CN108191640A - A kind of highly efficiency compositional polymerization inhibitor and its application in acroleic acid polymerization is inhibited - Google Patents
A kind of highly efficiency compositional polymerization inhibitor and its application in acroleic acid polymerization is inhibited Download PDFInfo
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- CN108191640A CN108191640A CN201711397683.9A CN201711397683A CN108191640A CN 108191640 A CN108191640 A CN 108191640A CN 201711397683 A CN201711397683 A CN 201711397683A CN 108191640 A CN108191640 A CN 108191640A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Abstract
The present invention provides a kind of highly efficiency compositional polymerization inhibitor and its application in acroleic acid polymerization is inhibited.Highly efficiency compositional polymerization inhibitor provided by the invention is 10 30 including mass ratio:1‑15:10 30 component A, component B and component C, the component A includes aromatic hydrocarbons aminated compounds, and the component B includes compound oxygen radical of nitrogen, and the component C includes phosphite ester compound.The compound polymerization inhibitor of the present invention is applied to inhibit acroleic acid polymerization, has dosage few, inhibits the features such as efficient.
Description
Technical field
The present invention relates to inhibit acroleic acid polymerization polymerization inhibitor field, more particularly to a kind of highly efficiency compositional polymerization inhibitor and its
Using.
Background technology
Acrylic acid is a kind of unrighted acid and a kind of important Organic Chemicals.Acrylic acid has unsaturation
Double bond and polar molecular structure.With alcohol esterification synthesizing methyl acrylate, ethyl acrylate, propylene can occur for acrylic acid
Acid butyl ester, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate etc..Acrylic acid can also autohemagglutination synthesis scale remover,
Water-reducing agent, flocculant, builder, thickener etc..
Acrylic acid has the property of vinyl olefins, and polymerization activity is high.Acrylic acid can just polymerize at normal temperatures,
Can all it polymerize when refining, storing.Especially in subtractive process, since gas-liquid phase transition is very easy to polymerize.Cause
This, in refined polymerization, column plate, pipeline can often block, and not only waste monomer, influence device continuously runs, increases parking maintenance
Cost, and also increase acrylic acid production cost.In order to slow down the autohemagglutination that acrylic acid occurs in the process in production, storage,
Polymerization inhibitor need to be usually added in production, storage.
The usually used polymerization inhibitor of acrylic acid industry is broadly divided into two class of true polymerization inhibitor and retarder at present.Wherein, true resistance
The poly- agent such as inhibition such as NO free radical class compound is efficient, and inhibition induction period is long, and polymerization is nearly free within induction period
Object, but there is the shortcomings of easily being consumed by free radical, service life is short in it.The chemical property such as retarder such as phenthazine are stablized, inhibition
Process consumption is few, rate of polymerization can be reduced, but induction period is shorter, so polymer can slowly increase.
Shanghai Huayi Acrylic Acid Co., Ltd. discloses a kind of for production third in Chinese patent application CN1821207A
The compound polymerization inhibitor of olefin(e) acid and ester.The polymerization inhibitor is compounded using NO free radical type compound with mantoquita.Shanghai chemistry examination
Co., Ltd of agent research institute discloses a kind of for acrylic acid production process in Chinese patent application CN104370730 A
Ternary built polymerization inhibitor, the polymerization inhibitor are compounded using substituted phenol, organic amine and long-chain mantoquita, phenols substituent group tool
There is In frared spectra.China National Petroleum Co., Ltd discloses one kind in Chinese patent application CN105732360 A
For the polymerization inhibitor that acrylic monomers refines, which is compounded using hydroquinone, chlorpromazine, fenazil, passes through resistance
The polymerization inhibiting capacity of poly- agent Modified lift compound polymerization inhibitor.Northeast refinery Engineering Co., Ltd of China Petroleum group is in Chinese patent
A kind of polymerization inhibitor applied in acrylic acid subtractive process is disclosed in application CN103848735 A, which uses nitrogen oxygen
Free radical type compound is compounded with mantoquita.
