CN110396042A - A kind of preparation method of pungent certain herbaceous plants with big flowers acid stannous - Google Patents
A kind of preparation method of pungent certain herbaceous plants with big flowers acid stannous Download PDFInfo
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- CN110396042A CN110396042A CN201910689753.0A CN201910689753A CN110396042A CN 110396042 A CN110396042 A CN 110396042A CN 201910689753 A CN201910689753 A CN 201910689753A CN 110396042 A CN110396042 A CN 110396042A
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- Prior art keywords
- stannous
- herbaceous plants
- big flowers
- certain herbaceous
- flowers acid
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- 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
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- 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
-
- 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
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- 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)
- Polyurethanes Or Polyureas (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to chemical fields, provide a kind of preparation method of new certain herbaceous plants with big flowers acid stannous, first new certain herbaceous plants with big flowers acid and stannous oxide are weighed according to material ratio, the molar ratio of the stannous oxide and new certain herbaceous plants with big flowers acid is 1.0:2.0~5.0, by new certain herbaceous plants with big flowers acid, stannous oxide investment reaction kettle, starts stirring, vacuum pump, in 100~115 DEG C of dehydrations until being come out without fraction, then proceed to reaction 1~2 hour, cooling down filtering obtains new certain herbaceous plants with big flowers acid stannous.Gel catalyst can be used as polyurethane foam industry using new certain herbaceous plants with big flowers acid stannous prepared by the present invention, relatively traditional stannous octoate catalyst is more environmentally-friendly, and stable storage is more preferable.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of new certain herbaceous plants with big flowers acid stannous, specifically a kind of preparation of new certain herbaceous plants with big flowers acid stannous
Method and its application in polyurethane foam.
Background technique
Flexible polyurethane foams are usually by polyether polyol or polyester polyol, water, amines catalyst, organosilyl surface
Activating agent, tin catalyst, physical blowing agent, other auxiliary agents and isocyanates mix under high velocity agitation, polyalcohol, water with it is different
Cyanate under the effect of the catalyst fast reaction formed reticular structure foams, while physical blowing agent volatilize, water with it is different
Polyisocyanate reactant generates bulk gas and is filled in foams, causes foams ceaselessly to expand, the gas of final foam Interior
Body is evaporated from foams, and foams reach maximum volume, and foams are slightly fallen after rise after gaseous volatilization, is base after five minutes
This molding.
The existing tin catalyst for preparing polyurethane flexible foam is stannous octoate, and chemical name is that 2 ethyl hexanoic acid is sub-
Tin, is pale yellow transparent viscous oil-like liquid, and unstable chemcial property is easily oxidized.And have always in stannous octoate
The remaining complete isooctyl acid of unreacted (2 ethyl hexanoic acid) is sending out skin, the irritating effect of mucous membrane health hazard
It is released after being thermally decomposed during bubble and has irritating acid mist, stannous octoate easily reacts for methyl tin three (isooctyl thioglycolate)
(abbreviation MMT, CAS No:57583-34-3), automobile industry are≤8ug/g to the isooctyl acid content requirement in sponge；To sponge
In MMT require as≤1ppm.
It is existing to have no the domestic synthetic method reported in relation to new certain herbaceous plants with big flowers acid stannous and its in the application of polyurethane foam.This hair
It is bright to provide a kind of preparation method of new certain herbaceous plants with big flowers acid stannous by technological innovation, and it is applied to polyurethane foam industry.This hair
Bright new certain herbaceous plants with big flowers acid stannous catalyst can be obviously improved the volatility of polyurethane flexible foam body, be free of isooctyl acid and methyl tin three
(isooctyl thioglycolate).Octanoic acid is essentially identical to using the polyurethane foam performance that new certain herbaceous plants with big flowers acid stannous of the invention is prepared
Stannous.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of new certain herbaceous plants with big flowers acid stannous, the preparation of this new certain herbaceous plants with big flowers acid stannous
Method will solve the tin catalyst unstable chemcial property for preparing polyurethane flexible foam in existing record, easily be oxidized
The technical issues of.
The present invention provides a kind of preparation methods of new certain herbaceous plants with big flowers acid stannous, first weigh new certain herbaceous plants with big flowers acid according to material ratio and oxidation is sub-
The molar ratio of tin, the stannous oxide and new certain herbaceous plants with big flowers acid is 1.0:2.0~5.0, and new certain herbaceous plants with big flowers acid, stannous oxide are put into reaction kettle
In, starting stirring, vacuum pump use nitrogen in reaction process so that the vacuum degree in reaction kettle is that -0.6MPa arrives -0.1Mpa
Protection, in 100~115 DEG C of dehydrations until coming out without fraction, the reaction was continued 1~2 hour, and then cooling down filters,
Obtain new certain herbaceous plants with big flowers acid stannous.
