CN115093529A - Preparation method of stannous octoate complexing agent with strong antioxidant effect - Google Patents
Preparation method of stannous octoate complexing agent with strong antioxidant effect Download PDFInfo
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- CN115093529A CN115093529A CN202210774754.7A CN202210774754A CN115093529A CN 115093529 A CN115093529 A CN 115093529A CN 202210774754 A CN202210774754 A CN 202210774754A CN 115093529 A CN115093529 A CN 115093529A
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- stannous octoate
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000008139 complexing agent Substances 0.000 title claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 title claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 40
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940074391 gallic acid Drugs 0.000 claims abstract description 17
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- -1 stannous octoate compound Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- JUGZFZJHNWPDCS-UHFFFAOYSA-N 4-[2-(2,2-dimorpholin-4-ylethoxy)-1-morpholin-4-ylethyl]morpholine Chemical compound C1COCCN1C(N1CCOCC1)COCC(N1CCOCC1)N1CCOCC1 JUGZFZJHNWPDCS-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000574 octyl gallate Substances 0.000 description 3
- 235000010387 octyl gallate Nutrition 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 2
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 101100081581 Chlamydomonas reinhardtii ODA1 gene Proteins 0.000 description 1
- 101100224940 Chlamydomonas reinhardtii ODA2 gene Proteins 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a stannous octoate complexing agent with strong antioxidation effect, which takes gallic acid and n-octanol as raw materials, and is added with a catalyst prepared from dimorpholinylethyl ether, and under the action of the catalyst, n-octyl gallate with strong antioxidation is formed. And then, the n-octyl gallate and the stannous octoate are compounded and used for preparing polyurethane together, so that the problem of instability of the stannous octoate is solved, and the catalytic effect of the stannous octoate is enhanced.
Description
Technical Field
The invention relates to the field of polyurethane preparation, and in particular relates to a preparation method of a stannous octoate compound with a strong antioxidant effect.
Background
Polyurethanes, all known as polyurethane formates, are generally prepared by reacting a polyisocyanate and a polyol. From the view of molecular structure, the polyurethane macromolecule chain segment phase region is divided into a soft segment phase region and a hard segment phase region, the soft segment is composed of oligomer polyol, the hard segment is composed of isocyanate, chain extender and cross-linking agent, microscopic phase separation can be generated between the soft segment phase region and the hard segment phase region, intermolecular interaction forces such as hydrogen bonds and the like exist, physical cross-linking structures can be generated between chain segments, and the material forms a complex network system in the material, so that the polyurethane material has more excellent mechanical properties, wear resistance and other properties.
The polyurethane product has simple forming method, wider adjustable range of the formula and controllable product performance, so the polyurethane product is used for manufacturing various high polymer materials, such as foaming materials, water-based coatings, elastomers, sizing agents, spandex, sealants and the like. Can be widely applied to various fields of national economy such as light industry, petrifaction, energy, military industry and the like.
The synthesis of polyurethane can control the reaction rate by adding a catalyst, thereby controlling the molecular weight and molecular weight distribution of polyurethane, during the reaction process, the loss of polyol can be caused by violent reaction heat release, the reaction is incomplete, and the important way for controlling the reaction process is to adjust the proportion of dihydric alcohol and dibasic acid, use a step-type temperature rise process and select a specific catalyst. There are many kinds of catalysts used for the esterification reaction, including tin-based, antimony-based, and titanium-based catalysts. In the conventional polyester resin synthesis process, an organotin compound is generally used as an esterification catalyst. The organic tin compound is a metal organic compound formed by directly combining carbon element and tin element, has few side reactions when being used as a catalyst, does not influence the characteristics of the product such as purity, quality and the like, has good catalytic effect, has thermal stability and no corrosivity, does not need to be separated after the reaction is finished, does not need post-treatment, is convenient to produce, and can greatly shorten the process period. Stannous octoate is a traditional high-efficiency organic tin catalyst which is widely applied.