Therefore at present, the polymerization inhibitor of acrylic acid industry be generally the true polymerization inhibitor of free radical type and phenols, amine or
Copper salt kind retarder is compounded or is modified on the basis of polymerization inhibitor, and polymerization inhibition effect has certain promotion, but still deposits
It is not solved in problems with：1st, hydroperoxides can be still generated after inhibiting, can further be decomposed to form free radical polymerization；
2nd, polymerization inhibitor is mostly toxic powders, not environmentally protective enough during extemporaneous preparation；3rd, polymerization cannot be prevented to accumulate in the device.
Invention content
The present invention is makes up the deficiencies in the prior art, provide a kind of highly efficiency compositional polymerization inhibitor and its is inhibiting third
Application in olefin(e) acid polymerization.The compound polymerization inhibitor of the present invention is applied to inhibit acroleic acid polymerization, has dosage few, inhibits effect
The features such as rate is high.
For the present invention to reach its purpose, the technical solution of use is as follows：
First aspect present invention provides a kind of highly efficiency compositional polymerization inhibitor, is 10-30 including mass ratio:1-15:10-30's
Component A, component B and component C, proportions are more preferably 20-30:5-10:10-20；The component A includes aromatic hydrocarbons amine
Class compound, the component B include compound oxygen radical of nitrogen, and the component C includes phosphite ester compound.The present invention
By the combination collocation of component A, component B and component C, each component synergistic effect, overcome true polymerization inhibitor in the prior art and
The deficiency of retarder, can effectively decompose the hydroperoxides that inhibition is formed in the process, and prevention re-forms free radical, makes resistance
Poly- agent significantly improves the polymerization inhibition effect of acroleic acid polymerization.
The present invention highly efficiency compositional polymerization inhibitor, it is preferred that the aromatic hydrocarbons aminated compounds include following structure formula (I)-
(IV) it is one or more in compound shown in：
Wherein, the R in formula (I), (II), (III) or (IV)1And R2It is identical or different, R1And R2It is independently selected from
Hydrogen, methyl, ethyl, isopropyl, tertiary butyl, phenyl, benzyl, phenethyl, 2- (4- methyl amyls), 2- (3,3- dimethyl-pentens
Base), 2- (5,6- dimethyl heptyl), 2- (2,4,4- tri-methyl-amyls), 2- (2- methyl amyls), 2- (2- Methyl Octyls),
Any one of benzene isopropyl.
The highly efficiency compositional polymerization inhibitor of the present invention, it is preferred that the aromatic hydrocarbons aminated compounds includes but not limited to bis- (4- benzene
Isopropyl phenyl) amine, 4- tert-butyl diphenylamines, N- phenyl -4- (2,4,4- trimethyl -2- amyls) aniline, bis- (4- tertiary butyls
Phenyl) amine, bis- (4- (2- methyl -2- amyls)) aniline, bis- (4- (2- methyl -2- octyl groups)) aniline, phenthazine, N, N- hexichol
Base -1,4- phenylenediamines, N- phenyl-N- benzyl -1,4- phenylenediamines, N- phenyl-N- phenethyl -1,4- phenylenediamines, N- (4- first
Base -2- amyls)-N- phenyl -1,4- phenylenediamines, N- (3,3- dimethyl -2- amyls)-N- phenyl -1,4- phenylenediamines, N- (5,6-
Dimethyl -2- heptyl)-N- phenyl -1,4- phenylenediamines, the different ethyl, N-phenyl -1,4- phenylenediamines of N-, N- (methylphenylamine) N-
Phenyl -1,4- phenylenediamines, N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines, N- (N-3,3- dimethyl -2- amylbenzenes
Amine) it is one or more in N- phenyl -1,4- phenylenediamines.These compounds can be obtained with commercial channel, can also use ability
Preparation process known to domain, which makes by oneself, to be obtained, such as N- (methylphenylamine) N- phenyl-Isosorbide-5-Nitrae-phenylenediamine, N- (N- tert-butyl benzenes
Amine) packet may be used in N- phenyl -1,4- phenylenediamines, N- (N-3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- phenylenediamines
Include the method synthesis of following steps：(1) it at 140 DEG C, under the conditions of 35kPa, to N, is added dropwise in N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine
