CN106117041B - A kind of synthetic method of isooctyl acid bismuth - Google Patents
A kind of synthetic method of isooctyl acid bismuth Download PDFInfo
- Publication number
- CN106117041B CN106117041B CN201610500208.9A CN201610500208A CN106117041B CN 106117041 B CN106117041 B CN 106117041B CN 201610500208 A CN201610500208 A CN 201610500208A CN 106117041 B CN106117041 B CN 106117041B
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- Prior art keywords
- isooctyl acid
- bismuth
- reaction
- catalyst
- bismuth oxide
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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
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Abstract
The present invention relates to technical field of organic synthesis, more particularly to a kind of synthesis technical field of bismuth organic compound, specifically disclose a kind of synthetic method of isooctyl acid bismuth, reaction generation isooctyl acid bismuth is carried out under catalyst action using isooctyl acid and powdery bismuth oxide, the catalyst is composite solid superacid SO4 2‑/ZrO2‑TiO2‑Fe2O3, the wherein mass ratio of Fe, Ti, Zr is 2:3:1.The method of the present invention synthesis reaction temperature is low, and reaction process keeps negative pressure and distillates reaction product water condensation, economical environment-protective, and the isooctyl acid bismuth of generation has good catalytic activity in polyurethane synthesis.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of synthesis technical fields of bismuth organic compound.
Background technology
Isooctyl acid bismuth is weak yellow liquid, not soluble in water, is dissolved in petroleum ether, polyalcohol etc., is a kind of environment-protecting polyurethane
Catalyst, for catalyzing and synthesizing for the fields such as polyurethane resin, adhesive, coating, elastomer, mainly to isocyanate group and hydroxyl
Reaction between the active hydrogens such as base, amido has strong facilitation.Current isooctyl acid bismuth is all by saponification-double decomposition legal system
Standby, this method is to have waste water generation there are problem.
Another production method of isooctyl acid bismuth is：It is directly reacted with isooctyl acid and bismuth oxide, after evaporating a small amount of moisture,
Obtain finished product.The route is generated without " three wastes ", but there is also some problems：A height of 160 DEG C~180 DEG C of reaction temperature, causes
The poor catalytic activity of product, production cost are high.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic methods of isooctyl acid bismuth, can reduce reaction temperature,
Reaction is generated without waste, and the isooctyl acid bismuth of generation has good catalytic activity in polyurethane synthesis.
In order to solve the above technical problems, the technical solution used in the present invention is：A kind of synthetic method of isooctyl acid bismuth, bag
It includes and reaction raw materials isooctyl acid and bismuth oxide is heated to reaction under catalyst, isooctyl acid bismuth is made；The catalyst is multiple
Mould assembly solid super-strong acid SO4 2-/ZrO2-TiO2-Fe2O3, the mass ratio of wherein Fe, Ti, Zr are preferably 2:3:1.
The present invention synthetic reaction equation be：
Composite solid superacid refers to the surface acid strength of solid acid more stronger than 100 % sulfuric acid, is a kind of new
Catalysis material, wherein SO4 2-/ZrO2-TiO2-Fe2O3Type catalyst is with more its unique acidity, high activity, highly selective etc.
Advantage.The synthetic reaction of isooctyl acid bismuth of the present invention uses composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3As catalysis
Agent strengthens the affinity of bismuth oxide and isooctyl acid, reduces the activation energy of reaction, therefore can reduce reaction temperature.
Further, after reaction raw materials are mixed with catalyst, heated for controlling temperature to 110 DEG C~120 DEG C reactions.
Further, bismuth oxide is powdery, and control reaction carries out under negative pressure, and the water generated in reaction process is with steam shape
The condensed recycling of formula.Reaction system is made to be in negative pressure state, reaction generation water is distillated in low temperature, can also reduce reaction temperature.
Preferably, control reaction vacuum degree absolute pressure is less than 1013Pa.
Preferably, reaction raw materials isooctyl acid and powdery bismuth oxide and catalysis are added in the reactor equipped with condenser
Agent is stirred and heated, until at 80 DEG C, starts to vacuumize, has condensing drip to distillate in condenser, continues heated for controlling temperature to 110 DEG C
~120 DEG C, when distillated in condenser without water droplet and in reactor bismuth oxide completely disappear when stop heating, reaction terminate be made
Isooctyl acid bismuth.
