CN117180803B - Preparation method and application of rare earth element modified siloxane defoamer - Google Patents
Preparation method and application of rare earth element modified siloxane defoamer Download PDFInfo
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- CN117180803B CN117180803B CN202311464725.1A CN202311464725A CN117180803B CN 117180803 B CN117180803 B CN 117180803B CN 202311464725 A CN202311464725 A CN 202311464725A CN 117180803 B CN117180803 B CN 117180803B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 54
- 239000013530 defoamer Substances 0.000 title claims abstract description 48
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 25
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 13
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229920001661 Chitosan Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 25
- 239000006260 foam Substances 0.000 abstract description 21
- 241000222122 Candida albicans Species 0.000 abstract description 9
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 9
- 229940095731 candida albicans Drugs 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002518 antifoaming agent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001122 Mischmetal Inorganic materials 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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Landscapes
- Silicon Polymers (AREA)
Abstract
The invention provides a preparation method and application of a rare earth element modified siloxane defoamer. The preparation method comprises the steps of firstly modifying allyl glycidyl ether, then fully reacting the modified allyl glycidyl ether with allyl polyoxyethylene polyoxypropylene methyl ether, hydrogen-containing silicone oil and an organic solvent to obtain an intermediate, fully reacting the intermediate, lanthanum nitrate and mixed rare earth, placing a reaction system in an acetic acid aqueous solution, sequentially adding liquid paraffin, an emulsifying agent and ethyl acetate, adding a formaldehyde solution for reaction, adjusting reaction conditions, adding epichlorohydrin for full reaction, and obtaining the rare earth element modified siloxane defoamer. The rare earth element modified siloxane defoamer prepared by the preparation method provided by the application has good centrifugal stability, good defoaming property and foam inhibition property even after being placed for a long time, and high inhibition rate to staphylococcus aureus and candida albicans, and good bactericidal property.
Description
Technical Field
The invention belongs to a defoaming agent, and particularly relates to a preparation method and application of a rare earth element modified siloxane defoaming agent.
Background
An antifoaming agent is a substance that can reduce the surface tension of water, solutions, suspensions, etc., prevent foam formation, or reduce or eliminate original foam. The defoaming agent has strong defoaming capability and small dosage; the surface tension is small; the heat resistance is good; the diffusivity and the permeability are good; the chemical property is stable, and the oxidation resistance is strong; high safety, and the like, and is widely applied to paper industry, water treatment, oil extraction industry, printing and dyeing industry, paint industry, detergent industry, rubber latex industry, aerosol industry, daily chemical industry, medical industry, dairy industry, and the like.
The common defoamers on the market at present comprise organic defoamers, polyether defoamers, organosilicon defoamers and polyether modified siloxane defoamers. The research of the organic defoaming agent is early, and the organic defoaming agent has the advantages of mature production process, easily available raw materials, high environmental protection performance, low production cost and the like, but has the defects of low defoaming efficiency, strong specialization, harsh use condition and the like; the polyether defoamer has the greatest advantages that the foam inhibition capability is strong, part of products also have excellent performances such as high temperature resistance, strong acid resistance, strong alkali resistance and the like, but the products have the defects of limited use conditions, poor foam inhibition capability, low foam breaking rate and the like; the organic silicon defoamer has the advantages of strong defoaming performance, quick foam breaking capability, low volatility, no toxicity to the environment, no physiological inertia, wide application range and the like, thus having wide application prospect and huge market potential, but poor foam inhibition performance; the polyether modified siloxane defoamer is an emerging product, and has the advantages of both polyether defoamer and organosilicon defoamer, but the product is still in the research and development stage, has fewer product types on the market, has higher production cost, and can influence the foam inhibition and defoaming performance when stored for a long time.