The concentrated sulfuric acid of 98wt%, N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine are 1 with sulfuric acid molar ratio:1, react 2h；(2) add into reaction solution
Enter sodium hydrate solid, sulfuric acid and sodium hydroxide molar ratio are 1 in reaction solution:2.5,300 DEG C are warming up to, reacts 1h；(3) it is anti-
Liquid is answered to be washed using cold water, until can't detect sodium sulphate；(4) product adds in the hydrochloric acid acidification of 10wt%；(5) it is quiet after reacting
It puts, discharges water phase, be dried；(6) triethyl phosphate catalysis under, under 280-300 DEG C, 0.7MPa, respectively with methylamine,
Tert-butylamine or the reaction of 3,3- dimethyl -2- amylamines be made respectively N- (methylphenylamine) N- phenyl -1,4- phenylenediamines,
N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines or N- (N-3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- benzene
Diamines；Vacuum distillation removing methylamine, tert-butylamine at 20kPa, 100 DEG C after reaction, obtain target product (embodiment
In used N- (methylphenylamine) N- phenyl -1,4- phenylenediamines, N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines,
N- (N-3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- phenylenediamines are made according to the method).
The highly efficiency compositional polymerization inhibitor of the present invention, in a kind of preferred embodiment, including component A, component B, component C and group
Point D, the component D include amides dispersant, component A, component B, component C and component D mass ratio be 10-30:1-15:
10-30:1-10, preferably 20-30:5-10:10-20:1-5.Preferably, the amides dispersant is stearic for ethylenebis
Amide.The compound polymerization inhibitor of the present invention with the optimization formula that component A, component B, component C and component D are combined, can effectively hinder
The only accumulation of polymer in the device increases the solubility of polymer, improves polymerization inhibition effect, extends the device cycle of operation, and drop
Low production cost.
The highly efficiency compositional polymerization inhibitor of the present invention, in a kind of more preferred embodiment, including component A, component B, component
C, component D and component E, the component E include amides compound, component A, component B, component C, component D and component E matter
Amount is than being 10-30:1-15:10-30:1-10:25-80, preferably 20-30:5-10:10-20:1-5:40-60.Preferably,
The component E includes but not limited to one in N-Methyl pyrrolidone, N,N-dimethylformamide and N, N- diethyl acetamide
Kind is a variety of.Preferably, component A, component B, component C and component D are dissolved in component E.The compound polymerization inhibitor of the present invention,
It is preferred that with component A, component B, component C, component D and component E combination collocations, each component synergy, not only inhibit it is efficient,
The accumulation of polymer is avoided, polymerization inhibition effect is more preferably；And polymerization inhibitor occurs in liquid form, avoids dust, and be easy to use,
Noxious material is also reduced simultaneously to use, it is environmentally protective.
The highly efficiency compositional polymerization inhibitor of the present invention, in a kind of preferred embodiment, including component A, component B, component C and
Component E, the component E include amides compound, component A, component B, component C and component E mass ratio be 10-30:1-
15:10-30:25-80, preferably 20-30:5-10:10-20:40-60.Preferably, the component E includes but not limited to N- first
It is one or more in base pyrrolidones, N,N-dimethylformamide and N, N- diethyl acetamide；Preferably, component A, group
B and component C is divided to be dissolved in component E.
The highly efficiency compositional polymerization inhibitor of the present invention, it is preferred that the compound oxygen radical of nitrogen includes but not limited to 2,2,6,
6- tetramethyl piperidine nitrogen oxygen free radicals, 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 1- carbonyls -2,2,6,6- four
Methyl piperidine NO free radical, 4- acetylaminohydroxyphenylarsonic acid 2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 4- amino -2,2,6,6- four
It is one or more in methyl piperidine NO free radical.
