CN107473923A - Polymerization inhibitor and its preparation technology for phenyl ethylene rectification - Google Patents
Polymerization inhibitor and its preparation technology for phenyl ethylene rectification Download PDFInfo
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- CN107473923A CN107473923A CN201610407905.XA CN201610407905A CN107473923A CN 107473923 A CN107473923 A CN 107473923A CN 201610407905 A CN201610407905 A CN 201610407905A CN 107473923 A CN107473923 A CN 107473923A
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- polymerization inhibitor
- phenyl ethylene
- ethylene rectification
- preparation technology
- vinylacetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Abstract
The present invention relates to a kind of polymerization inhibitor and its preparation technology for phenyl ethylene rectification, belong to chemical production technical field.The described polymerization inhibitor for phenyl ethylene rectification, is made up of the raw material of following mass percent：4 50% tetramethyl piperidine nitrogen oxygen free radical of 4 hydroxyl 2,2,6,6,6 40% vinylacetate, 10 90% solvent；Described preparation technology is that the tetramethyl piperidine nitrogen oxygen free radical of 4 hydroxyl 2,2,6,6, vinylacetate are added in solvent, after being stirred dissolving under normal temperature, obtains the polymerization inhibitor for phenyl ethylene rectification.The present invention solves the problems, such as that existing compound polymerization inhibitor easily crystallizes, revolutionize when conventional polymerization inhibitor uses in the winter time because crystallization occurring and the phenomenon of blocking pipeline, with polymerization inhibition effect it is good the characteristics of, free radical caused by triggering at high temperature with oxygen rapidly, which is combined, generates highly stable molecule, so as to reduce the generating rate of polymer, ensure the operation of production of styrene system safety and steady, increase economic efficiency.
Description
Technical field
The present invention relates to a kind of polymerization inhibitor and its preparation technology for phenyl ethylene rectification, belong to chemical production technical field.
Background technology
Styrene (SM) is the basic product of petrochemical industry, and purposes is quite varied, is mainly used in synthesizing various polystyrenes
Row resin and butadiene-styrene rubber, it also can be used in the industries such as coating, dyestuff, pharmacy and ore dressing.
Styrene is that a few has one of material of hot autohemagglutination performance, and it is at room temperature with regard to the slow autohemagglutination of energy, temperature
Liter high energy acceleration polymerisation progress.90% Styrene Process all uses ethylbenzene vapor catalytic dehydrogenation work in the world
Skill, in its dehydrogenation product crude styrene in addition to containing styrene, also a small amount of ethylbenzene, benzene, toluene and tar etc., essence need to be passed through
The styrene product of high-purity could be obtained by evaporating means.But in distillation process, high temperature, metal ion and trace oxygen are deposited
Easily causing styrene that Raolical polymerizable occurs, this not only results in the decline of styrene yield, while the polyphenyl generated
Ethene is also easily gathered in Ta Nei and pipeline, is caused frequently stop clear tower, replacing pipeline, is improved production cost, reduce production
Efficiency.
CN201010211593 discloses a kind of double solvents of extracting, rectifying and separating phenylethylene, by 50-95% mass point
The monoalky lether composition of the glycol of several DMAs and the C2-C6 of 5-50% mass fractions glycol or C2-C6,
The low boiling point of main solvent DMA, has certain inhibition, and can effectively reduce styrene in still-process gathers
Close, the higher cosolvent of boiling point and main solvent complex effect, it is possible to increase ortho-xylene is with respect to the relative volatility of styrene, drop
Low energy consumption.
CN1392127A discloses a kind of styrene polymerization inhibitor and purposes, and the polymerization inhibitor selects NO free radical and phenol generalization
Compound is compounding component, is formed according to a certain ratio, and preferable dosage is 400-800mg/kg, under conditions of 2h is heated, polymerization
Thing content is 0.17wt%, and the compound polymerization inhibitor of formation is significantly improved compared with the polymerization inhibition effect of the one-component of same concentration, poison
Property is lower than phenolic compound, and temperature in use is higher, suitable for the distillation process of styrene.
CN201010182390 discloses the efficient and environment-friendly type polymerization inhibitor and its application method of a kind of styrene.The compounding hinders
Poly- agent is made up of NO free radical class compound, hydroxylamine compound, nitro-phenolic compound and phosphite ester compound,
Each component mass ratio is 6-12:5:5-21:3-12, the compound polymerization inhibitor are relative to the mass concentration of monomer mass
0.0001%-0.2%.
It is able to know that in the prior art more than, compound polymerization inhibitor has the spy of the polymerization inhibition effect better than any single dose
Point, but above-mentioned compound polymerization inhibitor in the winter time lower temperature use when can occur crystallization and the phenomenon of blocking pipeline, once occur
Such phenomenon, device the whole series loading system steam tracing is gently then increased, because filling pipeline blocks when serious, the addition of polymerization inhibitor
Drastically decline, cause styrene polymerization degree to increase, the danger that easy generating means pipeline blocks.
