CN113698429B - Amino acid stannous and application thereof in polyurethane foam - Google Patents
Amino acid stannous and application thereof in polyurethane foam Download PDFInfo
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- CN113698429B CN113698429B CN202110919730.1A CN202110919730A CN113698429B CN 113698429 B CN113698429 B CN 113698429B CN 202110919730 A CN202110919730 A CN 202110919730A CN 113698429 B CN113698429 B CN 113698429B
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- amino acid
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 66
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 18
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 18
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- -1 amino acid stannous oxide Chemical class 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 150000007942 carboxylates Chemical class 0.000 abstract description 4
- 229940107700 pyruvic acid Drugs 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N pyruvic aldehyde Natural products CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 11
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KPRZOPQOBJRYSW-UHFFFAOYSA-N 2-(aminomethyl)phenol Chemical compound NCC1=CC=CC=C1O KPRZOPQOBJRYSW-UHFFFAOYSA-N 0.000 description 1
- NIXLJQORAUOBAU-UHFFFAOYSA-K 6-methylheptyl 2-[methyl-bis[[2-(6-methylheptoxy)-2-oxoethyl]sulfanyl]stannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](C)(SCC(=O)OCCCCCC(C)C)SCC(=O)OCCCCCC(C)C NIXLJQORAUOBAU-UHFFFAOYSA-K 0.000 description 1
- CRKYAPTXDZUXEM-UHFFFAOYSA-N C(C)C(C(=O)O)CCCC.C(CCCCC(C)C)(=O)O Chemical compound C(C)C(C(=O)O)CCCC.C(CCCCC(C)C)(=O)O CRKYAPTXDZUXEM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CAXODRAFHZHUHJ-UHFFFAOYSA-K [methyl-bis[(8-methyl-2-sulfanylnonanoyl)oxy]stannyl] 8-methyl-2-sulfanylnonanoate Chemical compound [Sn+3]C.CC(C)CCCCCC(S)C([O-])=O.CC(C)CCCCCC(S)C([O-])=O.CC(C)CCCCCC(S)C([O-])=O CAXODRAFHZHUHJ-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of chemical industry, in particular to an organotin catalyst, and specifically relates to amino acid stannous and application thereof in preparation of polyurethane foam. Firstly, pyruvic acid and aldehyde are used as raw materials to synthesize amino acid in three steps, and then the amino acid reacts with stannous oxide to prepare the amino acid stannous. Compared with the traditional stannous carboxylate, only carboxyl in the traditional stannous carboxylate is coordinated with the tin center, and the amino group and carboxyl in the amino acid stannous provided by the invention are simultaneously coordinated with the tin center, so that the complex is more stable and has higher catalytic activity. In addition, the method for synthesizing the amino acid is not reported in published literature, and the method has the advantages of low reagent cost, simpler formula, more convenient operation, environment friendliness, safety, high efficiency and environment friendliness and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to an organotin catalyst, and specifically relates to amino acid stannous and application thereof in preparation of polyurethane foam.
Background
The soft polyurethane foam is generally formed by mixing polyether polyol or polyester polyol, water, amine catalysts, an organosilicon surfactant, tin catalysts, a physical foaming agent, other assistants and isocyanate under the high-speed stirring, wherein the polyol, the water and the isocyanate react rapidly under the action of the catalysts to form a foam body with a net structure, meanwhile, the physical foaming agent volatilizes, a large amount of gas is generated by the reaction of the water and the isocyanate and filled in the foam body, the foam body is continuously expanded, the gas in the foam body volatilizes from the foam body finally, the foam body reaches the maximum volume, the foam body slightly falls back after the gas volatilizes, and the foam body is basically molded after five minutes.
The existing tin catalyst for preparing the polyurethane soft foam is stannous octoate, the chemical name of which is stannous 2-ethylhexanoate, and is light yellow transparent viscous oily liquid, the chemical property of which is unstable and is easy to oxidize. The stannous octoate always has residual unreacted and complete isooctanoic acid (2-ethylhexanoic acid), has stimulation to the skin and mucous membrane, emits irritating acid mist after being heated and decomposed in the foaming process, is easy to react into methyl tin tri (isooctyl thioglycolate) (MMT for short, CAS No. 57583-34-3), and the requirement of the automobile industry on the isooctanoic acid content in the sponge is less than or equal to 8ug/g; MMT requirements in the sponge are less than or equal to 1ppm.