The highly efficiency compositional polymerization inhibitor of the present invention, it is preferred that the phosphite ester compound includes but not limited to phosphorous acid
Trimethyl, triethyl phosphite, tributyl phosphite, triphenyl phosphite, three different monooctyl ester of phosphorous acid, phosphorous acid cyclohexyl, Asia
One kind in phosphoric acid dicyclohexyl maleate, bis- different fork bis-phenol (12-14) carbon Arrcostabs of phosphorous acid 4,4-, diisooctyl phenyl phosphite
It is or a variety of.
Second aspect of the present invention provides the application of highly efficiency compositional polymerization inhibitor described above, the highly efficiency compositional polymerization inhibitor
For inhibiting acroleic acid polymerization；Especially suitable for the negative pressure distillation process of acrylic acid, such as negative pressure high temperature distillation process；It is described
The pressure of negative pressure high temperature distillation process is preferably 1kPa-20kPa, and temperature is preferably 60-100 DEG C.The compound polymerization inhibitor of the present invention
In use, usage amount is less, relative to the weight of acrylic acid, the addition of the highly efficiency compositional polymerization inhibitor is preferably
0.0100wt%-0.0500wt%.The compound polymerization inhibitor of the present invention, when in use, by being incorporated to rectifier column reflux pipeline, point
It is added in rectifying column after dissipating uniformly, there is more preferably using effect.
Technical solution provided by the invention has the advantages that：
Highly efficiency compositional polymerization inhibitor provided by the invention, applied to inhibit acroleic acid polymerization, have dosage it is few, inhibition efficiency
The features such as high, polymerization inhibitor is easy to remove, is environmentally protective, reaches and extends the acrylic acid refining plant cycle of operation, reduce acrylic acid essence
The purpose of device production unit consumption processed.The highly efficiency compositional polymerization inhibitor of the present invention is especially suitable for acrylic acid negative pressure high temperature distillation process.
Description of the drawings
Fig. 1 is N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamine mass spectrograms.
Specific embodiment
For a better understanding of the technical solution of the present invention, with reference to the embodiment content that the present invention is further explained,
But present disclosure is not limited only to following embodiment.
Used N- (methylphenylamine) N- phenyl -1,4- phenylenediamines, N- (N- tertiary butyls aniline) in following embodiment
N- phenyl -1,4- phenylenediamines, N- (N-3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- phenylenediamines, which use, includes following step
Rapid method synthesis：
(1) at 140 DEG C, under the conditions of 35kPa, to N, the concentrated sulfuric acid of 98wt% is added dropwise in N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine,
N, N- diphenyl -1,4- phenylenediamines are 1 with sulfuric acid molar ratio:1, react 2h；
(2) sodium hydrate solid is added in into reaction solution, sulfuric acid and sodium hydroxide molar ratio are 1 in reaction solution:2.5, it rises
Temperature reacts 1h to 300 DEG C；
(3) reaction solution is washed using cold water, until can't detect sodium sulphate；
(4) product adds in the hydrochloric acid acidification of 10wt%；(5) it is stood after reacting, discharges water phase, be dried；(6) in phosphorus
Under triethylenetetraminehexaacetic acid ester catalysis, under 280-300 DEG C (in this preparation process be specially 290 DEG C or so), 0.7MPa, respectively with methylamine,
Tert-butylamine or the reaction of 3,3- dimethyl -2- amylamines be made respectively N- (methylphenylamine) N- phenyl -1,4- phenylenediamines,
N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines or N- (N-3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- benzene
Diamines；Vacuum distillation (purpose is removing methylamine or tert-butylamine etc.) at 20kPa, 100 DEG C after reaction, examines through mass spectrum
It surveys confirmation and obtains target product.Fig. 1 show the Mass Spectrometer Method result of N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines.
