CN106278868A - A kind of method cleaning production organic bismuth catalyst isooctyl acid bismuth - Google Patents
A kind of method cleaning production organic bismuth catalyst isooctyl acid bismuth Download PDFInfo
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- CN106278868A CN106278868A CN201610580307.2A CN201610580307A CN106278868A CN 106278868 A CN106278868 A CN 106278868A CN 201610580307 A CN201610580307 A CN 201610580307A CN 106278868 A CN106278868 A CN 106278868A
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- 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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Abstract
A kind of method cleaning production organic bismuth catalyst isooctyl acid bismuth, belongs to catalyst preparation technical field.The present invention is with bismuth oxide, acetic anhydride and isooctyl acid as primary raw material, it is solvent with acetic acid, prepares isooctyl acid bismuth through two-step reaction, utilize infrared spectrum (FT IR) that its structure is characterized, the method using EDTA complexometry, records the content of metal ion bismuth in isooctyl acid bismuth.Raw material of the present invention is easy to get, cheap, solvent is recyclable to be reused, and produces without the three wastes, the isooctyl acid bismuth prepared can be as a kind of new and effective, nontoxic, environmental type elastic polyurethane body catalyst, to replace the bigger organotin of currently used toxicity, lead, hydrargyrum class heavy metal catalyst.
Description
Technical field
The present invention relates to a kind of method cleaning and producing organic bismuth catalyst isooctyl acid bismuth, product isooctyl acid bismuth can be as poly-
The catalyst of urethane elastomer.This catalyst has efficient, nontoxic, the advantage of environmental protection, to replace currently used toxicity
Bigger organotin, lead, hydrargyrum class heavy metal catalyst, belong to catalyst preparation technical field.
Background technology
Polyurethane elastomer is a kind of uniqueness, soft chain segment and hard segment alternately inlay and to form, containing many amino
The polar polymer of carbamate group.Its soft chain segment is generally made up of oligomer polyol, and hard segment is generally by two Carbimide .s
Ester and small molecule chain extender composition.By selecting suitable soft, hard segment structure and ratio, the physical mechanical of polyurethane elastomer
Performance can in very large range be changed, adjust；And the micro phase separation structure that the strong electrostatic interaction between hard segment is formed,
Making it have again good biology and blood compatibility, it is easily processed into type to add polyurethane, and usual way can be used to go out
The advantages such as bacterium so that it is the application in biomedical sector is the most extensively got up.
In the synthesis of polyurethane elastomer, in order to add the speed of fast response, reach fast setting purpose, generally require and add
Enter catalyst.Conventional catalyst has tertiary amines, organotin, Organic leadP and organic mercury class catalyst.Organic acid bismuth is in recent years
The Novel non-toxic for synthesis of polyurethane material of exploitation, environmental type catalyst, be applied in polyurethane elastomer compare stannum
Compound has more preferable stability to hydrolysis resistance, and application result shows, it is possible to substantially reduce the generation of the bubble of product, and permissible
Increase substantially response speed.Its reaction mechanism and organic tin have obvious difference, it can promote isocyanate group (-NCO) and
Hydroxyl (-OH) reacts and avoids the side reaction of-NCO.It is possible not only to improve the speed of polyurethane synthetic reaction but also permissible
The polyhydric alcohol of the different relative molecular mass of regulation and the reactivity of isocyanates so that the polyurethane prepolymer of preparation has relatively
Narrow molecular vibrational temperature and relatively low viscosity；Such catalyst also has nontoxic simultaneously, harmless with human contact, and safe is excellent
Point, therefore can be used for synthesis of medical and daily polyurethane material, to replace the bigger organotin of currently used toxicity, lead, hydrargyrum
Class heavy metal catalyst.
Isooctyl acid bismuth is a kind of efficiently organic bismuth catalyst, can be used for Synthetic Leather slurry, coating, adhesive, close
The production of the products such as sealing, runway glue, elastomer and foam plastics.Also PVC system can be joined as heat stabilizer
In product, improve its heat stability.