The rare earth element is lanthanide in the periodic table, along with the continuous development of science and technology, the more the functionality of the rare earth element is found, such as special chemical activity, deoxidizing capability, luminescence property and the like, and the rare earth raw material has low price, and has defoaming and foam inhibition capabilities, so how to modify the siloxane defoaming agent by using the rare earth element, so that the prepared defoaming agent has good defoaming, foam inhibition performance, centrifugal stability and high antibacterial effect, and the problem to be solved in the invention is urgent.
Disclosure of Invention
The invention aims to provide a preparation method and application of a rare earth element modified siloxane defoamer, which are used for solving the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: in one aspect, the invention provides a method for preparing a rare earth element modified siloxane defoamer, which comprises the following steps:
(1.1) fully dissolving chitosan in an acid solution, then regulating the pH value to 2-5, dropwise adding allyl glycidyl ether for full reaction, and after the reaction is finished, precipitating, filtering and washing to obtain modified allyl glycidyl ether;
(1.2) adding allyl polyoxyethylene polyoxypropylene methyl ether, hydrogen-containing silicone oil and an organic solvent into a reaction kettle, adding a platinum-containing catalyst for full reaction, then adding the modified allyl glycidyl ether prepared in the step (1.1) for continuous reaction, and after the reaction is finished, carrying out suction filtration and washing to obtain an intermediate;
(1.3) mixing the intermediate prepared in the step (1.2), lanthanum nitrate and mixed rare earth, adding deionized water, and stirring until the mixture fully reacts;
(1.4) placing the system reacted in the step (1.3) into an acetic acid aqueous solution, fully stirring until the mixture is uniform, standing for 20-40h at normal temperature, sequentially adding liquid paraffin, an emulsifying agent and ethyl acetate while stirring, adding formaldehyde solution for reaction, reacting for 5-30min, adjusting the pH value of the reaction system to 7-9 and the temperature to 50-80 ℃, adding epichlorohydrin for full reaction, and washing and suction filtering after the reaction is finished to obtain the rare earth element modified siloxane defoamer.
As a further improvement, the mass ratio of the chitosan and the allyl glycidyl ether in the step (1.1) is 1 (0.2-0.5).
As a further improvement, the content of the platinum-containing catalyst in the step (1.2) is 0.05-2 per mill of the mass of the hydrogen-containing silicone oil.
As a further improvement, the mass ratio of the total mass of lanthanum nitrate and mixed rare earth to the intermediate in the step (1.3) is 1: (3-15); the mass ratio of the lanthanum nitrate and the mischmetal in the step (1.3) is (2-5): 1, wherein the mass ratio of the total mass of the lanthanum nitrate and the mischmetal in the step (1.3) to the intermediate refers to the total mass of the lanthanum nitrate and the mischmetal in the step (1.3) and the mass of the intermediate in the step (1.3).
As a further improvement, the mixed rare earth contains 60-75wt% of lanthanum, 20-39% of cerium, 0.15-5% of praseodymium, 0.001-0.005% of lutetium and 0.05-0.25% of neodymium.
As a further improvement, the mass-to-volume ratio of the intermediate in the step (1.3) (referring to the mass of the intermediate used in the step (1.3)) to the formaldehyde solution in the step (1.4) is 1g (2-5) mL; the mass-volume ratio of the intermediate in the step (1.3) (referring to the mass of the intermediate used in the step (1.3)) to the epichlorohydrin in the step (1.4) is 1g (1-3) mL.
As a further improvement, the platinum-containing catalyst is a Karstedt catalyst.
As a further improvement, the formaldehyde content of the formaldehyde solution is 35-40wt%.
As a further improvement, the acidic solution is an aqueous acetic acid solution.
On the other hand, the invention also provides application of the rare earth element modified siloxane defoamer prepared by the preparation method of the rare earth element modified siloxane defoamer in the papermaking and printing and dyeing industries.