Chinese patent CN 105237729 a discloses an abrasion-resistant polyurethane material, which comprises the following raw materials: polytetrahydrofuran ether glycol, dimethyl diphenyl diisocyanate, dimethylolbutyric acid, triisopropanolamine, hydroquinone dihydroxyethyl ether, nano titanium dioxide, 3-isocyanatopropyl triethoxysilane and stannous octoate; during the preparation process of the abrasion-resistant polyurethane, taking dried polytetrahydrofuran ether glycol, heating, dropwise adding a dimethyl biphenyl diisocyanate solution, preserving heat, stirring, heating, dropwise adding a dimethylolbutyric acid solution, preserving heat, stirring, cooling, dropwise adding a triisopropanolamine solution and a hydroquinone dihydroxyethyl ether solution, preserving heat, stirring, and purifying to obtain an intermediate material; and introducing nitrogen, taking the intermediate material solution, adding stannous octoate, heating, dropwise adding the modified nano titanium dioxide solution, keeping the temperature, stirring, and purifying to obtain the abrasion-resistant polyurethane material. The invention has good wear resistance, good corrosion resistance and high mechanical property. However, in the prior art, stannous octoate is easy to hydrolyze in acidic and alkaline aqueous solutions, has a small stable pH value range, and is easy to be oxidized and decomposed by oxygen in the air and other oxidants, so that corresponding antioxidant substances are required to be added for compounding.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a stannous octoate compound agent with strong antioxidant effect, which has the following technical scheme:
a preparation method of a stannous octoate compound agent with strong antioxidation effect comprises the following steps:
s1, mixing dimorpholinylethyl ether and n-butyl bromide for reaction to prepare an intermediate;
s2, adding sulfuric acid into the intermediate prepared in the step S1 to react to obtain a mixture;
s3, mixing gallic acid powder and n-octyl alcohol uniformly, adding the mixture prepared in the step S2, heating for reaction, crystallizing the product to obtain white crystals, and performing suction filtration and drying to obtain n-octyl gallate;
s4, mixing the n-octyl gallate prepared in the step S3 with stannous octoate according to the mass ratio of 2-3: 9-13 to obtain the stannous octoate complexing agent.
Specifically, the preparation method of the stannous octoate compound agent with strong antioxidant effect comprises the following steps:
s1 bis-morpholinoethyl ether and n-butyl bromide are mixed according to a molar ratio of 1: 2-4, continuously introducing nitrogen for protection, stirring for 10-12 hours at 20-25 ℃, filtering to obtain a white solid, dissolving the white solid in absolute ethyl alcohol, carrying out reduced pressure rotary evaporation at 90-95 ℃ to remove the absolute ethyl alcohol, washing for 2-3 times by using ethyl acetate and petroleum ether respectively, and carrying out vacuum drying at 70-80 ℃ for 5-7 hours to obtain an intermediate;
s2, adding 75-80 wt% of sulfuric acid aqueous solution into the intermediate prepared in the step S1 under the protection of nitrogen, and stirring for 10-12 hours at 20-25 ℃; respectively washing the mixture with ethyl acetate and petroleum ether for 2-3 times, then carrying out vacuum drying at 50-60 ℃ for 6-8 h, and cooling to room temperature to obtain a mixture;
s3, mixing gallic acid powder and n-octyl alcohol uniformly, adding the mixture prepared in the step S2, heating at 50-65 ℃ for 60-80 min, carrying out reduced pressure rotary evaporation to remove excessive n-octyl alcohol, dissolving the residue with 90-95 wt% ethanol water solution, carrying out rotary evaporation again to 1/8-1/5 of the volume of the residue to obtain a concentrated solution, adding 3-8 times of volume of ultrapure water into the concentrated solution, placing the mixture at 0-4 ℃ for crystallization for 20-24 h to obtain white crystals, carrying out suction filtration for 2-3 times, and carrying out freeze drying at-40-30 ℃ for 7-8 h to obtain n-octyl gallate;
s4, mixing the n-octyl gallate prepared in the step S3 with stannous octoate according to the mass ratio of 2-3: and mixing the components in a ratio of 9-13 to obtain the stannous octoate complexing agent.