Embodiment 1
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 1).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：Fen thiophene
Piperazine is 20wt%, 701 is (for 4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide, commercially available, purity ＞ 99%)
5wt%, triphenyl phosphite 20wt%, dispersant EBS (ethylenebis stearic amide, commercially available) are 5wt%, N- methyl
Pyrrolidones is 50wt%.The addition of composite polymerzation inhibitor is the 0.0200wt% of reflux acrylic acid.Experimental result is shown in Table 1 institute
Show.
Table 1
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals；EBS is ethylenebisstearamide.
Embodiment 2
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 2).Wherein, in composite polymerzation inhibitor used, the mass percent of each ingredient is：N-
(methylphenylamine) N- phenyl -1,4- phenylenediamines 30wt%, 701 are (for 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogens oxygen freedom
Base, commercially available, purity ＞ 99%) it is 10wt%, triphenyl phosphite 20wt%, dispersant EBS (ethylenebis stearic acid acyls
Amine, commercially available) it is 1wt%, N-Methyl pyrrolidone 49wt%.The addition of composite polymerzation inhibitor is reflux acrylic acid
0.0200wt%.Experimental result is shown in Table shown in 2.
Table 2
| The rectifying time/h | Polymer content/wt% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0 |
| 144 | 0 | 0 |
| 192 | 0 | 0.5 |
| 240 | 0.12 | 0.7 |
| 288 | 0.2 | 1.2 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals；EBS is ethylenebisstearamide.
Embodiment 3
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 3).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：N-(N-
Methylaniline) N- phenyl-Isosorbide-5-Nitrae-phenylenediamine for 30wt%, 701 (4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide,
Commercially available, purity ＞ 99%) for 10wt%, triphenyl phosphite 10wt%, dispersant EBS (ethylenebis stearic amide,
It is commercially available) it is 2wt%, N,N-dimethylformamide 48wt%.The addition of composite polymerzation inhibitor is reflux acrylic acid
0.0200wt%.Experimental result is shown in Table shown in 3.
Table 3
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0 |
| 144 | 0 | 0 |
| 192 | 0 | 0 |
| 240 | 0.08 | 0 |
| 288 | 0.13 | 0.3 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals；EBS is ethylenebisstearamide.
Embodiment 4
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 4).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：N-(N-
Tertiary butyl aniline) N- phenyl -1,4- phenylenediamines are 60wt%, 701 (4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogens oxygen is free
Base, commercially available, purity ＞ 99%) it is 20wt%, triphenyl phosphite 20wt%.The addition of composite polymerzation inhibitor is reflux third
The 0.0200wt% of olefin(e) acid.Experimental result is shown in Table shown in 4.
Table 4
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0.2 |
| 144 | 0 | 0.4 |
| 192 | 0.03 | 0.7 |
| 240 | 0.10 | 0.9 |
| 288 | 0.15 | 1.0 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals.
Embodiment 5
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 5).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：N-(N-
3,3- dimethyl -2- amyl anilines) N- phenyl -1,4- phenylenediamines for 60wt%, 701 (4- hydroxyl -2,2,6,6- tetramethyl piperazines
Pyridine NO free radical, commercially available, purity ＞ 99%) it is 19wt%, triphenyl phosphite 19wt%, dispersant EBS (ethylidene
Double stearic amides, commercially available) it is 2wt%.The addition of composite polymerzation inhibitor is the 0.0200wt% of reflux acrylic acid.Experiment knot
Fruit is shown in Table 5.
Table 5
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0 |
| 144 | 0 | 0 |
| 192 | 0 | 0.2 |
| 240 | 0.10 | 0.4 |
| 288 | 0.14 | 0.5 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals；EBS is ethylenebisstearamide.
Embodiment 6
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 6).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：N,N-
Diphenyl-Isosorbide-5-Nitrae-phenylenediamine is 30wt%, 701 (4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide, commercially available, purity
＞ 99%) it is 10wt%, triphenyl phosphite 10wt%, N,N-dimethylformamide 50wt%.Composite polymerzation inhibitor
Addition is the 0.0200wt% of reflux acrylic acid.Experimental result is shown in Table shown in 6.