Compared with the prior art, the invention has the beneficial effects that: the rare earth element modified siloxane defoamer prepared by the preparation method provided by the application has good centrifugal stability, good defoaming property and foam inhibition property even after being placed for a long time, and high inhibition rate to staphylococcus aureus and candida albicans, and good bactericidal property.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
In the following examples, the remaining compound monomers and related reagents used were commercially available except Karstedt's catalyst, rare earth modified silicone defoamers A-E, allyl polyoxyethylene polyoxypropylene methyl ether, wherein chitosan, having an average molecular weight of 800, was purchased from Shanghai Kabushiki Kaisha, inc.; allyl glycidyl ether was purchased from shandong from new materials inc; the hydrogen-containing silicone oil is low hydrogen-containing silicone oil, the hydrogen content is 0.175%, and the viscosity is 80mm 2 S, available from Huagu silicone limited in bergamot; liquid paraffin is purchased from Shanghai Yi Lubricant technology Co., ltd, with the product number of 68#; span-80 is purchased from Nantong Hongshan chemical industry Co., ltd, and the model is S-80; the emulsifier A-110 was purchased from Jining Huipong chemical Co., ltd.
The preparation method of the allyl polyoxyethylene polyoxypropylene methyl ether comprises the following steps:
(a) Placing 110g of allyl alcohol and 4g of sodium hydroxide into a reaction kettle, vacuumizing at room temperature until the pressure reaches-0.095 MPa, heating to 80 ℃ while stirring, slowly introducing 812g of ethylene oxide and 1085g of propylene oxide, controlling the temperature at 120 ℃, and stopping the reaction after the reaction is carried out until the reaction kettle is under negative pressure to obtain allyl polyoxyethylene polyoxypropylene ether;
(b) Transferring the allyl polyoxyethylene polyoxypropylene ether obtained in the step (a) into a sealing kettle, adding 146g of sodium methoxide, controlling the temperature to 70 ℃ while stirring for 30min, removing methanol, heating the reaction kettle to 75 ℃, continuing stirring for 30min, introducing nitrogen for replacement, vacuumizing, closing a vacuum valve after the pressure reaches-0.095 MPa, slowly introducing 110g of chloromethane, keeping the kettle temperature at 85 ℃, controlling the pressure to be less than or equal to 0.5MPa, continuously reacting for 1h, and recovering excessive chloromethane after the reaction is finished to obtain a crude product;
(c) Transferring the crude product obtained in the step (b) into a water separator, adding 250g of purified water, stirring while controlling the temperature at 70 ℃, standing for layering, transferring the allyl polyoxyethylene polyoxypropylene methyl ether into a distillation kettle after water separation, adding 50g of magnesium silicate, stirring, keeping the kettle temperature at about 70 ℃, adsorbing for 30min, starting heating, distilling under reduced pressure, dehydrating, starting to blow nitrogen when the temperature is raised to 100 ℃, ending the operation after the temperature is raised to 105 ℃, and performing pressure filtration to obtain the allyl polyoxyethylene polyoxypropylene methyl ether (molecular weight is 1060); wherein, when allyl polyoxyethylene polyoxypropylene methyl ether is used, the stirring speed is 80r/min.
A method for preparing Karstedt catalyst, comprising the steps of:
450mL of isopropanol, 8g of chloroplatinic acid and 180g of 1, 3-divinyl-1, 3-tetramethyldisiloxane are placed into a reaction kettle for reflux reaction, the reaction temperature is 82 ℃, the reaction time is 4 hours, the reaction is finished, the temperature is reduced to room temperature, 11g of sodium carbonate solid is added for full stirring, and then filtration and dehydration are carried out, so that the Karstedt catalyst is prepared.