The prior method for synthesizing the stannous amino acid and the application of the stannous amino acid in polyurethane foam are not reported in China. The invention provides a preparation method of amino acid stannous through technical innovation, and the amino acid stannous is applied to the polyurethane foam industry. The amino acid stannous catalyst can obviously improve the volatility of polyurethane soft foam, and does not contain isooctanoic acid and methyltin tris (isooctyl thioglycolate). The polyurethane foam prepared by the amino acid stannous of the invention has better performance than stannous octoate.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of amino acid stannous, which comprises the steps of weighing amino acid and stannous oxide according to a material ratio, wherein the molar ratio of the stannous oxide to the amino acid is 1.0: (2.0-2.2), putting amino acid and stannous oxide into a reaction kettle, starting stirring and a vacuum pump to ensure that the vacuum degree in the reaction kettle is between-0.6 MPa and-0.1 MPa, adopting nitrogen protection in the reaction process, carrying out dehydration reaction at 100-115 ℃ until no fraction comes out, continuing the reaction for 1-2 hours, and then cooling, cooling and filtering to obtain the amino acid stannous.
Wherein the amino acid has the following structural characteristics:
in the structure, R is selected from straight-chain or branched alkyl with 4-12 carbon atoms, such as n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-heptyl and the like.
The amino acids are synthesized by the following synthetic route:
wherein the first step is performed by reacting pyruvic acid with aldehydeSynthesizing a compound A in the presence of potassium hydroxide as a raw material;
the second step of hydrogenation reaction with compound B as material and Pd-C as catalyst, and acidifying to obtain compound B;
and thirdly, preparing the amino acid by taking o-hydroxybenzyl ammonia as a raw material and tetrabutylammonium bromide as a catalyst.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of amino acid stannous. Firstly, pyruvic acid and aldehyde are used as raw materials to synthesize amino acid in three steps, and then the amino acid reacts with stannous oxide to prepare the amino acid stannous. Compared with the traditional stannous carboxylate, only carboxyl in the traditional stannous carboxylate is coordinated with the tin center, and the amino group and carboxyl in the amino acid stannous provided by the invention are simultaneously coordinated with the tin center, so that the complex is more stable and has higher catalytic activity. In addition, the method for synthesizing the amino acid is not reported in published literature, and the method has the advantages of low reagent cost, simpler formula, more convenient operation, environment friendliness, safety, high efficiency and environment friendliness and is suitable for industrial production.
Detailed Description
General Synthesis procedure one (Synthesis of Compound A)
Under ice bath conditions, 120mmol of pyruvic acid and 100mmol of aldehyde are takenPlacing the mixture in a single-neck flask, adding 250mL of methanol for dissolution, adding 150mmol of 100mL of potassium hydroxide solution into the flask, adding the solution twice (adding 100mmol of solution in 30min, adding the rest of solution once again rapidly), stirring at 40 ℃ for half an hour, then reacting for 12 hours under the ice bath condition of 0 ℃, monitoring the reaction by a TLC plate to determine that a large amount of yellow solid is generated at the bottom of the flask, flushing with 50mL of methanol and 20mL of diethyl ether to obtain a yellow filter cake, and vacuum drying the filter cake for 12 hours to obtain the pure compound A.
General Synthesis procedure two (Synthesis of Compound B)
Adding 50 g of compound A and 250mL of ethanol into a hydrogenation reaction kettle, uniformly stirring, adding 1 g of palladium-carbon, connecting hydrogen, regulating the pressure of the hydrogen to 3 atmospheres, stirring at room temperature for reaction for 8 hours, stopping the reaction, opening the reaction kettle, filtering the palladium-carbon, concentrating the filtrate to 100mL, adding dilute hydrochloric acid to regulate the pH value to 3-4, extracting with ethyl acetate, collecting and drying the organic layer, and concentrating to obtain the compound B.