Further, the molar ratio of the addition of reaction raw materials isooctyl acid and bismuth oxide is 6:1.
Preferably, catalyst charge is the 0.7 ‰ of isooctyl acid and bismuth oxide total material quality.
It is using advantageous effect caused by above-mentioned technical proposal：The method of the present invention uses isooctyl acid and powdery bismuth oxide
Reaction generation isooctyl acid bismuth is carried out under catalyst action, compared with prior art, reaction temperature reduces, can be to avoid generation
Isooctyl acid bismuth partial oxidation and polymerization improve reaction yield and ensure it with good catalytic activity, while industrializing
Implement that energy consumption can be substantially reduced in production, no waste water generates, energy conservation and environmental protection.
Reaction of the invention is liquid-solid reaction system, and the water of generation constantly deviates from reaction system during the reaction through distilling,
Be conducive to the positive progress of reaction, while realize the separation of product, liquid isooctyl acid bismuth product can be directly obtained.
Specific embodiment
Composite solid superacid SO of the present invention as catalyst4 2-/ZrO2-TiO2-Fe2O3Using sol-gel method
Prepare, and pass through orthogonal experiment to the catalytic activity of catalyst carry out verification and preferably.
Sol-gel method prepares composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3Method be：
By the FeCl of different ratio3•6H2O、ZrCl4•5H2O and TiCl4•5H2O is dissolved in absolute ethyl alcohol respectively, is obtained reddish brown
Color iron alcoholic solution, transparent zirconium alcoholic solution and transparent titanium alcoholic solution, and it is about 8~9 or so that ammonium hydroxide is added dropwise respectively to pH, is allowed to
Hydrolyze to form gelatinous precipitate.After room temperature ageing for 24 hours, three parts of precipitations are added in into 5 drop methanol after mixing, are stirred with magnetic stirring apparatus
Mix 1h.It filters, dry, 110 mesh sieves are crossed in grinding.
By a certain amount of ZrO of gained2-TiO2-Fe2O3Precursor is placed in the H of various concentration by 10mL2SO4Dipping is taken out up to 1h
Filter, drying, takes out, for use after a certain period of time in Muffle kiln roasting.
It is found by orthogonal experiment, is 2 in Fe, Ti, Zr mass ratio:3:When 1, the catalytic activity of the solid super-strong acid is most
It is good, and reaction yield is 95.5%.
It is 2 using Fe, Ti, Zr mass ratio:3:1 composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3As urging
Agent synthesizes isooctyl acid bismuth, is exemplified below 1-9.
Embodiment 1
A kind of synthetic method of isooctyl acid bismuth, comprises the following steps：
（1）Isooctyl acid is added in the 500ml flasks equipped with heating unit, agitating device, condenser and negative port
185.8g, powdery bismuth oxide 100g, catalyst 0.2g；
（2）Heating and agitating device are opened, mixing speed is more than 130rpm, by step（1）Raw material in flask is heated to
At 80 DEG C, start to vacuumize, vacuum degree is less than 1013Pa, has condensing drip to distillate in condenser, as temperature raises condensed water
It constantly distillates, continues to be heated to temperature and reach 115 DEG C, it is 110 DEG C ~ 120 DEG C to maintain temperature, when being distillated simultaneously without water droplet in condenser
And stop heating reaction when powdery bismuth oxide completely disappears in flask and terminate, obtain the faint yellow isooctyl acid bismuth liquid of 274g.
Isooctyl acid, bismuth oxide, catalyst used in the present embodiment are all the industrial goods that purity is more than 99%.
The effect example and comparative example of embodiment 1
The made isooctyl acid bismuth of the present embodiment and the frothing test correction data of the made isooctyl acid bismuth of saponification-double decomposition are as follows
Table：
Table 1
By 1 data of table, the made isooctyl acid bismuth of the present embodiment 1 is with the made isooctyl acid bismuth of saponification-double decomposition in poly- ammonia
Catalytic performance is suitable in Lipase absobed, and catalytic effect is good.