The required components and the contents of the components in the mixed rare earth A-C are shown in the table 1:
TABLE 1
The preparation method of the rare earth element modified siloxane defoamer A comprises the following steps:
(1.1.1) adding 20g of chitosan into 980g of acetic acid aqueous solution with volume fraction of 1.8%, stirring until the chitosan is fully dissolved, then adjusting the pH to 3.5 by using 0.15mol/L hydrochloric acid, dropwise adding 4g of allyl glycidyl ether for reaction, wherein the reaction temperature is 65 ℃, the reaction time is 24 hours, precipitating by using absolute ethyl alcohol after the reaction is finished, filtering, and washing 5 times by using absolute ethyl alcohol to obtain modified allyl glycidyl ether;
(1.2.1) adding 232g of allyl polyoxyethylene polyoxypropylene methyl ether, 780g of hydrogen-containing silicone oil and 500mL of toluene into a reaction kettle, stirring and heating to 58 ℃, then adding 1.2g of Karstedt catalyst, continuously heating to 100 ℃, carrying out heat preservation reaction for 3 hours, then continuously adding 12g of modified allyl glycidyl ether prepared in the step (1.1.1), carrying out heat preservation reaction for 2 hours, removing an organic solvent in vacuum, adding 1mL of water, heating to 50 ℃, and washing for 5 times to obtain an intermediate A;
(1.3.1) mixing 20g of the intermediate A prepared in the step (1.2.1), 1.6g of lanthanum nitrate and 0.4g of mixed rare earth A, adding 100mL of deionized water, and stirring until the mixture is fully reacted;
(1.4.1) placing the system after the reaction in the step (1.3.1) into 100mL of acetic acid aqueous solution with the volume fraction of 4%, fully stirring until the mixture is uniform, standing for 30h at normal temperature, sequentially adding 100mL of liquid paraffin, 30mL of span-80 and 40mL of ethyl acetate while stirring, adding 45mL of formaldehyde solution with the formaldehyde content of 35wt% for reaction, regulating the pH value of the reaction system to 8 and the temperature of 65 ℃ after 30min of reaction, adding 20mL of epichlorohydrin, after 5h of reaction, washing with absolute ethyl alcohol, vacuum filtering, washing with deionized water (6 times), and drying (the temperature is 55 ℃ for 4 h), thereby preparing the rare earth element modified siloxane defoamer A.
The preparation method of the rare earth element modified siloxane defoamer B comprises the following steps:
(1.1.2) adding 10g of chitosan into 490g of acetic acid aqueous solution with volume fraction of 1.75%, stirring until the chitosan is fully dissolved, then adjusting the pH to 3.5 by using 0.1mol/L hydrochloric acid, dropwise adding 2g of allyl glycidyl ether for reaction, wherein the reaction temperature is 60 ℃, the reaction time is 26 hours, precipitating by using absolute ethyl alcohol after the reaction is finished, filtering, and washing 5 times by using absolute ethyl alcohol to obtain modified allyl glycidyl ether;
(1.2.2) adding 120g of allyl polyoxyethylene polyoxypropylene methyl ether, 400g of hydrogen-containing silicone oil and 500mL of toluene into a reaction kettle, stirring and heating to 60 ℃, then adding 0.8g of Karstedt catalyst, continuously heating to 100 ℃, keeping the temperature for 2.5 hours, continuously adding 6.5g of modified allyl glycidyl ether prepared in the step (1.1.2), keeping the temperature for 1.5 hours, removing the organic solvent in vacuum, adding 0.5mL of water, heating to 48 ℃, and washing for 5 times to prepare an intermediate B;
(1.3.2) mixing 20g of intermediate B prepared in the step (1.2.2), 2.1g of lanthanum nitrate and 0.9g of mixed rare earth B, adding 100mL of deionized water, and stirring until the mixture is fully reacted;
(1.4.2) placing the system after the reaction in the step (1.3.2) into 100mL of acetic acid aqueous solution with the volume fraction of 4%, fully stirring until the mixture is uniform, standing for 26h at normal temperature, sequentially adding 100mL of liquid paraffin, 30mL of span-80 and 40mL of ethyl acetate while stirring, adding 40mL of formaldehyde solution with the formaldehyde content of 38wt% for reaction, regulating the pH value of the reaction system to 7.5 after the reaction is carried out for 30min, adding 20mL of epichlorohydrin after the reaction is carried out for 5h, washing with absolute ethyl alcohol, vacuum filtering, washing with deionized water (for 7 times), and drying (with the temperature of 60 ℃ for 4 h), thus obtaining the rare earth element modified siloxane defoamer B.