Further, the stannous oxide is using stannous chloride solution and the preparation of the compound containing sodium element, wherein chlorine
The molar ratio for changing stannous and the compound containing sodium element is 1.0:2.0~2.1.
Further, the compound containing sodium element be sodium hydroxide, sodium bicarbonate and sodium carbonate it is therein any one or
Two or more mixtures.
Further, the mass percentage of the stannous chloride solution Central Asia tin element is 35%~45%.
Further, the molar ratio of the stannous oxide and new certain herbaceous plants with big flowers acid is preferably 1: 4.
The present invention also provides the new certain herbaceous plants with big flowers acid stannous obtained using any of the above-described method to prepare poly- ammonia as catalyst
Application in ester flexible foam.
Specifically, above-mentioned stannous oxide the preparation method comprises the following steps:
(1) tin grain and hydrochloric acid reaction being prepared into stannous chloride, the molar ratio of above-mentioned hydrochloric acid and tin grain is 2.1~2.5: 1,
It is to slowly warm up to 110-120 DEG C of concentration, the hydrogen chloride gas of generation uses lye spray-absorption, is concentrated into the quality of stannous element
Percentage composition is the stannous chloride solution of 35%-45%, and cooling nitrogen protection is press-filtered out unreacted tin slab, while in protochloride
The metal tin particles that 5ppm is added in solution of tin prevent stannic generation；
(2) by sodium hydroxide, sodium bicarbonate and sodium carbonate is one such or a variety of mixtures are configured to quality percentage and contain
Amount is that the deionized water solution of 8-10% is put into the reaction kettle of step (1), and step (1) preparation is slowly added dropwise at 18~22 DEG C
Stannous chloride aqueous solution will be anti-when the pH value of sodium bicarbonate aqueous solution is gradually decrease to slightly biased acidity for reaction end
Stannous oxide is obtained by filtration by centrifugal dehydration in reaction solution after answering.
It, can also be with specifically, raw material stannous oxide used in reaction process can be prepared voluntarily according to the method described above
It buys on the market.
The present invention is compared with prior art, its technical effect is that actively and apparent.New certain herbaceous plants with big flowers acid stannous of the invention is stablized
Storage is better than stannous octoate, and new certain herbaceous plants with big flowers acid stannous prepared by the present invention can be used as gel catalyst for polyurethane foam row
Industry, relatively traditional stannous octoate catalyst is more environmentally-friendly, and stable storage is more preferable.
Specific embodiment
Embodiment 1
(1) preparation of stannous chloride solution: there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and lead to
In the four-hole boiling flask for having the 1000ml of nitrogen, 250g tin grain is put into flask, 435.75g mass percent concentration is then added dropwise
For 37% hydrochloric acid solution, stirring at normal temperature 24 hours, it is to slowly warm up to 110-120 DEG C, stannous chloride solution, temperature-rise period is concentrated
Reaction kettle is in cooling for reflux state, and the temperature for the refrigerated brine that flows back is -15 DEG C, and the hydrogen for reacting generation is put with blow-down pipe to alkali
The mass percentage that stannous chloride solution is concentrated into stannous is 37% by liquid spray equipment, and reaction kettle is down to room temperature, will react
Liquid carries out filters pressing under nitrogen protection, filters out unreacted tin grain and obtains stannous chloride solution.
(2) preparation of stannous oxide: there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and be connected with nitrogen
In the four-hole boiling flask of the 1000ml of gas, 71.75g soda is configured to the aqueous solution that mass percentage is 10% and is put into four mouthfuls of burnings
In bottle, blow valve is opened, in the 211.86g stannous chloride solution of 23 DEG C of a dropping steps (1) preparation, control pH value 6.2 to reaction
Reaction solution after reaction is obtained stannous oxide by centrifugal filtration by terminal.
(3) preparation of new certain herbaceous plants with big flowers acid stannous: there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and be connected with
In the four-hole boiling flask of the 500ml of nitrogen, the ratio that stannous oxide and new certain herbaceous plants with big flowers acid are 1: 4.5 in molar ratio is put into reaction kettle,
Start stirring, vacuum pump, nitrogen protection in reaction process, at 100 DEG C by dehydration, so that the vacuum degree in reaction kettle
- 0.1MPa is arrived for -0.6MPa, until being filtered after when coming out subsequent continuous insulation reaction 1 without fraction using cooling down, can be obtained
To the new certain herbaceous plants with big flowers acid stannous of finished product, density 1.16g/cm3, index of refraction 1.491, viscosity 4500mPa.s, the quality percentage of stannous
Content is 24.55%.