Table 6
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0 |
| 144 | 0 | 0.1 |
| 192 | 0 | 0.2 |
| 240 | 0.08 | 0.4 |
| 288 | 0.13 | 0.5 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals.
Comparative example 1
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 7).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：Bis- (4-
Benzene isopropyl phenyl) amine (i.e. 4,4'- bis- (propyloxy phenyl base) diphenylamines) is 50wt%, (ethylenebis is stearic by dispersant EBS
Sour amide, commercially available) it is 2wt%, N, N- diethyl acetamides are 48wt%.The addition of composite polymerzation inhibitor is reflux acrylic acid
0.0200wt%.Experimental result is shown in Table shown in 7.
Table 7
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0.1 | 0 |
| 96 | 0.2 | 0 |
| 144 | 0.4 | 0.2 |
| 192 | 0.5 | 0.4 |
| 240 | 0.09 | 0.7 |
| 288 | 0.15 | 1.0 |
Note：EBS is ethylenebisstearamide.
Comparative example 2
Composite polymerzation inhibitor is incorporated to rectifier column reflux pipeline, pure acrylic acid essence is carried out at 15kPa, 95 DEG C of bottom temperature
Experiment is evaporated, is sampled from tower bottoms at regular intervals, the production quantity of polymer is measured with refractive index, when one section
Between record rectifying column pressure drop (being specifically shown in Table 8).Wherein, in composite polymerzation inhibitor used, each ingredient percent is：701
(4- hydroxyls -2,2,6,6-tetramethylpiperidine nitroxide, commercially available, purity ＞ 99%) is 50wt%, dispersant EBS (sub- second
The double stearic amides of base, commercially available) it is 2wt%, n,N-Dimethylformamide 48wt%.The addition of composite polymerzation inhibitor is back
Flow the 0.0200wt% of acrylic acid.Experimental result is shown in Table shown in 8.
Table 8
| The rectifying time/h | Polymer content/% | Pressure drop/kPa |
| 48 | 0 | 0 |
| 96 | 0 | 0 |
| 144 | 0.08 | 0 |
| 192 | 0.2 | 0.3 |
| 240 | 0.38 | 0.7 |
| 288 | 0.63 | 1.3 |
Note：701 be 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals；EBS is ethylenebisstearamide.
Comparative example 3 (existing industrial inhibition system)
P methoxy phenol polymerization inhibitor is dissolved in, inhibitor solution is made into acrylic acid, be then incorporated into rectifier column reflux pipe
Line is reacted at 120 DEG C, is sampled from reaction solution at regular intervals, and the generation of polymer is measured with refractive index
Amount records rectifying column pressure drop at regular intervals.The addition of polymerization inhibitor is the 0.0500wt% of reflux acrylic acid.Experiment knot
Fruit is shown in Table 9.
Table 9
| The rectifying time/h | Polymer content/wt% | Pressure drop/kPa |
| 48 | 0.10 | 0.2 |
| 96 | 0.19 | 0.6 |
| 144 | 0.31 | 1.3 |
| 192 | 0.52 | 1.9 |
| 240 | 1.20 | 2.8 |
| 288 | 3.71 | 3.5 |
Comparative example 4 (existing industrial inhibition system)
Phenothiazine polymerization inhibitor is dissolved in, inhibitor solution is made into acrylic acid, be then incorporated into rectifier column reflux pipeline,
It is reacted at 120 DEG C, is sampled from reaction solution at regular intervals, the production quantity of polymer is measured with refractive index, often
Rectifying column pressure drop is recorded every a period of time.The addition of polymerization inhibitor is the 0.0500wt% of reflux acrylic acid.Experimental result is shown in Table
10。
Table 10
| The rectifying time/h | Polymer content/wt% | Pressure drop/kPa |
| 48 | 0.05 | 0.0 |
| 96 | 0.10 | 0.0 |
| 144 | 0.21 | 1.0 |
| 192 | 0.42 | 1.1 |
| 240 | 0.70 | 1.8 |
| 288 | 1.71 | 2.5 |
By above-mentioned experiment it is found that composite polymerzation inhibitor in the embodiment of the present invention 1-6 polymerization inhibition effect (polymer content,
Rectifying column pressure drop) comparative example 1-4 will be better than.The composite polymerzation inhibitor of the present invention can significantly reduce the coking amount of acrylic acid, gather
It closes object to be substantially reduced, effective requirement of polymerization inhibitor is reduced, and without dissolving, can be used directly, toxicity weakens, and has reached environmental protection
The requirement of high-efficiency and economic.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of highly efficiency compositional polymerization inhibitor, which is characterized in that including mass ratio be 10-30:1-15:Component A, the component B of 10-30
Include aromatic hydrocarbons aminated compounds with component C, the component A, the component B includes compound oxygen radical of nitrogen, the component C packets
Include phosphite ester compound.