The preparation method of the rare earth element modified siloxane defoamer C comprises the following steps:
(1.1.3) adding 30g of chitosan into 1470g of acetic acid aqueous solution with volume fraction of 1.8%, stirring until the chitosan is fully dissolved, then adjusting the pH to 3.5 by using 0.12mol/L hydrochloric acid, dropwise adding 8g of allyl glycidyl ether for reaction, wherein the reaction temperature is 60 ℃, the reaction time is 30 hours, precipitating by using absolute ethyl alcohol after the reaction is finished, filtering, and washing 5 times by using absolute ethyl alcohol to obtain modified allyl glycidyl ether;
(1.2.3) adding 470g of allyl polyoxyethylene polyoxypropylene methyl ether, 1500g of hydrogen-containing silicone oil and 1000mL of toluene into a reaction kettle, stirring and heating to 62 ℃, then adding 2.1g of Karstedt catalyst, continuously heating to 100 ℃, keeping the temperature for reaction for 5 hours, then continuously adding 20g of modified allyl glycidyl ether prepared in the step (1.1.3), keeping the temperature for reaction for 3 hours, removing the organic solvent in vacuum, adding 1mL of water, heating to 45 ℃, and washing for 5 times to prepare an intermediate C;
(1.3.3) mixing 20g of intermediate C obtained in the step (1.2.3), 1.6g of lanthanum nitrate and 0.4g of mixed rare earth C, adding 100mL of deionized water, and stirring until the mixture is fully reacted;
(1.4.3) placing the system after the reaction in the step (1.3.3) into 100mL of acetic acid aqueous solution with the volume fraction of 4%, fully stirring until the mixture is uniform, standing for 28h at normal temperature, sequentially adding 100mL of liquid paraffin, 30mL of span-80 and 40mL of ethyl acetate while stirring, adding 45mL of formaldehyde solution with the formaldehyde content of 35wt% for reaction, regulating the pH value of the reaction system to 9 and the temperature of 65 ℃ after 30min of reaction, adding 20mL of epichlorohydrin, after 4h of reaction, washing with absolute ethyl alcohol, vacuum filtering, washing with deionized water (6 times), and drying (the temperature is 55 ℃ for 4 h), thereby preparing the rare earth element modified siloxane defoamer C.
The preparation method of the modified siloxane defoamer D is basically the same as that of the rare earth element modified siloxane defoamer A, and the difference is that: step (1.3.1) and step (1.4.1) are not used.
The preparation method of the modified siloxane defoamer E is basically the same as that of the rare earth element modified siloxane defoamer A, and the difference is that: step (1.3.1) is replaced by: and (3) mixing 20g of the intermediate A prepared in the step (1.2.1), 1.6g of lanthanum nitrate and 0.4g of mixed rare earth A, stirring until the mixture fully reacts, and drying to prepare the modified siloxane defoamer E.
Respectively taking 20g of defoamer, 5g of emulsifier A-110 and 80g of mixed solvent (the mixed solvent is water and ethanol with the mass ratio of 1:1), and stirring until the materials are fully mixed to obtain a sample 1-6 to be tested, wherein the stirring speed is 100r/min, and the stirring time is 5min, wherein the defoamer used by the sample 1-6 to be tested is shown in Table 2:
TABLE 2
The centrifugal stability test is carried out on the prepared sample 1-6 to be tested, and the defoaming property, the foam inhibition property and the antibacterial property are tested after the prepared sample 1-6 to be tested is placed for 10 days at room temperature, and the specific test method is as follows:
defoaming test: pouring 30mL of 3wt% sodium dodecyl benzene sulfonate aqueous solution into a 500mL measuring cylinder at room temperature, oscillating up and down for multiple times to ensure that the height of foaming liquid reaches 150mL, adding 0.04g of sample to be tested, starting a stopwatch to test the time for complete disappearance of foam, repeating the experiment for three times as the time is shorter and the defoaming performance is better, and taking an average value;
bubble suppression test: at room temperature, 100mL of 3wt% sodium dodecyl benzene sulfonate aqueous solution is poured into a 1L measuring cylinder, 0.1g of foaming liquid is added into the sample to be measured, nitrogen is introduced into the foaming liquid, the time for the foam to reach 300mL scale is recorded, the longer the time is, the better the foam inhibition performance is, the experiment is repeated for three times, and the average value is obtained.
