CN100443455C - Process for prohibiting polymerization of styrene - Google Patents
Process for prohibiting polymerization of styrene Download PDFInfo
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- CN100443455C CN100443455C CNB2005101102802A CN200510110280A CN100443455C CN 100443455 C CN100443455 C CN 100443455C CN B2005101102802 A CNB2005101102802 A CN B2005101102802A CN 200510110280 A CN200510110280 A CN 200510110280A CN 100443455 C CN100443455 C CN 100443455C
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Abstract
The invention discloses a resisting method of phenylethene without polymerizing, which is characterized by the following: adding polymerization inhibitor with water solvent solubility more than 50PPm in the 5-99% phenylethene system, wherein the density of polymerization inhibitor is composed of a) 20-80% nitrite, b) 10-50% quinone compounds, c) 1-35% nitrophenols and derivant.
Description
Technical field
The present invention relates to a kind of method that is used for prohibiting polymerization of styrene, particularly C about obtaining from steam cracking with extraction fractional distillation in the petrochemical industry
8The method that is used for prohibiting polymerization of styrene in the cut in the cinnamic process of separation and Extraction.
Background technology
Vinylbenzene is the important monomer of producing polystyrene, ABS resin and SBS.Yet the same with most of vinyl aromatic compounds, vinylbenzene has autohemagglutination character.Usually just polymerization can take place at normal temperatures, temperature is high more, and polymerization velocity is fast more.Industrially be widely used in transportation, store cinnamic low temperature, the normal temperature stopper is the 4-tert-butyl catechol (4-tert-butylcatechol is abbreviated as TBC).But TBC only is suitable for using at normal temperatures, and when temperature raise, its polymerization inhibition effect significantly descended until forfeiture.
For suppressing the monomeric polymerization of vinyl aromatic compounds under the rectifying condition, a lot of stoppers have been used.2,2, 4-dinitrophenol is used by industry the earliest, but its toxicity is big especially.Since the eighties, people introduce methyl, ethyl, butyl etc. to it, have reduced the toxicity of compound, have improved its solubleness in vinylbenzene.Nitro-phenolic compound belongs to retarder, and whether its polymerization inhibition effect and air exist and concern not quite.USP4105506 discloses and has used 2, and the 6-dinitro-p-cresol is as the stopper of vinyl aromatic compounds.USP4182658 discloses and has used 4, and 6-dinitrobenzene-2-sec-butyl phenol is as the stopper of vinyl aromatic compounds.
In addition, the stopper system of binary or Recompounded multielement is emerged in large numbers one after another.USP4466904 discloses in the presence of oxygen, in rectifying tower, and 2, (phenothiazine) is composite for 6-dinitro-p-cresol and TBC and thiodiphenylamine, can reduce the molecular weight of polymkeric substance, makes less scaling, the obstruction of reboiler.USP4466905 discloses in the presence of oxygen, and in rectifying tower, phenylenediamine and 2,6-dinitro-p-cresol use together and reduce the polymerization amount that occurs.
Although what the stopper of prior art can ethene suppressing base aromatic substance is aggregated to a certain degree, following reason still makes people need new stopper system.Be elected to be the compound of stopper, must be efficiently, polluted product not, it is low and even nontoxic also should to pursue toxicity, bring ecological problem can not for the processing of distillation residue.The price of this compound own can not be expensive.In addition, most of still-process all are to carry out under the environment of anaerobic, so those stoppers that need use under aerobic environment are not suitable for technical field involved in the present invention.
Summary of the invention
Technical problem to be solved by this invention is to exist in the prior art to adopt extraction and distillation technology to reclaim pyrolysis gasoline C
8During vinylbenzene in the cut, tower still vinylbenzene loses too high technical problem because of polymerization, and a kind of new method that is used for prohibiting polymerization of styrene is provided.This method has the stopper low price of employing, and toxicity is little, and consumption is few and can effectively stop the advantage of styrene polymerization.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for prohibiting polymerization of styrene, to weight percent concentration is that the stopper that adds water-containing solvent dissolved 50～2000PPm in 5～99% the vinylbenzene Aquo System prevents cinnamic polymerization, and wherein stopper is made up of following component by weight percentage:
A) 20%～80% nitrite;
B) 10%～50% quinones;
C) 1%～35% nitrophenol, many nitrophenol or derivatives thereof;
Wherein nitrite is selected from least a in lithium nitrite, Sodium Nitrite or the potassium nitrite, the quinones joint compound is selected from least a in benzoquinones that benzoquinones, phenanthrenequione, anthraquinone or 3 carbon atom alkyls replace or the phenanthrenequione, nitrophenol, many nitrophenol or derivatives thereof are selected from 2,6-dinitro-p-cresol, 4,6-dinitrobenzene-2-sec-butyl phenol, 2,2, 4-dinitrophenol, at least a in the isomer of sylvan, phenol or nitrophenols.