Further, in the step S1, the adding ratio of the white solid to the absolute ethyl alcohol is 1: 5-10 g/mL.
Further, the mass ratio of the intermediate to the aqueous sulfuric acid solution in step S2 is 1: 2 to 3.
Further, in the step S3, the mass ratio of n-octanol to gallic acid powder is 15-28: 1.
further, in the step S3, the addition amount of the mixture is 3 to 6% of the total mass of the n-octanol and the gallic acid powder.
Further, the volume ratio of the residue to the ethanol aqueous solution in step S3 is 1: 6-8.
According to the invention, gallic acid and n-octanol are used as raw materials, the catalyst prepared from dimorpholinyl ethyl ether is added, under the action of the catalyst, n-octyl gallate with strong oxidation resistance is formed, and then the n-octyl gallate and stannous octoate are compounded on the basis and are jointly used for preparing polyurethane, so that the problems that stannous octoate is easy to hydrolyze in acidic and alkaline aqueous solutions, the stably existing pH value range is small, and the stannous octoate is easy to be oxidized and decomposed by oxygen in the air and other oxidants are solved, and the catalytic effect of the stannous octoate can be enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. The operations referred to in the examples are, unless otherwise specified, all those of ordinary skill in the art.
Some raw material parameters in the comparative examples and examples of the invention are as follows:
gallic acid powder, CAS: 149-91-7, mecarsine reagent.
Example 1
The preparation method of the stannous octoate compound agent with strong antioxidant effect comprises the following steps:
s1 bis-morpholinoethyl ether and n-butyl bromide are mixed according to a molar ratio of 1: 3, mixing, continuously introducing nitrogen for protection, stirring for 12 hours at 25 ℃, filtering to obtain a white solid, dissolving the white solid in absolute ethyl alcohol, carrying out reduced pressure rotary evaporation at 95 ℃ to remove the absolute ethyl alcohol, washing for 3 times by using ethyl acetate and petroleum ether respectively, and carrying out vacuum drying for 7 hours at 80 ℃ to obtain an intermediate;
s2, adding 80 wt% sulfuric acid aqueous solution into the intermediate prepared in the step S1 under the protection of nitrogen, and stirring for 12 hours at 25 ℃; respectively washing with ethyl acetate and petroleum ether for 3 times, vacuum drying at 50 deg.C for 8 hr, and cooling to room temperature to obtain mixture;
s3, mixing gallic acid powder and n-octanol uniformly, adding the mixture prepared in the step S2, heating at 60 ℃ for 70min, carrying out reduced pressure rotary evaporation to remove excess n-octanol, dissolving the residue with 95 wt% ethanol aqueous solution, carrying out rotary evaporation again to 1/8 of the volume of the residue to obtain a concentrated solution, adding 5 times of ultrapure water into the concentrated solution, placing the mixture at 2 ℃ for crystallization for 24h to obtain white crystals, carrying out suction filtration for 3 times, and carrying out freeze drying at-40 ℃ for 8h to obtain n-octyl gallate;
s4, mixing the n-octyl gallate prepared in the step S3 and stannous octoate according to the mass ratio of 2: 11 to obtain the stannous octoate complexing agent.
The adding ratio of the white solid to the absolute ethyl alcohol in the step S1 is 1: 8 g/mL.
The mass ratio of the intermediate to the sulfuric acid aqueous solution in the step S2 is 1: 2.
the mass ratio of the n-octanol to the gallic acid powder in the step S3 is 25: 1.
the addition amount of the mixture in the step S3 is 4% of the total mass of the n-octanol and the gallic acid powder.
