CN106117041A - A kind of synthetic method of isooctyl acid bismuth - Google Patents
A kind of synthetic method of isooctyl acid bismuth Download PDFInfo
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- CN106117041A CN106117041A CN201610500208.9A CN201610500208A CN106117041A CN 106117041 A CN106117041 A CN 106117041A CN 201610500208 A CN201610500208 A CN 201610500208A CN 106117041 A CN106117041 A CN 106117041A
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- isooctyl acid
- bismuth
- reaction
- synthetic method
- acid bismuth
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of organic synthesis, particularly relate to the synthesis technical field of a kind of bismuth organic compound, specifically disclose the synthetic method of a kind of isooctyl acid bismuth, using isooctyl acid and powdery bismuth oxide to carry out reaction under catalyst action and generate isooctyl acid bismuth, described catalyst is composite solid superacid SO4 2‑/ZrO2‑TiO2‑Fe2O3, wherein the mass ratio of Fe, Ti, Zr is 2:3:1.The inventive method synthesis reaction temperature is low, and course of reaction keeps negative pressure and reaction product water condensation distillated, economical environment-protective, and the isooctyl acid bismuth of generation has good catalysis activity in polyurethane synthesizes.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to the synthesis technical field of a kind of bismuth organic compound.
Background technology
Isooctyl acid bismuth is weak yellow liquid, water insoluble, is dissolved in petroleum ether, polyhydric alcohol etc., is a kind of environment-protecting polyurethane
Catalyst, for catalyzing and synthesizing, mainly to NCO and hydroxyl of the fields such as polyurethane resin, adhesive, coating, elastomer
Reaction between the active hydrogen such as base, amido has strong facilitation.Current isooctyl acid bismuth is all by saponification-double decomposition legal system
Standby, the method existing problems are to have waste water to produce.
Another production method of isooctyl acid bismuth is: use isooctyl acid and bismuth oxide direct reaction, after evaporating a small amount of moisture,
I.e. obtain finished product.This route produces 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 is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide the synthetic method of a kind of isooctyl acid bismuth, it is possible to reduce reaction temperature,
Reaction no waste produces, and the isooctyl acid bismuth of generation has good catalysis activity in polyurethane synthesizes.
For solving above-mentioned technical problem, the technical solution used in the present invention is: the synthetic method of a kind of isooctyl acid bismuth, bag
Include the reacting by heating under catalyst by reaction raw materials isooctyl acid and bismuth oxide, prepare isooctyl acid bismuth；Described catalyst is multiple
Mould assembly solid super-strong acid SO4 2-/ZrO2-TiO2-Fe2O3, wherein the mass ratio of Fe, Ti, Zr is preferably 2:3:1.
The synthetic reaction equation of the present invention is:
Composite solid superacid refers to the acid that the surface acid strength of solid is more higher than 100 % sulphuric acid, is a kind of novel catalysis
Material, wherein SO4 2-/ZrO2-TiO2-Fe2O3Type catalyst has more the advantages such as the acidity of its uniqueness, high activity, high selectivity.
The synthetic reaction of isooctyl acid bismuth of the present invention uses composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3As catalyst, add
The strong affinity of bismuth oxide and isooctyl acid, reduces the activation energy of reaction, therefore, it is possible to make reaction temperature reduce.
Further, after reaction raw materials is mixed with catalyst, heated for controlling temperature to 110 DEG C～120 DEG C of reactions.
Further, bismuth oxide is powdery, controls reaction and carries out under negative pressure, and the water produced in course of reaction is with steam shape
The condensed recovery of formula.Making reaction system be in negative pressure state, water generation reaction distillates at low temperature, it is also possible to reduce reaction temperature.
As preferably, control reaction vacuum absolute pressure less than 1013Pa.
As preferably, the reactor be furnished with condenser adds reaction raw materials isooctyl acid and powdery bismuth oxide and catalysis
Agent, stirs and heats, and during to 80 DEG C, starts evacuation, has condensing drip to distillate in condenser, continues heated for controlling temperature to 110 DEG C
～120 DEG C, the stopping heating when distillating without water droplet in condenser and in reactor, bismuth oxide is wholly absent, reaction terminates to prepare
Isooctyl acid bismuth.
Further, the mol ratio of the addition of reaction raw materials isooctyl acid and bismuth oxide is 6:1.
As preferably, catalyst charge is isooctyl acid and the 0.7 ‰ of the total material mass of bismuth oxide.
Use and have the beneficial effects that produced by technique scheme: the inventive method uses isooctyl acid and powdery bismuth oxide
Carrying out reaction under catalyst action and generate isooctyl acid bismuth, compared with prior art, reaction temperature reduces, and can avoid generation
Isooctyl acid bismuth partial oxidation and polymerization, improve reaction yield and ensure that it has good catalysis activity, simultaneously in industrialization
Production is implemented to be substantially reduced power consumption, produce without waste water, energy-conserving and environment-protective.
Present invention reaction is liquid-solid reaction system, and the water of generation constantly deviates from reaction system through distillation in course of reaction,
The forward being conducive to reaction is carried out, and is simultaneously achieved the separation of product, it is possible to directly obtain liquid isooctyl acid bismuth product.
Detailed description of the invention
The present invention is as the composite solid superacid SO of catalyst4 2-/ZrO2-TiO2-Fe2O3Use sol-gel process
Preparation, and by orthogonal experiment, the catalysis activity of catalyst is carried out checking with preferred.
