amplified by 50 times and used in application experiments, and the product spectra were consistent with those of the previous example.
Example 6
Preparation of rosinyl polyoxyethylene amine gemini surfactant:
washing the closed reaction kettle with methanol, drying, adding 3.2g of methanol and 0.01g of bimetallic cyanide complex (see example 1 in the Chinese patent application with the application number of 2012101070303 for preparation) at room temperature, replacing with nitrogen for several times at 110 ℃ to remove water, adding 62.4g of ethylene oxide, reacting at 115 ℃ until the pressure in the kettle is not reduced any more, cooling, and discharging at 80 ℃.
20g of the product, 3.0g of sodium bicarbonate and 40mL of toluene are added into a 100mL three-neck flask and are stirred uniformly; 5.7g of p-toluenesulfonyl chloride is dissolved in 10mL of toluene and then slowly dropped into a three-neck flask at low temperature; reacting at 40 deg.C for 16h, adding distilled water, extracting the water phase with ethyl acetate twice, collecting the organic phase, acid washing, water washing, drying, and removing solvent to obtain colorless mucus.
At normal temperature, 6.9g of acetone solution of benzyl trimethyl ammonium bromide is slowly dripped into the acetone solution of the colorless mucus, reflux reaction is carried out for 24 hours, the solvent is removed, the acetone solution is dissolved in water and extracted twice by ethyl acetate, and the organic phase is collected, dried and removed to obtain the light yellow waxy solid MPEGBR-1.
11.1g of alpha, omega-dibromopropane, 13.3g of sodium bicarbonate and 200mL of tetrahydrofuran were added to a 250mL three-necked flask, and 33.6g of dehydroabietylamine was dissolved in 50mL of tetrahydrofuran and then slowly added dropwise thereto; and (3) after reflux reaction for 16h, cooling to room temperature, filtering to remove solids, removing the solvent from the filtrate under reduced pressure to obtain mucus, carrying out acid washing, alkali washing, water washing, drying and solvent removal on the mucus to obtain a crude product, and recrystallizing the crude product to obtain white solid N, N' -di-dehydroabietyl-alpha, omega-propane diamine. 0.57g of N, N' -didehydro-abietyl-alpha, omega-diamine and 0.22g of sodium bicarbonate were placed in a 100mL three-necked flask equipped with a thermometer, a constant pressure dropping funnel and a cooling/heating reflux tube, and dissolved in 20mL of methanol with stirring, 5.82g of MPEGBR-1 was dissolved in 20mL of methanol at room temperature and slowly dropped into the flask, and the temperature was raised to 74 ℃ to react for 16 hours. After the reaction is finished, the rosin-based polyoxyethylene amine gemini surfactant is obtained through reduced pressure distillation, washing and vacuum drying, and the nuclear magnetic hydrogen spectrum diagram is shown in figure 4. The above preparation was amplified by 100 times and used in application experiments, and the obtained product spectrum was consistent with the above example.
Example 7
A biocidal scale inhibitor comprising: 170g of rosin-based quaternary ammonium salt, 180g of polyepoxysuccinic acid (PESA, purchased from Tangshan Yongshu water treatment agent Co., Ltd., the sources of the following examples are the same), 120g of polymerized rosin quaternary ammonium salt, 40g of rosin ester alcohol ether type quaternary ammonium salt surface activity, 25g of rosin-based polyoxyethylene amine type double surfactant and 650g of water which are used for preparing the efficient environment-friendly multifunctional cooling water biocide. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
Example 8
A biocidal scale inhibitor: the efficient environment-friendly multifunctional cooling water biocide comprises 200g of rosin-based quaternary ammonium salt, 150g of polyepoxysuccinic acid, 130g of polymerized rosin quaternary ammonium salt, 30g of rosin ester alcohol ether type quaternary ammonium salt surfactant, 20g of rosin-based polyoxyethylene amine type gemini surfactant and 650g of water. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
Comparative example 1
A biocidal scale inhibitor comprising: 180g of polyepoxysuccinic acid, 120g of polymerized rosin quaternary ammonium salt, 40g of rosin ester alcohol ether quaternary ammonium salt surfactant, 25g of rosin polyoxyethylene amine type bi-surfactant and 650g of water. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
Comparative example 2
A biocidal scale inhibitor comprises 170g of rosin-based quaternary ammonium salt, 120g of polymerized rosin quaternary ammonium salt, 40g of rosin ester alcohol ether type quaternary ammonium salt surfactant, 25g of rosin-based polyoxyethylene amine type bi-surfactant and 650g of water, wherein the rosin-based quaternary ammonium salt, the polymerized rosin alcohol ether type quaternary ammonium salt surfactant and the rosin ester alcohol ether type bi-surfactant are used for preparing a high-efficiency environment-friendly multifunctional cooling water biocide. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
Comparative example 3
A biocidal scale inhibitor comprises 170g of rosin-based quaternary ammonium salt, 180g of polyepoxysuccinic acid, 40g of rosin ester alcohol ether type quaternary ammonium salt surfactant, 25g of rosin-based polyoxyethylene amine type bi-surfactant and 650g of water, wherein the rosin-based quaternary ammonium salt, the polyepoxysuccinic acid, the rosin ester alcohol ether type quaternary ammonium salt surfactant and the rosin-based polyoxyethylene amine type bi-surfactant are used for preparing a high-efficiency environment-friendly multifunctional cooling water biocide. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
Comparative example 4
A biocidal scale inhibitor comprises 170g of rosin-based quaternary ammonium salt, 180g of polyepoxysuccinic acid, 120g of polymerized rosin quaternary ammonium salt, 25g of rosin-based polyoxyethylene amine type gemini surfactant and 650g of water, wherein the rosin-based quaternary ammonium salt, the polyepoxysuccinic acid and the polymerized rosin quaternary ammonium salt are used for preparing the efficient environment-friendly multifunctional cooling water biocide. Mixing the components, stirring at 65 deg.C and 800r/min for 30min, and cooling.