The volume ratio of the residue to the ethanol aqueous solution in the step S3 is 1: 7.
example 2
The preparation method of the stannous octoate compound agent with strong antioxidant effect comprises the following steps:
s1 mixing gallic acid powder and n-octanol uniformly, heating at 60 deg.C for 70min, rotary steaming under reduced pressure to remove excess n-octanol, dissolving the residue with 95 wt% ethanol water solution, rotary steaming again to 1/8 of the volume of the residue to obtain concentrated solution, adding 5 times volume of ultrapure water into the concentrated solution, placing at 2 deg.C for crystallization for 24h to obtain white crystal, vacuum filtering for 3 times, and freeze drying at-40 deg.C for 8h to obtain n-octyl gallate;
s2, mixing the n-octyl gallate prepared in the step S1 with stannous octoate according to the mass ratio of 2: 11 to obtain the stannous octoate complexing agent.
The mass ratio of the n-octanol to the gallic acid powder is 25: 1.
the volume ratio of the residue to the ethanol aqueous solution is 1: 7.
comparative example 1
The preparation method of the stannous octoate compound agent with strong antioxidant effect comprises the following steps:
mixing octyl gallate and stannous octoate according to the mass ratio of 2: 11 to obtain the stannous octoate complexing agent.
The octyl gallate is a commercially available product with CAS number of 1034-01-1 and is purchased from alatin.
Test example 1
Dissolving the n-octyl gallate prepared in the examples 1 and 2 and the octyl gallate in the comparative example 1 in pure methanol to obtain a solution with the weight percent of 3-5%, and then determining the DPPH free radical clearance: taking 3mL of the same volume of the solution to be detected and 2 multiplied by 10 ﹣4 mixing the solution of DPPH in mol/L (A1 tube); taking equal volume of absolute ethyl alcohol and 2 multiplied by 10 ﹣4 mol/Mixing L in DPPH (A2 tube); taking absolute ethyl alcohol with the same volume and uniformly mixing the absolute ethyl alcohol with a solution to be detected (A3 tube); after 30-DEG light-shielding reaction for 30min, the absorbance values of A1, A2 and A3 tubes were measured at 517nm using distilled water as a blank and recorded as ODA1, ODA2 and ODA3, respectively. DPPH radical clearance was calculated according to the following formula, and the test results are shown in table 1:
TABLE 1 DPPH radical scavenging rate test results table
As can be seen from table 1, in example 1, gallic acid and n-octanol are used as raw materials, and a catalyst prepared from dimorpholinylethyl ether is added, under the action of the catalyst, n-octyl gallate with the strongest oxidation resistance is formed, and the n-octyl gallate and stannous octoate are compounded and used for preparing polyurethane together, so that the problems that stannous octoate is easy to hydrolyze in acidic and alkaline aqueous solutions, the stable existing pH range is small, and stannous octoate is easy to be oxidized and decomposed by oxygen in the air and other oxidants can be effectively solved.
Claims (7)
1. A preparation method of a stannous octoate compound agent with strong antioxidant effect is characterized by comprising the following steps:
s1, mixing dimorpholinylethyl ether and n-butyl bromide for reaction to prepare an intermediate;
s2, adding sulfuric acid into the intermediate prepared in the step S1, and reacting to obtain a mixture;
s3, mixing gallic acid powder and n-octyl alcohol uniformly, adding the mixture obtained in the step S2, heating for reaction, crystallizing the product to obtain white crystals, and performing suction filtration and drying to obtain n-octyl gallate;
s4, mixing the n-octyl gallate prepared in the step S3 with stannous octoate according to the mass ratio of 2-3: 9-13 to obtain the stannous octoate complexing agent.