General Synthesis step three (Synthesis of amino acids)
70mmol of the compound B obtained in the previous step is dissolved in 150mL of toluene, 80mmol of o-hydroxyl An is added, stirring reaction is carried out at room temperature for 3 hours, then 7mmol of tetrabutylammonium iodide is added, stirring reaction is continued for 12 hours, filtration is carried out, a filter cake is washed 3 times with 15mL of diethyl ether, and vacuum drying is carried out for 12 hours, thus obtaining the pure amino acid.
General Synthesis step IV (Synthesis of stannous amino acid)
Weighing 50mmol of amino acid and stannous oxide, wherein the molar ratio of the stannous oxide to the amino acid is 1.0: (2.0-2.2), putting amino acid and stannous oxide into a reaction kettle, starting stirring and a vacuum pump to ensure that the vacuum degree in the reaction kettle is between-0.6 MPa and-0.1 MPa, adopting nitrogen protection in the reaction process, carrying out dehydration reaction at 100-115 ℃ until no fraction comes out, continuing the reaction for 1-2 hours, and then cooling, cooling and filtering to obtain the amino acid stannous.
Example one (synthesis of the amino acid stannous 1):
n-butyraldehyde is used as a raw material (R is n-propyl), a corresponding compound A is synthesized according to a general synthesis step I, a corresponding compound B is synthesized according to a general synthesis step II, a corresponding amino acid is synthesized according to a general synthesis step III, and a corresponding amino acid stannous 1 is synthesized according to a general synthesis step IV, wherein the yield is 86%. The Anal.calcd for C14H28N2O4Sn: C,41.31; h,6.93; n,6.88; sn,29.16.found: C,41.01; h,6.64; n,6.96; sn,29.48.
Example two (synthesis of amino acid stannous 2):
the method comprises the steps of taking isobutyraldehyde as a raw material (R is isopropyl), synthesizing a corresponding compound A according to a general synthesis step I, synthesizing a corresponding compound B according to a general synthesis step II, synthesizing a corresponding amino acid according to a general synthesis step III, and finally synthesizing a corresponding amino acid stannous 2 according to a general synthesis step IV, wherein the yield is 84%. The Anal.calcd for C14H28N2O4Sn: C,41.31; h,6.93; n,6.88; sn,29.16.found: C,41.11; h,6.56; n,6.92; sn,29.44.
Example three (synthesis of the amino acid stannous 3):
n-valeraldehyde is used as a raw material (R is n-butyl), a corresponding compound A is synthesized according to a first general synthesis step, a corresponding compound B is synthesized according to a second general synthesis step, a corresponding amino acid is synthesized according to a third general synthesis step, and a corresponding amino acid stannous 3 is synthesized according to a fourth general synthesis step, wherein the yield is 86%. Anal.calcd for C16H32N2O4Sn: C,44.16; h,7.41; n,6.44; sn,27.28.Found: C,44.51; h,7.18; n,6.12; sn,27.01.
Example four (synthesis of the amino acid stannous 4):
the method comprises the steps of taking isovaleraldehyde as a raw material (R is isobutyl), synthesizing a corresponding compound A according to a first general synthesis step, synthesizing a corresponding compound B according to a second general synthesis step, synthesizing a corresponding amino acid according to a third general synthesis step, and synthesizing corresponding amino acid stannous 4 according to a fourth general synthesis step, wherein the yield is 83%. Anal.calcd for C16H32N2O4Sn: C,44.16; h,7.41; n,6.44; sn,27.28.found: C,44.48; h,7.16; n,6.16; sn,27.05.
Example five (synthesis of the amino acid stannous 5):
n-hexanal is used as a raw material (R is n-amyl), a corresponding compound A is synthesized according to a general synthesis step I, a corresponding compound B is synthesized according to a general synthesis step II, a corresponding amino acid is synthesized according to a general synthesis step III, and a corresponding amino acid stannous 5 is synthesized according to a general synthesis step IV, wherein the yield is 83%. Anal.calcd for C18H36N2O4Sn: C,46.67; h,7.83; n,6.05; sn,25.63.Found: C,46.33; h,7.61; n,6.27; sn,25.32.