In technique scheme, the consumption preferable range of nitrite is 35～65% by weight percentage; The consumption preferable range of nitrophenol, many nitrophenol or derivatives thereof is 15～35% by weight percentage; The consumption preferable range of quinones joint compound is 15～35% by weight percentage; Vinylbenzene weight percent concentration preferable range is 30～95%; The consumption preferable range of stopper is 400～1200PPm, and more preferably scope is 400～1200PPm.
Prohibiting polymerization of styrene method disclosed in this invention realizes by adopting the Compositional type stopper, phenolic compound wherein belongs to retarder, and quinones belongs to true stopper, well-known retarder and true stopper is composite can produce synergy, improve polymerization inhibition effect, therefore it is more to adopt this thinking to carry out composite composite polymerzation inhibitor, but when the composite polymerzation inhibitor that the inorganic salts stopper is formed with this retarder and true stopper again was composite, we found that amazedly the effect of stopper has been strengthened greatly.Under 120 ℃, adding this new stopper 400～800PPm, can to make concentration expressed in percentage by weight be that 30% styrene polymerization rate is less than 1%, weight percent concentration is this stopper that adds 900PPm in 95% the vinylbenzene, vinylbenzene keeps 30 minutes percent polymerizations less than 1% down at 120 ℃, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
To 3 gram vinylbenzene, 7 gram (N-N-methyl-2-2-pyrrolidone N-+water, water 1 weight %) adds stopper 600PPm of the present invention in the mixed system, by weight percentage, consisting of of stopper: Sodium Nitrite 65%, benzoquinones+phenanthrenequione 20% (benzoquinones weight: phenanthrenequione weight=30: 1), DNBP15%.Above-mentioned mixture is sealed in 22 milliliters the head space bottle.Vibration shakes up, and 120 ℃ of Water Tank with Temp.-controlled heating 2 hours, takes out and cools off in ice-water bath immediately.Shake up, on the HP-6890 chromatogram, analyze with marker method.The styrene polymerization rate is 0.64% (weight).
[comparative example 1]
Get the mixture of 3 gram vinylbenzene, 7 grams (N-N-methyl-2-2-pyrrolidone N-+water, water 1 weight %), do not add stopper, experimental technique is with embodiment 1, styrene polymerization rate 28.4% (weight).
[embodiment 2]
Add embodiment 1 described stopper 2000PPm in the mixed system of 10 gram vinylbenzene, 10 grams (tetramethylene sulfide+water, water 1 weight %), experimental technique is with embodiment 1, styrene polymerization rate 0.15% (weight).
[embodiment 3]
To 9 gram vinylbenzene, 1 gram (tetramethylene sulfide+N-N-methyl-2-2-pyrrolidone N-+water, tetramethylene sulfide weight: N-N-methyl-2-2-pyrrolidone N-weight=2: 1, water 0.5 weight %) adds stopper 1200PPm of the present invention in the mixed system, the composition of stopper is with embodiment 1, experimental technique is with embodiment 1, but the residence time is 30 minutes, styrene polymerization rate 0.61% (weight).Here the reason that shortens the residence time is in distillation tower still (the highest zone of temperature in the tower), and residence time of material generally can be above 30 minutes.
[embodiment 4]
To 1 gram vinylbenzene, 19 gram (tetramethylene sulfides+N-N-methyl-2-2-pyrrolidone N-+water, tetramethylene sulfide weight: N-N-methyl-2-2-pyrrolidone N-weight=2: 1, water 0.5 weight %) adds stopper 50PPm of the present invention in the mixed system, the composition of stopper is with embodiment 1, experimental technique is with embodiment 1, but the residence time is 30 minutes, styrene polymerization rate 0.88% (weight).
[embodiment 5]
To 19 gram vinylbenzene, 1 gram (tetramethylene sulfide+N-N-methyl-2-2-pyrrolidone N-+water, tetramethylene sulfide weight: N-N-methyl-2-2-pyrrolidone N-weight=2: 1, water 0.5 weight %) adds stopper 1150PPm of the present invention in the mixed system, the composition of stopper is with embodiment 1, experimental technique is with embodiment 1, but the residence time is 30 minutes, styrene polymerization rate 0.76% (weight).
[embodiment 6]
To 3 gram vinylbenzene, 7 gram (tetramethylene sulfides+N-N-methyl-2-2-pyrrolidone N-+water, tetramethylene sulfide weight: N-N-methyl-2-2-pyrrolidone N-weight=2: 1, water 0.5 weight %) adds stopper 400PPm of the present invention in the mixed system, the composition of stopper is with embodiment 1, experimental technique is with embodiment 1, styrene polymerization rate 0.82% (weight).