Centrifugal stability test: and adding 0.4g of sample to be tested into 100mL of water, uniformly stirring, centrifuging for 5min at 3000r/min, and observing the centrifugal stability of the sample to be tested, wherein if layering does not exist, the centrifugal stability is proved to be good.
Antibacterial test: the inhibition activity of a sample to be tested on staphylococcus aureus and candida albicans is tested by adopting a turbidity method, and the specific operation steps are as follows:
A. adding 1000mL of sterilized distilled water into a 2000mL beaker, sequentially adding 5.0g of peptone, 1.0g of yeast powder, 10.0g of glucose and 3.0g of beef extract under electromagnetic stirring, and adjusting the pH to be neutral (7.2+/-0.2) by using a sodium hydroxide aqueous solution after uniformly stirring;
B. placing the test tubes on a test tube rack after cleaning and sterilizing, taking 4.0mL of the solution in the step A into each test tube by using a pipette, adding a rubber stopper, packaging each 6 test tubes once, and sterilizing for 20min at 121 ℃ by using a sterilizing pot for later use;
C. respectively weighing 0.00375-0.0042 g of sample to be tested in a centrifuge tube, dissolving with 150 mu L of dimethyl sulfoxide, respectively transferring 80 mu L of the dissolved sample into the numbered centrifuge tube after sterilization, and adding 4mL of Tween-20 into the centrifuge tube;
D. transferring 1mL to 3 pieces of solution in each separation tube into test tubes in the step B (operation before an alcohol lamp, preventing other bacteria from pollution);
E. taking a blank 96-well plate, measuring a blank OD value to exclude wells with an OD value greater than 0.05, adding 200 mu L of the solution in the test tube in the step D to each available well to measure the OD value and record, finally inoculating 40 mu L of activated staphylococcus aureus and candida albicans strains into each test tube, wrapping the test tubes with newspaper, carrying out shake culture in a constant-temperature shaking table at 30 ℃ and 180rpm for 24-48 hours, testing the OD value of the solution in the test tubes to track the growth state of bacteria, and taking 200 mu L of the solution in the test tubes to measure the OD value and record after the culture is finished;
F. the bacterial inhibition rate of the compound is calculated as follows:
corrected OD = sterile medium OD-sterile medium OD.
The toxic culture medium in the inhibition rate calculation formula is the culture medium containing the sample to be detected.