Sol-gel process 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 dehydrated alcohol respectively, obtains rufous ferrum
Alcoholic solution, transparent zirconium alcoholic solution and transparent titanium alcoholic solution, and dropping ammonia is about 8～about 9 to pH respectively, is allowed to hydrolyze
Form gelatinous precipitate.After room temperature ageing 24h, after three parts of precipitation mix homogeneously, add 5 methanol, use magnetic stirrer
1h.Sucking filtration, is dried, and grinds, and crosses 110 mesh sieves.
By a certain amount of for gained ZrO2-TiO2-Fe2O3Precursor is placed in the H of variable concentrations by 10mL2SO4Dipping reaches 1h, takes out
Filter, dries, and takes out after Muffle kiln roasting certain time, stand-by.
Being found by orthogonal experiment, when Fe, Ti, Zr mass ratio is 2:3:1, the catalysis activity of this solid super-strong acid is
Good, and reaction yield is 95.5%.
Utilize the composite solid superacid SO that Fe, Ti, Zr mass ratio is 2:3:14 2-/ZrO2-TiO2-Fe2O3As urging
Agent synthesis isooctyl acid bismuth, is exemplified below 1-9.
Embodiment 1
The synthetic method of a kind of isooctyl acid bismuth, comprises the following steps:
(1) in the 500ml flask be furnished with heater, agitating device, condenser and negative port, isooctyl acid 185.8g is added,
Powdery bismuth oxide 100g, catalyst 0.2g；
(2) opening heating and agitating device, mixing speed is more than 130rpm, the raw material in step (1) flask is heated to 80 DEG C
Time, starting evacuation, vacuum is less than 1013Pa, has condensing drip to distillate in condenser, along with temperature rising condensed water is continuous
Distillating, continue to be heated to temperature and reach 115 DEG C, maintaining temperature is 110 DEG C ~ 120 DEG C, when distillating without water droplet in condenser and burning
When in Ping, powdery bismuth oxide is wholly absent, stopping reacting by heating terminating, and obtains 274g faint yellow isooctyl acid bismuth liquid.
Isooctyl acid, bismuth oxide, catalyst used by the present embodiment are all the industrial goods that purity is more than 99%.
The effect example of embodiment 1 and comparative example
The present embodiment made isooctyl acid bismuth and the frothing test correction data such as following table of saponification-double decomposition made isooctyl acid bismuth:
Table 1
By table 1 data, the made isooctyl acid bismuth of the present embodiment 1 isooctyl acid bismuth made with saponification-double decomposition closes at polyurethane
In one-tenth, catalytic performance is suitable, and catalytic effect is good.
Embodiment 2
The synthetic method of a kind of isooctyl acid bismuth, comprises the following steps:
(1) in the 500ml flask be furnished with heater, agitating device, condenser and negative port, isooctyl acid 185.8g is added,
Powdery bismuth oxide 100g, catalyst 0.2g；
(2) opening heating and agitating device, mixing speed is more than 130rpm, the raw material in step (1) flask is heated to 80 DEG C
Time, starting evacuation, vacuum is less than 1013Pa, has condensing drip to distillate in condenser, along with temperature rising condensed water is continuous
Distillating, continue to be heated to temperature and reach 115 DEG C, maintaining temperature is 110 DEG C～120 DEG C, when condenser distillates without water droplet and
When in flask, powdery bismuth oxide is wholly absent, stopping reacting by heating terminating, and obtains 274.2g faint yellow isooctyl acid bismuth liquid.
Isooctyl acid, bismuth oxide, catalyst used by 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 with embodiment 2, and the quality of gained isooctyl acid bismuth product is as follows.
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 (8)
1. the synthetic method of an isooctyl acid bismuth, it is characterised in that: include reaction raw materials isooctyl acid and bismuth oxide at catalyst
The lower reacting by heating of catalysis, prepares isooctyl acid bismuth；Described catalyst is composite solid superacid SO4 2-/ZrO2-TiO2-Fe2O3。
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 1, it is characterised in that composite solid superacid
SO4 2-/ZrO2-TiO2-Fe2O3The mass ratio of middle Fe, Ti, Zr is 2:3:1.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 1 and 2, it is characterised in that by reaction raw materials with urge
After agent mixing, heated for controlling temperature to 110 DEG C～120 DEG C of reactions.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 3, it is characterised in that bismuth oxide is powdery, controls
Reaction is carried out under negative pressure, the most condensed recovery of water produced in course of reaction.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 4, it is characterised in that control reaction vacuum absolute
Pressure is less than 1013Pa.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 5, it is characterised in that be furnished with the reaction of condenser
Device adds reaction raw materials isooctyl acid and powdery bismuth oxide and catalyst, stirs and heat, during to 80 DEG C, start evacuation,
Condenser there is condensing drip distillate, continue heated for controlling temperature to 110 DEG C～120 DEG C, when condenser distillating without water droplet and instead
Stopping heating when answering bismuth oxide in device to be wholly absent, reaction terminates to prepare isooctyl acid bismuth.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 6, it is characterised in that reaction raw materials isooctyl acid and oxygen
The mol ratio of the addition changing bismuth is 6:1.
The synthetic method of a kind of isooctyl acid bismuth the most according to claim 7, it is characterised in that catalyst charge is different pungent
Acid and the 0.7 ‰ of the total material mass of bismuth oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (4)
| 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 |
| JP2003026751A (en) * | 2001-07-18 | 2003-01-29 | Nitto Kasei Co Ltd | Curing catalyst composition for polyurethane and urethane curable composition |
| 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 |
-
2016
- 2016-06-30 CN CN201610500208.9A patent/CN106117041B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| JP2003026751A (en) * | 2001-07-18 | 2003-01-29 | Nitto Kasei Co Ltd | Curing catalyst composition for polyurethane and urethane curable composition |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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