2. highly efficiency compositional polymerization inhibitor according to claim 1, which is characterized in that the aromatic hydrocarbons aminated compounds includes as follows
It is one or more in structure formula (I)-compound shown in (IV)：
Wherein, the R in formula (I), (II), (III) or (IV)1And R2It is identical or different, R1And R2It is independently selected from hydrogen, first
Base, ethyl, isopropyl, tertiary butyl, phenyl, benzyl, phenethyl, 2- (4- methyl amyls), 2- (3,3- dimethyl amyl groups), 2-
(5,6- dimethyl heptyl), 2- (2,4,4- tri-methyl-amyls), 2- (2- methyl amyls), 2- (2- Methyl Octyls), benzene isopropyl
Any one of.
3. highly efficiency compositional polymerization inhibitor according to claim 1 or 2, which is characterized in that the aromatic hydrocarbons aminated compounds is selected from
Bis- (4- benzene isopropyl phenyl) amine, 4- tert-butyl diphenylamines, N- phenyl -4- (2,4,4- trimethyl -2- amyls) aniline, bis- (4-
Tert-butyl-phenyl) amine, bis- (4- (2- methyl -2- amyls)) aniline, bis- (4- (2- methyl -2- octyl groups)) aniline, phenthazine, N, N-
Diphenyl -1,4- phenylenediamines, N- phenyl-N- benzyl -1,4- phenylenediamines, N- phenyl-N- phenethyl -1,4- phenylenediamines, N- (4-
Methyl -2- amyls)-N- phenyl -1,4- phenylenediamines, N- (3,3- dimethyl -2- amyls)-N- phenyl -1,4- phenylenediamines, N- (5,
6- dimethyl -2- heptyl)-N- phenyl -1,4- phenylenediamines, the different ethyl, N-phenyl -1,4- phenylenediamines of N-, N- (methylphenylamine)
N- phenyl -1,4- phenylenediamines, N- (N- tertiary butyls aniline) N- phenyl -1,4- phenylenediamines, N- (N-3,3- dimethyl -2- amylbenzenes
Amine) it is one or more in N- phenyl -1,4- phenylenediamines.
4. according to claim 1-3 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that further include component D, described group
Point D includes amides dispersant, component A, component B, component C and component D mass ratio be 10-30:1-15:10-30:1-10.
5. highly efficiency compositional polymerization inhibitor according to claim 4, which is characterized in that the amides dispersant is ethylenebis
Stearmide.
6. according to claim 4-5 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that further include component E, described group
Point E includes amides compound, component A, component B, component C, component D and component E mass ratio be 10-30:1-15:10-30:
1-10:25-80, preferably 20-30:5-10:10-20:1-5:40-60；
Preferably, the component E is included in N-Methyl pyrrolidone, n,N-Dimethylformamide and N, N- diethyl acetamide
It is one or more；Preferably, component A, component B, component C and component D are dissolved in component E.