2. The method for preparing a stannous octoate compound with strong antioxidant effect according to claim 1, comprising the following steps:
s1 bis-morpholinoethyl ether and n-butyl bromide are mixed according to a molar ratio of 1: 2-4, continuously introducing nitrogen for protection, stirring for 10-12 hours at 20-25 ℃, filtering to obtain a white solid, dissolving the white solid in absolute ethyl alcohol, carrying out reduced pressure rotary evaporation at 90-95 ℃ to remove the absolute ethyl alcohol, washing for 2-3 times by using ethyl acetate and petroleum ether respectively, and carrying out vacuum drying at 70-80 ℃ for 5-7 hours to obtain an intermediate;
s2, adding 75-80 wt% of sulfuric acid aqueous solution into the intermediate prepared in the step S1 under the protection of nitrogen, and stirring for 10-12 hours at 20-25 ℃; respectively washing the mixture with ethyl acetate and petroleum ether for 2-3 times, then carrying out vacuum drying at 50-60 ℃ for 6-8 h, and cooling to room temperature to obtain a mixture;
s3, mixing gallic acid powder and n-octanol uniformly, adding the mixture prepared in the step S2 into the mixture, heating the mixture at 50-65 ℃ for 60-80 min, carrying out reduced pressure rotary evaporation to remove excessive n-octanol, dissolving the residue with 90-95 wt% ethanol water solution, carrying out rotary evaporation again to 1/8-1/5 of the volume of the residue to obtain a concentrated solution, adding 3-8 times of volume of ultrapure water into the concentrated solution, placing the mixture at 0-4 ℃ for crystallization for 20-24 h to obtain white crystals, carrying out suction filtration for 2-3 times, and carrying out freeze drying at-40-30 ℃ for 7-8 h to obtain n-octyl gallate;
s4, mixing the n-octyl gallate prepared in the step S3 and stannous octoate according to the mass ratio of 2-3: and mixing the components in a ratio of 9-13 to obtain the stannous octoate complexing agent.
3. The method for preparing a stannous octoate compound agent with strong antioxidant effect according to claim 2, wherein the stannous octoate compound agent comprises the following components: the adding ratio of the white solid to the absolute ethyl alcohol in the step S1 is 1: 5-10 g/mL.
4. The method for preparing a stannous octoate compound agent with strong antioxidant effect according to claim 2, wherein the stannous octoate compound agent comprises the following components: the mass ratio of the intermediate to the sulfuric acid aqueous solution in the step S2 is 1: 2 to 3.
5. The method for preparing a stannous octoate compound agent with strong antioxidant effect according to claim 2, wherein the stannous octoate compound agent comprises the following components in percentage by weight: in the step S3, the mass ratio of n-octanol to gallic acid powder is 15-28: 1.
6. the method for preparing a stannous octoate compound agent with strong antioxidant effect according to claim 2, wherein the stannous octoate compound agent comprises the following components: in the step S3, the addition amount of the mixture is 3-6% of the total mass of the n-octanol and the gallic acid powder.
7. The method for preparing a stannous octoate compound agent with strong antioxidant effect according to claim 2, wherein the stannous octoate compound agent comprises the following components in percentage by weight: the volume ratio of the residue to the ethanol aqueous solution in step S3 is 1: 6-8.
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| CN1180691A (en) * | 1996-10-17 | 1998-05-06 | 云南锡业公司研究设计院 | Method for one-step manufacture of stannous caprylate |
| CN101643418A (en) * | 2009-09-07 | 2010-02-10 | 湖南先伟实业有限公司 | Preparation method of gallic acid alcohol ester |
| CN101781214A (en) * | 2009-12-10 | 2010-07-21 | 张家界奥威科技有限公司 | Overdosed esterification production technology for n-octyl gallate |
| CN107473955A (en) * | 2017-08-02 | 2017-12-15 | 南通恒光大聚氨酯材料有限公司 | A kind of stannous octoate T 9 and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180691A (en) * | 1996-10-17 | 1998-05-06 | 云南锡业公司研究设计院 | Method for one-step manufacture of stannous caprylate |
| CN101643418A (en) * | 2009-09-07 | 2010-02-10 | 湖南先伟实业有限公司 | Preparation method of gallic acid alcohol ester |
| CN101781214A (en) * | 2009-12-10 | 2010-07-21 | 张家界奥威科技有限公司 | Overdosed esterification production technology for n-octyl gallate |
| CN107473955A (en) * | 2017-08-02 | 2017-12-15 | 南通恒光大聚氨酯材料有限公司 | A kind of stannous octoate T 9 and preparation method thereof |
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