The content of the invention
It is an object of the invention to provide a kind of polymerization inhibitor for phenyl ethylene rectification, solves existing compound polymerization inhibitor and easily ties
The problem of brilliant, there is the characteristics of freezing point is low, polymerization inhibition effect is good；Present invention simultaneously provides its preparation technology.
Polymerization inhibitor of the present invention for phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 4-50%
Vinylacetate 6-40%
Solvent 10-90%
Wherein, the solvent is naphtha or heavy aromatics oil.
Preferably, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 20-30%
Vinylacetate 20-30%
Solvent 40-60%
The preparation technology of polymerization inhibitor of the present invention for phenyl ethylene rectification, it is by 4- hydroxyls -2,2,6,6- tetramethyls
Phenylpiperidines NO free radical, vinylacetate are added in solvent, after being stirred dissolving under normal temperature, obtain being used for styrene essence
The polymerization inhibitor evaporated.
In the present invention：
4- hydroxyls-TEMPO is a kind of polymerization inhibitor, i.e., true polymerization inhibitor, is inducing
Inhibition efficiency high in phase, can terminate the growth of living radical chain, and polymerization inhibition effect is more preferable.
The addition of vinylacetate effectively reduces the freezing point of polymerization inhibitor, and revolutionize conventional polymerization inhibitor makes in the winter time
Used time because occur crystallization and the phenomenon of blocking pipeline, the component have with 4- hydroxyls-TEMPO
Cooperative effect, polymerization inhibition effect is good, can trigger with oxygen, high temperature rapidly caused by free radical is combined the highly stable molecule of generation, from
And the generating rate of polymer is reduced, ensure the operation of production of styrene system safety and steady, increase economic efficiency.
Solvent can play a part of dissolving polymerization inhibitor, aid dispersion polymer using naphtha or heavy aromatics oil.
Beneficial effects of the present invention are as follows：
(1) freezing point of the polymerization inhibitor for phenyl ethylene rectification of the invention is relatively low, revolutionizes conventional polymerization inhibitor and exists
During use in winter because occur crystallization and the phenomenon of blocking pipeline, using the present invention polymerization inhibitor when, device the whole series loading system is not
Need steam tracing, can steam saving dosage, " race, Mao, drop, leakage " that and can remove device occurs by steam tracing is existing
As；
(2) polymerization inhibition effect is good, can ensure that production of styrene system safety and steady is run, increase economic efficiency.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 4%
Vinylacetate 6%
Naphtha 90%
Preparation technology is as follows：4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, vinylacetate are added to stone
In cerebrol, after being stirred dissolving under normal temperature, the polymerization inhibitor for phenyl ethylene rectification is obtained.
Embodiment 2
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 4%
Vinylacetate 40%
Naphtha 56%
Preparation technology is the same as embodiment 1.
Embodiment 3
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 50%
Vinylacetate 6%
Naphtha 44%
Preparation technology is the same as embodiment 1.
Embodiment 4
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 50%
Vinylacetate 40%
Naphtha 10%
Preparation technology is the same as embodiment 1.
Embodiment 5
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 20%
Vinylacetate 20%
Naphtha 60%
Preparation technology is the same as embodiment 1.
Embodiment 6
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 20%
Vinylacetate 30%
Naphtha 50%
Preparation technology is the same as embodiment 1.
Embodiment 7
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 30%
Vinylacetate 20%
Naphtha 50%
Preparation technology is the same as embodiment 1.
Embodiment 8
For the polymerization inhibitor of phenyl ethylene rectification, it is made up of the raw material of following mass percent：
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 30%
Vinylacetate 30%
Naphtha 40%
Preparation technology is the same as embodiment 1.
The polymerization inhibitor obtained in embodiment 1-8 is added in three mouthfuls or four-hole boiling flask with quantitative styrene respectively, so
Carry out nitrogen displacement 5min afterwards, to reduce the oxygen content in flask, then thermometer, reflux condenser, and carry out machinery or
Magnetic agitation, 2h, the content of sampling analysis polystyrene are then heated at 120 DEG C；Analysis method is determined using gravimetric method
The growing amount of polystyrene, using characteristic of the polymer insoluble in methanol, enough drying methanol is added in the sample so that poly-
Compound precipitates completely, then filters, dries, weighs, constant weight, finally obtains the quality of the polymer of generation, experimental result
It is shown in Table 1, the dosage of the polymerization inhibitor obtained in table in embodiment 1-8 used is identical.
The polymerization inhibition effect of the polymerization inhibitor obtained in the embodiment 1-8 of table 1
Using the polymerization inhibitor for phenyl ethylene rectification obtained in embodiment 8, different polymerization inhibitor dosages is investigated to inhibition
The influence of effect, the results are shown in Table 2.