JP2000178291A discloses a kind of method preparing isooctyl acid bismuth, first reacts prepared different with isooctyl acid and ammonia
Ammonium caprylate, prepares bismuth nitrate with bismuth oxide and dilute nitric acid reaction, then reacts with bismuth nitrate with isooctyl acid ammonium produced above, warp
Later process and obtain isooctyl acid bismuth product.This method metathesis reaction with water as solvent is due to reactant bismuth water-soluble not
Good, even if response speed is difficult to reaction completely the most slowly under transfer catalyst quaternary amine effect, and reaction raw materials is complicated,
Complex operation, cost is high, and productivity is low.
Summary of the invention
It is an object of the invention to overcome the weak point of above synthetic method, it is provided that a kind of cleaning produces organic bismuth catalyst
The method of isooctyl acid bismuth, this synthetic method is by a reactor successive reaction, and technique is simple, simple to operate, with short production cycle,
Productivity is high.Raw material and product are all asepsis environment-protectings, do not produce " three wastes ", environmentally safe, meet the green ring of country's promotion
Guaranteed request, has higher practical value.
Technical scheme, a kind of method cleaning production organic bismuth catalyst isooctyl acid bismuth, step is as follows:
(1) take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 15-16.31g(0.032mol ~ 0.035mol), acetic acid
Acid anhydride 2g(0.0196mol), with the rotating speed magnetic agitation of 400-600r/min, begin to warm up after slurry agitation is uniform, until warm
Degree reaches 120 DEG C；Continue to put into 8.7g(0.0854mol in there-necked flask) acetic anhydride, continues with the rotating speed of 600-800r/min
Continuous magnetic agitation is heated to 140 DEG C, and reaction is to upper solution clear；
(2) in batches by 30.28 g(0.21mol) isooctyl acid joins in above-mentioned system, maintain reaction temperature at 140 DEG C, decompression
Reaction, reaction, to steaming without acetic acid, obtains yellowish-brown transparence liquid, is product isooctyl acid bismuth.
The mol ratio of described reaction raw materials is: bismuth oxide acetic anhydride isooctyl acid=0.92 ~ 136.
With acetic acid as solvent, being effectively prevented the hydrolysis of isooctyl acid bismuth or alcoholysis, acetic acid is again product simultaneously, therefore acetic acid is permissible
Circulation is reused.Whole reaction process without " three wastes " produce, meet country promotion environmental protection, sustainable development want
Ask.Fixing acetic anhydride and the addition of isooctyl acid, control resultant metal ion concentration by the input amount of regulation bismuth oxide.
With bismuth ion content in EDTA compleximetry detection isooctyl acid bismuth product, specifically comprise the following steps that and weigh 0.15g's
Isooctyl acid bismuth, in clean 250mL conical flask, is sequentially added into 3mL nitric acid (wt%, 65.00%), and 10mL deionized water, at electric heating
Slight fever on stove, makes sample be dissolved into colourless transparent liquid, is cooled to room temperature, adds deionized water regulation solution ph, works as solution
During pH=1, dropping 5mL ascorbic acid solution (c=10g/L), shake up standing 5min, add 5 dimethyl phenol orange indicators, use
EDTA standard solution (c=0.01mol/L) titrates, and be titrated to solution being become glassy yellow from aubergine is terminal, and record consumes EDTA
The volume of standard solution, and it is calculated as follows the percentage composition of bismuth ion in isooctyl acid bismuth:
In formula:
0.209 bismuth ion milliequivalent, g；
The concentration of C EDTA standard solution, mol/ L；
V titrates the volume of the EDTA standard solution that auspicious product consume, mL；
The quality of the isooctyl acid bismuth that m weighs, g.
Making screening agent with ascorbic acid solution, make indicator with dimethyl phenol orange, make chelating agent with EDTA, the method is easy
Quickly, accuracy is high, highly sensitive, and favorable reproducibility can be used for instructing commercial production.