7. according to claim 1-3 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that further include component E, described group
Point E includes amides compound, component A, component B, component C and component E mass ratio be 10-30:1-15:10-30:25-
80, preferably 20-30:5-10:10-20:40-60；
Preferably, the component E is included in N-Methyl pyrrolidone, n,N-Dimethylformamide and N, N- diethyl acetamide
It is one or more；Preferably, component A, component B and component C are dissolved in component E.
8. according to claim 1-7 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that the NO free radical chemical combination
Object includes 2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 4- hydroxyl -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 1- carbonyls
Base -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 4- acetylaminohydroxyphenylarsonic acid 2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals, 4- ammonia
It is one or more in base -2,2,6,6- tetramethyl piperidine nitrogen oxygen free radicals.
9. according to claim 1-8 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that the phosphorous acid esters chemical combination
Object includes Trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, three different monooctyl ester of phosphorous acid, phosphorous
Sour cyclohexyl, phosphorous acid dicyclohexyl maleate, bis- different fork bis-phenol (12-14) carbon Arrcostabs of phosphorous acid 4,4-, one benzene two of phosphorous acid are different pungent
It is one or more in ester.
10. such as the application of claim 1-9 any one of them highly efficiency compositional polymerization inhibitors, which is characterized in that the highly efficiency compositional
Polymerization inhibitor is used to inhibit acroleic acid polymerization；It is preferred for the negative pressure distillation process of acrylic acid, the pressure of the negative pressure distillation process
Preferably 1kPa-20kPa, temperature are preferably 60-100 DEG C；
Preferably, relative to the weight of acrylic acid, the addition of the highly efficiency compositional polymerization inhibitor is 0.01wt%-0.05wt%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028770A (en) * | 2019-06-03 | 2020-12-04 | 中国石油天然气股份有限公司 | Environment-friendly polymerization inhibitor, preparation method thereof and application thereof in acrylic ester rectification process |
| CN114685854A (en) * | 2022-04-25 | 2022-07-01 | 萧县新秀新材料有限公司 | Stabilizer for trans-isoprene rubber and application |
| WO2024011191A1 (en) * | 2022-07-08 | 2024-01-11 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
| WO2024011171A1 (en) * | 2022-07-08 | 2024-01-11 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
| WO2024089565A1 (en) * | 2022-10-25 | 2024-05-02 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
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| CN1356970A (en) * | 1998-12-08 | 2002-07-03 | 巴斯福股份公司 | Method for stabilizing chemical compounds contg. at least one ethylenically unsaturated bond in order to prevent undesirable radical polymerization |
| WO2017041204A1 (en) * | 2015-09-07 | 2017-03-16 | Rhodia Operations | Use of polymerization inhibitor compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1356970A (en) * | 1998-12-08 | 2002-07-03 | 巴斯福股份公司 | Method for stabilizing chemical compounds contg. at least one ethylenically unsaturated bond in order to prevent undesirable radical polymerization |
| WO2017041204A1 (en) * | 2015-09-07 | 2017-03-16 | Rhodia Operations | Use of polymerization inhibitor compositions |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028770A (en) * | 2019-06-03 | 2020-12-04 | 中国石油天然气股份有限公司 | Environment-friendly polymerization inhibitor, preparation method thereof and application thereof in acrylic ester rectification process |
| CN112028770B (en) * | 2019-06-03 | 2023-04-07 | 中国石油天然气股份有限公司 | Environment-friendly polymerization inhibitor, preparation method thereof and application thereof in acrylic ester rectification process |
| CN114685854A (en) * | 2022-04-25 | 2022-07-01 | 萧县新秀新材料有限公司 | Stabilizer for trans-isoprene rubber and application |
| WO2024011191A1 (en) * | 2022-07-08 | 2024-01-11 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
| WO2024011171A1 (en) * | 2022-07-08 | 2024-01-11 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
| WO2024089565A1 (en) * | 2022-10-25 | 2024-05-02 | Ecolab Usa Inc. | Synergistic antifoulant compositions and methods of using the same |
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