The test results are shown in Table 3, and are specifically as follows:
TABLE 3 Table 3
As can be seen from comparison of the sample 1 to be tested and the sample 6 to be tested, lanthanum nitrate, rare earth elements and chitosan are used for modifying the silicone defoaming agent, so that the prepared rare earth element modified silicone defoaming agent has good centrifugal stability, good defoaming property and foam inhibition property after being placed for a long time, and high inhibition rate on staphylococcus aureus and candida albicans;
as can be seen from comparison of sample 1 to sample 4 to 5, when the silicone defoamer is modified by using chitosan, although the prepared modified silicone defoamer has good centrifugal stability, the defoaming property and foam inhibition property are reduced, the inhibition rate to staphylococcus aureus and candida albicans is also reduced, even if lanthanum nitrate and rare earth elements are added into the defoamer modified by the silicone defoamer by chitosan, the defoaming property and foam inhibition property of the defoamer and the inhibition rate to staphylococcus aureus and candida albicans can be improved to a certain extent, the improvement to the defoaming property and foam inhibition property of the defoamer and the inhibition rate to staphylococcus aureus and candida albicans is not obvious, and the centrifugal stability is poor, and a slight layering phenomenon appears;
in conclusion, the rare earth element modified siloxane defoamer prepared by the preparation method of the rare earth element modified siloxane defoamer provided by the application has good centrifugal stability, good defoaming property and foam inhibition property even after long-time standing, high inhibition rate on staphylococcus aureus and candida albicans, and good bactericidal property.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a rare earth element modified siloxane defoamer is characterized by comprising the following steps: the method comprises the following steps:
(1.1) fully dissolving chitosan in an acid solution, then regulating the pH value to 2-5, dropwise adding allyl glycidyl ether for full reaction, and after the reaction is finished, precipitating, filtering and washing to obtain modified allyl glycidyl ether;
(1.2) adding allyl polyoxyethylene polyoxypropylene methyl ether, hydrogen-containing silicone oil and an organic solvent into a reaction kettle, adding a platinum-containing catalyst for full reaction, then adding the modified allyl glycidyl ether prepared in the step (1.1) for continuous reaction, and after the reaction is finished, carrying out suction filtration and washing to obtain an intermediate;
(1.3) mixing the intermediate prepared in the step (1.2), lanthanum nitrate and mixed rare earth, adding deionized water, and stirring until the mixture fully reacts;
(1.4) placing the system reacted in the step (1.3) into an acetic acid aqueous solution, fully stirring until the mixture is uniform, standing for 20-40 hours at normal temperature, sequentially adding liquid paraffin, an emulsifying agent and ethyl acetate while stirring, adding formaldehyde solution for reaction, adjusting the pH value of the reaction system to 7-9 after reaction for 5-30 minutes and adding epichlorohydrin at 50-80 ℃, fully reacting, and washing and suction-filtering after the reaction is finished to obtain the rare earth element modified siloxane defoamer;
the mixed rare earth contains 60-75wt% of lanthanum, 20-39% of cerium, 0.15-5% of praseodymium, 0.001-0.005% of lutetium and 0.05-0.25% of neodymium.
2. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the mass ratio of the chitosan and the allyl glycidyl ether in the step (1.1) is 1 (0.2-0.5).
3. The method for preparing a rare earth element modified silicone defoamer according to claim 1 or 2, characterized in that: the content of the platinum-containing catalyst in the step (1.2) is 0.05-2 per mill of the mass of the hydrogen-containing silicone oil.
4. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the mass ratio of the total mass of lanthanum nitrate and mixed rare earth to the mass of the intermediate in the step (1.3) is 1: (3-15); the mass ratio of the lanthanum nitrate to the mixed rare earth in the step (1.3) is (2-5): 1.
5. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the mass volume ratio of the intermediate in the step (1.3) to the formaldehyde solution in the step (1.4) is 1g (2-5) mL; the mass volume ratio of the intermediate in the step (1.3) to the epichlorohydrin in the step (1.4) is 1g (1-3) mL.
6. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the platinum-containing catalyst is a Karstedt catalyst.
7. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the formaldehyde content of the formaldehyde solution is 35-40wt%.
8. The method for preparing the rare earth element modified siloxane defoamer according to claim 1, wherein the method comprises the following steps: the acidic solution is an aqueous acetic acid solution.
9. Use of a rare earth element modified silicone defoamer prepared by the method for preparing a rare earth element modified silicone defoamer according to any one of claims 1 to 8 in the paper and printing industry.
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| CN114949941A (en) * | 2022-08-01 | 2022-08-30 | 广州嘉德乐生化科技有限公司 | Defoaming agent containing glyceryl monostearate and application of defoaming agent in medical industry |
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| CN114949941A (en) * | 2022-08-01 | 2022-08-30 | 广州嘉德乐生化科技有限公司 | Defoaming agent containing glyceryl monostearate and application of defoaming agent in medical industry |
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