The white water from the paper mill was used as it was (the number of aquatic microorganisms was 3.52X 10)7Cfu/ml), adding the product with the concentration of 15PPM, and the sterilizing effect of each case is shown in the table 1.
TABLE 1
| Examples | The residual amount of the microorganisms is 24 h% |
| Example 1 | 0.001 |
| Example 2 | 0.003 |
| Comparative example 1 | 10.2 |
| Comparative example 2 | 8.6 |
| Comparative example 3 | 7.2 |
| Comparative example 4 | 2.9 |
Aiming at scale inhibition of a circulating cooling water system, various indexes of cooling water are as follows: the concentration multiple C is more than or equal to 4, the total alkali is more than or equal to 500mg/l calculated by calcium carbonate, the total hardness is more than or equal to 600mg/l calculated by calcium carbonate, and the pH is more than or equal to 8.6 mg/l. The amount of the added cooling water is 100mg/l, and each example is tested according to the test method of the water treatment agent in the analysis and test method of cooling water of the general company of petrochemical engineering, the product quality detection manual of water quality and water treatment agent of the department of chemical industry and the design specification of industrial circulating cooling water treatment of the national standard GB 50050-2007, wherein the addition amount of the biocide scale inhibitor is 15PPM, and the results are shown in Table 2.
TABLE 2
| Examples | Calcium carbonate scale inhibition rate% | Corrosion inhibition rate of carbon steel% | Test tube adhesion Rate (mcm) |
| Example 1 | 100 | 99.8 | 0.2 |
| Example 2 | 100 | 99.6 | 0.5 |
| Comparative example 1 | 92.3 | 89.1 | 5.1 |
| Comparative example 2 | 52.6 | 51.4 | 18.3 |
| Comparative example 3 | 93.6 | 91.9 | 4.2 |
| Comparative example 4 | 95.6 | 93.2 | 1.8 |
Claims (10)
1. A rosin-based quaternary ammonium salt for preparing a high-efficiency environment-friendly multifunctional cooling water biocide is characterized in that: the structural formula is as follows:
2. the preparation method of the rosin-based quaternary ammonium salt for preparing the high-efficiency environment-friendly multifunctional cooling water biocide as claimed in claim 1 is characterized in that: the method comprises the following steps:
(1) mixing acrylpimaric acid diamine and epichlorohydrin in an ethanol solvent, reacting for 10-24h at 10-30 ℃, and removing the solvent to obtain a product 1;
(2) and stirring the product 1 and N, N-dimethyl tetradecylamine in an ethanol solvent at 10-35 ℃ for 2-30h, and recrystallizing and drying in a mixed solvent of ethanol and ethyl acetate to obtain the rosin-based quaternary ammonium salt for preparing the efficient environment-friendly multifunctional cooling water biocide.
3. The method of claim 2, wherein: in the step 1), the mol ratio of the acrylpimaric acid diamine to the epichlorohydrin is (1:4) - (1: 8); the molar ratio of the epichlorohydrin to the ethanol is (1:1) - (1: 20).
4. The production method according to claim 2 or 3, characterized in that: in the step 2), the molar ratio of the product 1 to the N, N-dimethyl tetradecane is (1:4) - (1: 15); the molar ratio of the N, N-dimethyl tetradecane to the ethanol is (1:1) - (1: 5).
5. The production method according to claim 2 or 3, characterized in that: in the step 2), the volume ratio of the ethanol to the ethyl acetate in the mixed solvent of the ethanol and the ethyl acetate is (1:0.5) - (1: 25).
6. The method of claim 5, wherein: in the step 2), the volume ratio of the ethanol to the ethyl acetate in the mixed solvent of the ethanol and the ethyl acetate is (1:3) - (1: 8).
7. The use of the rosin-based quaternary ammonium salt for preparing a high-efficiency environmentally friendly multi-functional cooling water biocide of claim 1, wherein: the biocide antisludging agent is used for preparing a cooling water system.
8. The use of claim 7, wherein: the biocidal scale inhibitor comprises 15-20 parts of rosin-based quaternary ammonium salt, 15-20 parts of polyepoxysuccinic acid, 10-15 parts of polymerized rosin quaternary ammonium salt, 3-5 parts of rosin ester alcohol ether type quaternary ammonium salt surfactant, 2-3 parts of rosin-based polyoxyethylene amine type bi-surfactant and 50-80 parts of water, wherein the parts are parts by weight.
9. The use of claim 8, wherein: the polymerized rosin quaternary ammonium salt is polymerized by polymerizable rosin quaternary ammonium salt, and the structure of the polymerizable rosin quaternary ammonium salt is
The structural formula of the rosin ester alcohol ether type quaternary ammonium salt surfactant is as follows:
the structural formula of the rosinyl polyoxyethylene amine type gemini surfactant is as follows:
10. Use according to claim 8 or 9, characterized in that: the usage amount of the biocidal scale inhibitor is 15-20 PPM.
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