Example six (synthesis of amino acid stannous 6):
n-octanal is used as a raw material (R is n-heptyl), a corresponding compound A is synthesized according to a general synthesis step I, a corresponding compound B is synthesized according to a general synthesis step II, a corresponding amino acid is synthesized according to a general synthesis step III, and a corresponding amino acid stannous 6 is synthesized according to a general synthesis step IV, wherein the yield is 81%. Anal calculated for C22H44N2O4Sn C,50.88; h,8.54; n,5.39; sn,22.86.Found: C,50.45; h,8.29; n,5.13; sn,22.53.
Example six (amino acid stannous catalytic performance test):
the stannous amino acids prepared in examples 1 to 6 were used as catalysts for preparing slow rebound polyurethane foams as groups 1 to 6, respectively; meanwhile, the commercial stannous octoate T-9 is used as a control group to prepare the slow rebound polyurethane foam, and the raw materials are shown in table 1.
Table 1 formulation (numerical values in parts by weight) for preparing slow rebound polyurethane foam:
wherein Dow V-3010 is a polyol prepared by mixing glycerin as an initiator with 84% by mass of ethylene oxide and 16% by mass of propylene oxide, and has a hydroxyl value of 56mgKOH/g, produced by Dow chemical in the United states;
dow V-2070 is a special polyether polyol specifically designed for slow rebound polyurethane foam, produced by Dow chemical in the United states, having a hydroxyl number of 233mg KOH/g;
cell Opener BL-1300 is a Cell Opener specifically designed for slow rebound polyurethane foam, purchased from Shanghai Maihao chemical technology Co., ltd;
amine S-33 is an Amine catalyst with 33 mass percent of solid Amine and 67 mass percent of dipropylene glycol, and is produced by Shanghai Maihao chemical industry Co., ltd
Amine S-1 is an Amine catalyst, < ->Silicone BL-627M is an organosilicon surfactant, and is purchased from Shanghai Maihao chemical technology Co.
The performance parameters of the prepared slow rebound polyurethane foam were measured, and the obtained values are shown in table 2.
Table 2 performance parameters of slow rebound polyurethane foam:
the data in tables 1 and 2 show that compared with a control group, the amino acid stannous catalyst provided by the invention can replace stannous octoate to prepare a soft polyurethane foam, the required organotin catalyst dosage is lower, the MMT residues forbidden by European Union ROSH are smaller, and meanwhile, the prepared slow rebound polyurethane foam has excellent air permeability.
Claims (2)
1. A preparation method of amino acid stannous is characterized in that amino acid stannous is prepared by reacting amino acid with stannous oxide, and the amino acid has the structure ofWherein R is selected from n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and n-heptyl; the preparation method of the amino acid comprises the following synthetic routes:
firstly, weighing amino acid and stannous oxide according to a material ratio, wherein the molar ratio of the stannous oxide to the amino acid is 1.0: (2.0-2.2), putting amino acid and stannous oxide into a reaction kettle, starting stirring and a vacuum pump to ensure that the vacuum degree in the reaction kettle is between-0.6 MPa and-0.1 MPa, adopting nitrogen protection in the reaction process, carrying out dehydration reaction at 100-115 ℃ until no fraction comes out, continuing the reaction for 1-2 hours, and then cooling and filtering to obtain the amino acid stannous oxide, wherein the amino acid stannous oxide has a structure as follows:
2. use of the stannous amino acid obtained by the process of claim 1 as a catalyst in the preparation of polyurethane foam.
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| CN101265188A (en) * | 2008-04-21 | 2008-09-17 | 太仓市浦源化工有限公司 | Method for preparing ethyl 2-oxy-4-phenylbutyrate |
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| CN110092899A (en) * | 2019-05-23 | 2019-08-06 | 大连汇鹏达化工有限公司 | A kind of purposes of phenylalanine stannous complex |
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| CN101265188A (en) * | 2008-04-21 | 2008-09-17 | 太仓市浦源化工有限公司 | Method for preparing ethyl 2-oxy-4-phenylbutyrate |
| CN109336922A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A method of preparation alpha-keto ester containing phosphine is reacted using witting |
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