Embodiment 2
(1) preparation of stannous chloride solution: there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and lead to
In the four-hole boiling flask for having the 1000ml of nitrogen, 250g tin grain is put into flask, 531.4g mass percent concentration is then added dropwise
For 37% hydrochloric acid solution, stirring at normal temperature 24 hours, it is to slowly warm up to 110-120 DEG C, stannous chloride solution, temperature-rise period is concentrated
Reaction kettle is in cooling for reflux state, and the temperature for the refrigerated brine that flows back is -15 DEG C, and the hydrogen for reacting generation is put with blow-down pipe to alkali
The mass percentage that stannous chloride solution is concentrated into stannous is 35% by liquid spray equipment, and reaction kettle is down to room temperature, will react
Liquid carries out filters pressing under nitrogen protection, filters out unreacted tin grain and obtains stannous chloride solution.
(2) preparation of stannous oxide: there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and be connected with nitrogen
In the four-hole boiling flask of the 500ml of gas, 70g sodium bicarbonate is configured to the aqueous solution that mass percentage is 10% and is put into four mouthfuls of burnings
In bottle, blow valve is opened, prepares 137.9g stannous chloride solution in 20 DEG C of a dropping steps (1), control pH value 6.0 to reaction is eventually
Reaction solution after reaction is obtained stannous oxide by centrifugal filtration by point.
(3) there is fixed device, temperature incubation function, mechanical stirring, thermocouple at one and be connected with four mouthfuls of 500ml of nitrogen
In flask, there is the four-hole boiling flask of fixed device, temperature incubation function, mechanical stirring, thermocouple and the 500ml for being connected with nitrogen at one
In, the ratio that stannous oxide and new certain herbaceous plants with big flowers acid are 1: 2 in molar ratio is put into reaction kettle, starting stirring, vacuum pump, nitrogen are protected
Shield, in 115 DEG C of dehydrations, so that the vacuum degree in reaction kettle is that -0.6MPa arrives -0.1MPa, until after coming out without fraction
It is filtered after when continuing insulation reaction 1 using cooling down, the new certain herbaceous plants with big flowers acid stannous of finished product, density 1.23g/cm can be obtained3, refractive power
Rate is 1.494, viscosity 4800mPa.s, and the mass percentage of stannous is 25.05%.
Test example 1
By density flexible polyurethane foam in the new certain herbaceous plants with big flowers acid stannous catalyst preparation of Examples 1 to 2 preparation；It selects simultaneously
Commercially available stannous octoate T-9 is prepared for 35kg/m as a control group3Flexible polyurethane foam, it is raw materials used as shown in table 3.
Table 1 prepares high density flexible polyurethane foam formula used
Wherein, Dow V-3010 is the ethylene oxide and quality by glycerol as initiator and mass percent for 84%
The polyalcohol of the propylene oxide that percentage is 16% being mixed with out, is produced, hydroxyl value 56mgKOH/ by Dow Chemical
g；
TDI 80/20 be 2, the 4- toluene di-isocyanate(TDI) that mass percent is 80% and mass percent be 20% 2,
The mixture of 6- toluene di-isocyanate(TDI)；
Silicone BL-868 is that the organosilyl surface from Shanghai Mai Hao Chemical Industry Science Co., Ltd is living
Property agent；
Amine S-33 is solid amine mass percentage 33%, dipropylene glycol mass percentage 67%
Amines catalyst is produced by Shanghai Mai Hao Chemical Industry Science Co., Ltd；
Stannous octoate T-9 is bought from air chemical company, the U.S..
Measured performance parameter is carried out to the flexible polyurethane foam of preparation, obtained numerical value is as shown in table 4.
The performance parameter of 2 flexible polyurethane foam of table
Test example 2
Using Examples 1 to 2 prepare new certain herbaceous plants with big flowers acid stannous catalyst preparation slow rebound polyurethane foam body as group 1 He
Group 2；Commercially available stannous octoate T-9 is selected to be prepared for slow rebound polyurethane foam body as a control group simultaneously, it is raw materials used such as table 1
It is shown.
Table 3 prepares slow rebound polyurethane foam body formula used
Wherein, Dow V-2070 is specially designed to the special polyether polyol of slow rebound polyurethane foam body, by beauty
The production of state's DOW Chemical, hydroxyl value are 233mg KOH/g；
Cell Opener BL-1300 is specially designed to the aperture of slow rebound polyurethane foam body
Agent is bought from Shanghai Mai Hao Chemical Industry Science Co., Ltd；
Amine S-1、Amine S-33 andsilicone BL-627M
It is bought from Shanghai Mai Hao Chemical Industry Science Co., Ltd, other raw materials are the same as embodiment 1.