Influence of the polymerization inhibitor dosage of table 2 to polymerization inhibition effect
| Experiment numbers | Polymerization inhibitor dosage/% | Polystyrene mass content/% |
| 1 | 0.01 | 2.94 |
| 2 | 0.04 | 1.85 |
| 3 | 0.06 | 1.03 |
| 4 | 0.08 | 0.91 |
| 5 | 0.10 | 0.84 |
| 6 | 0.18 | 0.65 |
| 7 | 0.20 | 0.43 |
As shown in Table 2, as the increase of polymerization inhibitor dosage, polymerization inhibition effect significantly improve.In practical application, used from polymerization inhibitor
Amount and economic benefit consider, and currently preferred polymerization inhibitor dosage is 0.03-0.10wt%.
Comparative example：
Under the same terms, the freezing point of polymerization inhibitor and existing polymerization inhibitor to the present invention is evaluated.
4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radical, 25 part of acetic acid of the polymerization inhibitor of the present invention by 25 parts
Vinyl acetate, 60 parts of naphtha are made；DNBP, 25 part of 4- hydroxyl -2,2,6,6- tetramethyl piperazine of the existing polymerization inhibitor by 25 parts
Pyridine NO free radical, 60 parts of ethylbenzene are made, and then two kinds of polymerization inhibitors are added separately in three-necked flask, and thermometer is correct
Insert in three-necked flask, observed and record data every 5min after being put into refrigerator, the results are shown in Table 3.
The measure of 3 different polymerization inhibitors of table freezing point under the same conditions
| Time/min | Temperature/DEG C | Existing polymerization inhibitor state | Polymerization inhibitor state of the present invention |
| 0 | 5 | Liquid | Liquid |
| 5 | 0 | Liquid | Liquid |
| 10 | -5 | Liquid | Liquid |
| 15 | -10 | Liquid, consolidate | Liquid |
| 20 | -12 | Liquid, consolidate | Liquid |
| 25 | -15 | Gu | Liquid, consolidate |
| 30 | -17 | Gu | Liquid, consolidate |
| 35 | -20 | Gu | Liquid, consolidate |
| 40 | -25 | Gu | Gu |
As shown in Table 3, existing polymerization inhibitor for solid-liquid and deposits state at -10 DEG C to -12 DEG C, and freezing point is -15 DEG C, and this
Invention polymerization inhibitor for solid-liquid and deposits state at -15 DEG C to -20 DEG C, and freezing point is -25 DEG C, therefore, polymerization inhibitor of the invention
Freezing point is significantly lower than existing polymerization inhibitor.
Claims (2)
- A kind of 1. polymerization inhibitor for phenyl ethylene rectification, it is characterised in that：It is made up of the raw material of following mass percent：4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals 4-50%Vinylacetate 6-40%Solvent 10-90%Wherein, the solvent is naphtha or heavy aromatics oil.
- A kind of 2. preparation technology of the polymerization inhibitor for phenyl ethylene rectification described in claim 1, it is characterised in that：By 4- hydroxyls Base-TEMPO, vinylacetate are added in solvent, after being stirred dissolving under normal temperature, Obtain the polymerization inhibitor for phenyl ethylene rectification.
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| CN201610407905.XA CN107473923A (en) | 2016-06-07 | 2016-06-07 | Polymerization inhibitor and its preparation technology for phenyl ethylene rectification |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396140A (en) * | 2023-04-26 | 2023-07-07 | 江苏太湖新材料控股有限公司 | Styrene polymerization inhibitor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910232A (en) * | 1998-06-10 | 1999-06-08 | Nalco/Exxon Energy Chemicals, L.P. | Method for inhibiting polymer formation in styrene processing |
| CN101423449A (en) * | 2007-11-02 | 2009-05-06 | 赢创德固赛有限责任公司 | Method for stabilising olefinically unsaturated monomers |
| CN106554246A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Polymerization inhibitors for styrene rectification |
-
2016
- 2016-06-07 CN CN201610407905.XA patent/CN107473923A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910232A (en) * | 1998-06-10 | 1999-06-08 | Nalco/Exxon Energy Chemicals, L.P. | Method for inhibiting polymer formation in styrene processing |
| CN101423449A (en) * | 2007-11-02 | 2009-05-06 | 赢创德固赛有限责任公司 | Method for stabilising olefinically unsaturated monomers |
| CN106554246A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Polymerization inhibitors for styrene rectification |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396140A (en) * | 2023-04-26 | 2023-07-07 | 江苏太湖新材料控股有限公司 | Styrene polymerization inhibitor and preparation method thereof |
| CN116396140B (en) * | 2023-04-26 | 2023-10-27 | 江苏太湖新材料控股有限公司 | Styrene polymerization inhibitor and preparation method thereof |
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