Embodiment 2
A kind of synthetic method of isooctyl acid bismuth, comprises the following steps：
（1）Isooctyl acid is added in the 500ml flasks equipped with heating unit, agitating device, condenser and negative port
185.8g, powdery bismuth oxide 100g, catalyst 0.2g；
（2）Heating and agitating device are opened, mixing speed is more than 130rpm, by step（1）Raw material in flask is heated to
At 80 DEG C, start to vacuumize, vacuum degree is less than 1013Pa, has condensing drip to distillate in condenser, as temperature raises condensed water
It constantly distillates, continues to be heated to temperature and reach 115 DEG C, it is 110 DEG C~120 DEG C to maintain temperature, when being distillated in condenser without water droplet
And stop heating reaction when powdery bismuth oxide completely disappears in flask to terminate, obtain the faint yellow isooctyl acid bismuth liquid of 274.2g.
Isooctyl acid, bismuth oxide, catalyst used in the present embodiment are all the industrial goods that purity is more than 99%.
Embodiment 3-9
The synthetic method of the isooctyl acid bismuth of embodiment 3-9 is the same as embodiment 2, the following institute of quality of gained isooctyl acid bismuth product
Show.
Table 2
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Isooctyl acid bismuth/g | 273 | 273.9 | 273.5 | 273.7 | 273.1 | 273.5 | 273.6 |
Claims (3)
1. a kind of synthetic method of isooctyl acid bismuth, it is characterised in that：Including by reaction raw materials isooctyl acid and bismuth oxide in catalyst
The molar ratio of the addition of the lower heating reaction of catalysis, reaction raw materials isooctyl acid and bismuth oxide is 6:1, heated for controlling temperature to 110 DEG C~
120 DEG C, control reaction absolute pressure is less than 1013Pa, and catalyst charge is isooctyl acid and bismuth oxide total material quality
0.7 ‰, isooctyl acid bismuth is made；The catalyst is composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3, and it is described compound
Type solid super-strong acid SO4 2-/ZrO2-TiO2-Fe2O3The mass ratio of middle Fe, Ti, Zr are 2:3:1.
2. the synthetic method of a kind of isooctyl acid bismuth according to claim 1, which is characterized in that bismuth oxide is powdery, control
Reaction carries out under negative pressure, the water generated in reaction process condensed recycling in vapour form.
3. the synthetic method of a kind of isooctyl acid bismuth according to claim 1, which is characterized in that in the reaction equipped with condenser
Reaction raw materials isooctyl acid and powdery bismuth oxide and catalyst are added in device, stirs and heats, until at 80 DEG C, starts to vacuumize,
There is condensing drip to distillate in condenser, continue heated for controlling temperature to 110 DEG C~120 DEG C, when being distillated in condenser without water droplet and instead
It answers and stops heating when bismuth oxide completely disappears in device, reaction terminates that isooctyl acid bismuth is made.
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| CN108101773A (en) * | 2017-12-27 | 2018-06-01 | 清远先导材料有限公司 | A kind of preparation method of isooctyl acid bismuth |
| CN111484047A (en) * | 2020-04-20 | 2020-08-04 | 黑龙江大学 | Preparation method and application of environment-friendly concrete surface anti-freezing coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6002031A (en) * | 1998-09-04 | 1999-12-14 | International Business Machines Corporation | Metal alkoxyalkoxidecarboxylates and use to form films |
| CN1793101A (en) * | 2005-12-23 | 2006-06-28 | 华东师范大学 | Process for hydrothermal synthesizing bismuth citrate |
| CN105198726A (en) * | 2015-09-07 | 2015-12-30 | 珠海市金团化学品有限公司 | Preparation method of organic bismuth subgallate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003026751A (en) * | 2001-07-18 | 2003-01-29 | Nitto Kasei Co Ltd | Curing catalyst composition for polyurethane and urethane curable composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6002031A (en) * | 1998-09-04 | 1999-12-14 | International Business Machines Corporation | Metal alkoxyalkoxidecarboxylates and use to form films |
| CN1793101A (en) * | 2005-12-23 | 2006-06-28 | 华东师范大学 | Process for hydrothermal synthesizing bismuth citrate |
| CN105198726A (en) * | 2015-09-07 | 2015-12-30 | 珠海市金团化学品有限公司 | Preparation method of organic bismuth subgallate |
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