Beneficial effects of the present invention: raw material of the present invention is easy to get, cheap, solvent is recyclable to be reused, without " three wastes "
Producing, the isooctyl acid bismuth prepared can be as a kind of Novel non-toxic, environmental type elastic polyurethane body catalyst, to replace at present
The bigger organotin of toxicity that uses, lead, hydrargyrum class heavy metal catalyst.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Fig. 2 is the infared spectrum of product isooctyl acid bismuth.
Detailed description of the invention
The following examples are that the present invention is expanded on further, but the invention is not restricted to this.
Embodiment 1
Take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 15.45g, acetic anhydride 2g, turning with 400-600 r/min
Speed magnetic agitation, begins to warm up, when temperature reaches 120 DEG C after slurry agitation is uniform；Continue to put into 8.7g in there-necked flask
Acetic anhydride, continues magnetic agitation with the rotating speed of 600-800r/min and is heated to 140 DEG C, react to upper solution clear, then
It is dividedly in some parts 30.28 g isooctyl acids, keeps temperature constant, decompression distillation, react to not having acetic acid to steam and be reaction end,
Obtain yellow transparent liquid, be isooctyl acid bismuth.And with the content of EDTA complexometric titration bismuth ion, mass balance table has
Body is as shown in table 1.
The infared spectrum of isooctyl acid bismuth is as shown in Figure 2.In the infared spectrum of isooctyl acid bismuth, at 1544 cm-1Place is carboxylate radical
Asymmetrical stretching vibration peak, at 1460 cm-1With 1401 cm-1Place is the symmetrical stretching vibration peak of carboxylate radical, it was demonstrated that isooctyl acid
The successful synthesis of bismuth.At 1704 cm-1Place occurs in that the carbonyl vibration peak of the acetic acid of more weak non-Ex-all.
Embodiment 2
Take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 16.05g, acetic anhydride 2g, turning with 400-600 r/min
Speed magnetic agitation, begins to warm up, when temperature reaches 120 DEG C after slurry agitation is uniform；Continue to put into 8.7g in there-necked flask
Acetic anhydride, continues magnetic agitation with the rotating speed of 600-800r/min and is heated to 140 DEG C, react to upper solution clear, then
It is dividedly in some parts 30.28 g isooctyl acids, keeps temperature constant, decompression distillation, react to not having acetic acid to steam and be reaction end,
Obtain yellow transparent liquid, be isooctyl acid bismuth.And with the content of EDTA complexometric titration bismuth ion, mass balance table has
Body is as shown in table 1.
Embodiment 3
Take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 16.19g, acetic anhydride 2g, turning with 400-600 r/min
Speed magnetic agitation, begins to warm up, when temperature reaches 120 DEG C after slurry agitation is uniform；Continue to put into 8.7g in there-necked flask
Acetic anhydride, continues magnetic agitation with the rotating speed of 600-800r/min and is heated to 140 DEG C, react to upper solution clear, then
It is dividedly in some parts 30.28g isooctyl acid, keeps temperature constant, decompression distillation, react to not having acetic acid to steam and be reaction end,
To yellow transparent liquid, it is isooctyl acid bismuth.And with the content of EDTA complexometric titration bismuth ion, mass balance table is concrete
As shown in table 1.
Embodiment 4
Take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 16.31g, acetic anhydride 2g, turning with 400-600 r/min
Speed magnetic agitation, begins to warm up, when temperature reaches 120 DEG C after slurry agitation is uniform；Continue to put into 8.7g in there-necked flask
Acetic anhydride, continues magnetic agitation with the rotating speed of 600-800r/min and is heated to 140 DEG C, react to upper solution clear, then
It is dividedly in some parts 30.28 g isooctyl acids, keeps temperature constant, decompression distillation, react to not having acetic acid to steam and be reaction end,
Obtain yellow transparent liquid, be isooctyl acid bismuth.And with the content of EDTA complexometric titration bismuth ion, mass balance table has
Body is as shown in table 1.