[embodiment 7]
To 3 gram vinylbenzene, 7 gram (tetramethylene sulfides+N-N-methyl-2-2-pyrrolidone N-+water, tetramethylene sulfide weight: N-N-methyl-2-2-pyrrolidone N-weight=2: 1, water 0.5 weight %) adds stopper 800PPm of the present invention in the mixed system, the composition of stopper is with embodiment 1, experimental technique is with embodiment 1, styrene polymerization rate 0.55% (weight).
[embodiment 8]
Press each condition and the step of embodiment 1, just change the composition of stopper, be by weight percentage: Sodium Nitrite 80%, benzoquinones 10%, DNBP10%, styrene polymerization rate 0.52% (weight).
[embodiment 9]
Press each condition and the step of embodiment 1, just change the composition of stopper, be by weight percentage: Sodium Nitrite 20%, benzoquinones 50%, DNPC30%, styrene polymerization rate 0.41% (weight).
[embodiment 10]
Press each condition and the step of embodiment 1, change the composition of stopper, be by weight percentage: Sodium Nitrite 50%, benzoquinones 15%, DNPC35%, the consumption of stopper are 1000PPm, styrene polymerization rate 0.33% (weight).
Claims (7)
1, a kind of method that is used for prohibiting polymerization of styrene, to weight percent concentration is that the stopper that adds water-containing solvent dissolved 50～2000PPm in 5～99% the vinylbenzene Aquo System prevents cinnamic polymerization, and wherein stopper is made up of following component by weight percentage:
A) 20%～80% nitrite;
B) 10%～50% quinones;
C) 1%～35% nitrophenol, many nitrophenol or derivatives thereof;
Wherein nitrite is selected from least a in lithium nitrite, Sodium Nitrite or the potassium nitrite, the quinones joint compound is selected from least a in benzoquinones that benzoquinones, phenanthrenequione, anthraquinone or 3 carbon atom alkyls replace or the phenanthrenequione, nitrophenol, many nitrophenol or derivatives thereof are selected from 2,6-dinitro-p-cresol, 4,6-dinitrobenzene-2-sec-butyl phenol, 2,2, 4-dinitrophenol, at least a in the isomer of sylvan, phenol or nitrophenols.
2, the method that is used for prohibiting polymerization of styrene according to claim 1 is characterized in that the consumption of nitrite is 35～65% by weight percentage.
3, the method that is used for prohibiting polymerization of styrene according to claim 1 is characterized in that the consumption of nitrophenol, many nitrophenol or derivatives thereof is 15～35% by weight percentage.
4, the method that is used for prohibiting polymerization of styrene according to claim 1 is characterized in that the consumption of quinones joint compound is 15～35% by weight percentage;
5, the method that is used for prohibiting polymerization of styrene according to claim 1 is characterized in that cinnamic by weight percentage concentration is 30～95%.
6, the method that is used for prohibiting polymerization of styrene according to claim 1, the addition that it is characterized in that stopper is 400～2000PPm.
7, according to claim 1 or the 6 described methods that are used for prohibiting polymerization of styrene, the addition that it is characterized in that stopper is 400～1200PPm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101102802A CN100443455C (en) | 2005-11-11 | 2005-11-11 | Process for prohibiting polymerization of styrene |
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| CNB2005101102802A CN100443455C (en) | 2005-11-11 | 2005-11-11 | Process for prohibiting polymerization of styrene |
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| CN1962582A CN1962582A (en) | 2007-05-16 |
| CN100443455C true CN100443455C (en) | 2008-12-17 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0903005D0 (en) | 2009-02-23 | 2009-04-08 | Nufarm Ltd | Composition for controlling polymerisation |
| GB201011594D0 (en) | 2010-07-09 | 2010-08-25 | Nufarm Uk Ltd | Retarder composition |
| CN103012235A (en) * | 2012-12-13 | 2013-04-03 | 中盐安徽红四方股份有限公司 | Rectification polymerization inhibition method of N-vinylpyrrolidone (NVP) |
-
2005
- 2005-11-11 CN CNB2005101102802A patent/CN100443455C/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 略谈二烯烃阻聚剂类型. 张自义.兰州大学学报(自然科学版)，第3期. 1977 |
| 略谈二烯烃阻聚剂类型. 张自义.兰州大学学报(自然科学版)，第3期. 1977 * |
| 苯乙烯精馏阻聚剂的研究进展. 菅秀君，刘福胜等.精细石油化工，第3期. 2000 |
| 苯乙烯精馏阻聚剂的研究进展. 菅秀君，刘福胜等.精细石油化工，第3期. 2000 * |
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