Measured performance parameter is carried out to the slow rebound polyurethane foam body of preparation, obtained numerical value is as shown in table 4.
The performance parameter of 4 slow rebound polyurethane foam body of table
Table 2 and table 4 statistics indicate that, compared with the control group, new certain herbaceous plants with big flowers acid stannous catalyst provided by the invention can replace
The isooctyl acid residual that stannous octoate prepares flexible polyurethane foam is lower, and the MMT methyl tin residual that European Union ROSH forbids is smaller,
The slow rebound polyurethane foam body gas permeability prepared simultaneously is excellent.
Claims (5)
1. a kind of preparation method of new certain herbaceous plants with big flowers acid stannous, it is characterised in that: first weigh new certain herbaceous plants with big flowers acid and stannous oxide, institute according to material ratio
The molar ratio of the stannous oxide and new certain herbaceous plants with big flowers acid stated is 1.0:2.0~5.0, by new certain herbaceous plants with big flowers acid, stannous oxide investment reaction kettle, is started
Stirring, vacuum pump use nitrogen protection, In in reaction process so that the vacuum degree in reaction kettle is that -0.6MPa arrives -0.1MPa
100~115 DEG C of dehydrations without fraction until come out, and the reaction was continued 1~2 hour, and then cooling down filters, and obtains new certain herbaceous plants with big flowers
Sour stannous.
2. a kind of preparation method of new certain herbaceous plants with big flowers acid stannous according to claim 1, it is characterised in that: the stannous oxide is adopted
It is prepared with stannous chloride solution with the compound containing sodium element, wherein the molar ratio of stannous chloride and the compound containing sodium element
For 1.0:2.0~2.1.
3. a kind of preparation method of new certain herbaceous plants with big flowers acid stannous according to claim 2, it is characterised in that: the change containing sodium element
Conjunction object is sodium hydroxide, sodium bicarbonate and sodium carbonate any one or two or more mixtures therein.
4. a kind of preparation method of new certain herbaceous plants with big flowers acid stannous according to claim 2, it is characterised in that: the stannous chloride
The mass percentage of solution Central Asia tin element is 35%~45%.
5. the new certain herbaceous plants with big flowers acid stannous obtained using any one of claim 1-4 method is preparing polyurethane flexible bubble as catalyst
Application in foam body.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910689753.0A CN110396042A (en) | 2019-07-29 | 2019-07-29 | A kind of preparation method of pungent certain herbaceous plants with big flowers acid stannous |
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| CN201910689753.0A CN110396042A (en) | 2019-07-29 | 2019-07-29 | A kind of preparation method of pungent certain herbaceous plants with big flowers acid stannous |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957285A (en) * | 2020-08-13 | 2020-11-20 | 南通恒光大聚氨酯材料有限公司 | Stannous octoate production process and intelligent reaction device thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775293A (en) * | 2011-05-13 | 2012-11-14 | 江苏大明科技有限公司 | Preparation process of stannous octanoate |
| CN105968339A (en) * | 2015-03-10 | 2016-09-28 | 赢创德固赛有限公司 | Antioxidants for producing low-emission PUR systems |
| US20160347901A1 (en) * | 2015-06-01 | 2016-12-01 | Air Products And Chemicals, Inc. | Reactive amine catalysts for polyurethane applications |
| CN109963909A (en) * | 2016-08-01 | 2019-07-02 | 斯塔尔国际有限公司 | The polymeric dispersions that acetaldehyde burst size reduces |
-
2019
- 2019-07-29 CN CN201910689753.0A patent/CN110396042A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775293A (en) * | 2011-05-13 | 2012-11-14 | 江苏大明科技有限公司 | Preparation process of stannous octanoate |
| CN105968339A (en) * | 2015-03-10 | 2016-09-28 | 赢创德固赛有限公司 | Antioxidants for producing low-emission PUR systems |
| US20160347901A1 (en) * | 2015-06-01 | 2016-12-01 | Air Products And Chemicals, Inc. | Reactive amine catalysts for polyurethane applications |
| CN107922579A (en) * | 2015-06-01 | 2018-04-17 | 赢创德固赛有限公司 | Reactive amine catalysts for polyurethane application |
| CN109963909A (en) * | 2016-08-01 | 2019-07-02 | 斯塔尔国际有限公司 | The polymeric dispersions that acetaldehyde burst size reduces |
Non-Patent Citations (1)
| Title |
|---|
| 李汾: "聚氨酯弹性体的新进展", 《化学推进剂与高分子材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111957285A (en) * | 2020-08-13 | 2020-11-20 | 南通恒光大聚氨酯材料有限公司 | Stannous octoate production process and intelligent reaction device thereof |
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