Table 1 mass balance table
In Chemical Manufacture, yield, productivity and mass balance are important evaluation indexes.Wherein, yield refers at chemical reaction
Or during relevant chemical industry produces, the product yield of the actual production that input unit's quantity raw material obtains and the product of Theoretical Calculation
The ratio of product yield.Productivity=actual production/theoretical yield, theoretical yield refers to by reaction equation, the benchmark raw material of actual consumption
It is completely converted into the quality of product.In actual chemical reaction, owing to there is side reaction, reaction carries out not exclusively and separates
The reasons such as the loss caused in purification process, actual production is often below theoretical yield.Mass balance is material in Study system
Amount and the change of composition.The system herein said is exactly in the range of mass balance, and it can be an equipment or several equipment, also
Can be a unit operation or whole chemical process.Mass balance is most basic in Chemical Engineering Calculation, is also most important content
One of, it is the basis of energy balance.
By mass balance, yield and the metal ion content of table 1 it can be seen that the product that the feed ratio of 2# obtains has
Effect composition is the highest, and yield is the highest.3#, 4# product is cooled to room temperature and has partial white crystallization, affects product appearance.
It is thus determined that 2# experiment is optimum charging ratio.
Claims (2)
1. one kind is cleaned the method producing organic bismuth catalyst isooctyl acid bismuth, it is characterised in that step is as follows:
(1) take 50g acetic acid in 100mL there-necked flask, add bismuth oxide 15-16.31g i.e. 0.032mol ~ 0.035mol, acetic acid
Acid anhydride 2g i.e. 0.0196mol, with the rotating speed magnetic agitation of 400-600r/min, begins to warm up after slurry agitation is uniform, until warm
Degree reaches 120 DEG C；Continue to put into 8.7g i.e. 0.0854mol acetic anhydride in there-necked flask, continue with the rotating speed of 600-800r/min
Continuous magnetic agitation is heated to 140 DEG C, and reaction is to upper solution clear；
(2) 30.28 g i.e. 0.21mol isooctyl acid is joined in above-mentioned system in batches, maintain reaction temperature at 140 DEG C, reduce pressure
Reaction, reaction, to steaming without acetic acid, obtains yellowish-brown transparence liquid, is product isooctyl acid bismuth.
The method that the most according to claim 1, cleaning produces organic bismuth catalyst isooctyl acid bismuth, it is characterised in that: described reaction
The mol ratio of raw material is: bismuth oxide acetic anhydride isooctyl acid=0.92 ~ 136.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113024373A (en) * | 2021-03-12 | 2021-06-25 | 湖南柿竹园有色金属有限责任公司 | Production method of catalyst bismuth octoate for synthesizing polyurethane material |
Citations (5)
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| US4488998A (en) * | 1982-08-27 | 1984-12-18 | Atlantic Richfield Company | Preparation of higher antimony tricarboxylates in improved yields using an inert gas |
| CN1053424A (en) * | 1991-03-14 | 1991-07-31 | 中国石油化工总公司 | The preparation of metallic passivating agent of cracking catalyst and passivating agent products |
| JP2000178291A (en) * | 1998-12-21 | 2000-06-27 | Mitsubishi Materials Corp | Synthesis of bismuth 2-ethylhexanoate |
| CN101456806A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for preparing bismuth carboxylate |
| 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
- 2016-07-22 CN CN201610580307.2A patent/CN106278868B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4488998A (en) * | 1982-08-27 | 1984-12-18 | Atlantic Richfield Company | Preparation of higher antimony tricarboxylates in improved yields using an inert gas |
| CN1053424A (en) * | 1991-03-14 | 1991-07-31 | 中国石油化工总公司 | The preparation of metallic passivating agent of cracking catalyst and passivating agent products |
| JP2000178291A (en) * | 1998-12-21 | 2000-06-27 | Mitsubishi Materials Corp | Synthesis of bismuth 2-ethylhexanoate |
| CN101456806A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for preparing bismuth carboxylate |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| TIMOTHY R. KOCH 等: "New Method f o r the Preparation of Bismuth(II1) Triesters", 《J. ORG. CHERN.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113024373A (en) * | 2021-03-12 | 2021-06-25 | 湖南柿竹园有色金属有限责任公司 | Production method of catalyst bismuth octoate for synthesizing polyurethane material |
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