CN102516005A - Combination for nitroxyl compounds and application of combination - Google Patents
Combination for nitroxyl compounds and application of combination Download PDFInfo
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- CN102516005A CN102516005A CN2011103739469A CN201110373946A CN102516005A CN 102516005 A CN102516005 A CN 102516005A CN 2011103739469 A CN2011103739469 A CN 2011103739469A CN 201110373946 A CN201110373946 A CN 201110373946A CN 102516005 A CN102516005 A CN 102516005A
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Abstract
The invention relates to a combination for nitroxyl compounds and an application of combination. The combination for the nitroxyl compounds provided by the invention is used for preventing the polymerization of vinyl aromatic hydrocarbon. In the combination, at least one nitroxyl compound is added into a 4-hydroxy-2,2,6,6-tetramethylpiperidine oxy group or a 4-oxo-2,2,6,6-tetramethylpiperidine oxy group, so that the problem of low solubility of the 4-hydroxy-2,2,6,6-tetramethylpiperidine oxy group in a solvent at low temperature and the problem of over-high content-reducing speed when the 4-oxo-2,2,6,6-tetramethylpiperidine oxy group is used are solved, the use temperature scope of the 4-hydroxy-2,2,6,6-tetramethylpiperidine oxy group is widened, and the stability of the content of the 4-oxo-2,2,6,6-tetramethylpiperidine oxy group is increased. The combination for the nitroxyl compounds is used for preventing the polymerization in a vinyl aromatic hydrocarbon refining process, and the performance of the combination for the nitroxyl compounds is equal to the performance of single nitroxyl compound.
Description
Technical field
The present invention relates to a kind of prevention vinyl-arene polymeric nitroxyl compound combination and method of use thereof.
Background technology
Nitroxyl compound is widely used in vinyl-arene because having the radical with inhibition, in the particularly cinnamic treating process, is used to stop the polymerization of unsaturated double-bond.The most frequently used nitroxyl compound is a 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base and 4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base.
Vinyl-arene, vinylbenzene for example, Vinylstyrene because have undersaturated pair of key, at high temperature is very easy to polymerization.The vinyl-arene that suitability for industrialized production obtains all has by product and unconverted raw material completely, so must be through the refining requirement that just can meet further use.Polymerization in that the vinyl-arene treating process takes place has reduced cinnamic yield.The tar meeting occluding device that produces, serious meeting has influence on normally carrying out of treating process.
In order to stop the polymerization of vinyl-arene in the treating process, a lot of compounds have been used as stopper, and nitroxyl compound is exactly one of them.The flat 1-165534 of japanese discloses nitroxyl compound and has been used for cinnamic resistance and gathers.Russian patent 1,558,888 disclose the method that stops styrene polymerization with a kind of nitroxyl compound.Chinese patent CN1084155A discloses the resistance that nitroxyl compound and aromatic nitro compound be used for vinyl-arene and has gathered.Chinese patent CN1392127A discloses 4-hydroxyl-2,2,6, and 6-tetramethyl-piperidyl oxygen base and 2-sec.-butyl-4,6-dinitrobenzene are used for vinylbenzene combination and are used for cinnamic resistance and gather.4-hydroxyl-2,2 is disclosed among the U.S. Pat 20090114878A1,6; 6-tetramethyl-piperidyl oxygen base or 4-oxo-2,2,6; 6-tetramethyl-piperidyl oxygen base and 2-sec.-butyl-4; 6-dinitrophenol(DNP) or 4-phenylmethylene-2,6-di-t-butyl-2,5-cyclohexadiene-1-ketone is as cinnamic stopper.
In the industrial applications process, use 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base or 4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base has run into some actual difficulties.
4-hydroxyl-2,2,6, during 6-tetramethyl-piperidyl oxygen base low temperature, zero degree for example, the solubleness in ethylbenzene is very little.When using water as solvent, the fusing point that receives water is the restriction of zero degree, 4-hydroxyl-2,2,6, the aqueous solution of 6-tetramethyl-piperidyl oxygen base can not use at low temperatures, otherwise winter during low temperature whole solution can become a bulk of solid.Above-mentioned phenomenon has seriously limited 4-hydroxyl-2,2,6, the use temperature scope of 6-tetramethyl-piperidyl oxygen base during as stopper.
4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base, at organic solvent, for example the solubleness in the ethylbenzene is bigger under the low temperature, and its solubleness can satisfy the requirement in market.But because active α hydrogen arranged, itself less stable.When temperature is higher, rotten very fast.In order to guarantee the stable of nitroxyl compound content, need refrigeration usually, store like this, transport 4-oxo-2,2,6, the cost of 6-tetramethyl-piperidyl oxygen base is higher.Receive the requirement of cost control, 4-oxo-2,2,6, restriction has been received in the use of 6-tetramethyl-piperidyl oxygen base nitroxyl compound.
4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base or 4-oxo-2,2,6, the These characteristics of 6-tetramethyl-piperidyl oxygen base cannot satisfy the requirement in market, and market presses for a kind of can the use at low temperatures, and the more stable product of content.
Summary of the invention
An object of the present invention is to provide a kind of nitroxyl compound combination that can use at a lower temperature.
Second purpose of the present invention provides the more stable nitroxyl compound combination of a kind of content.
The 3rd purpose of the present invention provides a kind of stopper of well behaved vinyl-arene treating process.
Embodiment
The present invention relates to a kind of combination of nitroxyl compound, this combination contains at least two kinds of nitroxyl compounds, and its nitroxyl compound is selected from:
2,2,6,6-tetramethyl-piperidyl oxygen base (hereinafter to be referred as TEMPO);
4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base (hereinafter to be referred as H-TEMPO);
4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base (hereinafter to be referred as Oxo-TEMPO);
1-oxygen-2,2,6,6-tetramethyl piperidine-4 carbamate;
1-oxygen-2,2,6,6-tetramethyl piperidine-4 yl acetate;
1-oxygen-2,2,6, the basic 2-ethylhexanoate of 6-tetramethyl piperidine-4;
1-oxygen-2,2,6, the basic stearate of 6-tetramethyl piperidine-4;
1-oxygen-2,2,6,6-tetramethyl piperidine-4 yl benzoic acid ester;
1-oxygen-2,2,6, the basic 4-p t butylbenzoic acid of 6-tetramethyl piperidine-4 ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) succinate;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) adipic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) sebate (hereinafter to be referred as SE-TEMPO);
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) n-butylmalonic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) phthalic ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) isophthalic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) terephthalate;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 bases) are to the cyclohexyl dicarboxylic acid ester;
Three (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) phosphorous acid ester (hereinafter to be referred as PH-TEMPO).
Having a kind of nitroxyl compound in this combination at least is 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base or 4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base.
Have at least a kind of content of nitroxyl compound to surpass 1% (weight percent) in this combination.
Nitroxyl compound of the present invention is made up the treating process that is used for vinyl-arene, and its suitable concentration in vinyl-arene is 1～2000ppm.
Nitroxyl compound of the present invention is made up the treating process that is used for vinyl-arene, itself and at least a retarder synergy, its retarder is selected from:
2,2, 4-dinitrophenol (DNP);
2-nitro-4-methyl phenol (being called for short NPC);
2,6-dinitrobenzene-4-methylphenol (being called for short DNPC);
2,4-dinitrobenzene-6-sec-butyl phenol (being called for short DNBP);
4-phenylmethylene-2,6-di-t-butyl-2,5-cyclohexadiene-1-ketone (being called for short DTBMeOQM).
The weight ratio that is fit between nitroxyl compound and the retarder is 1: 99～99: 1.
With embodiment the present invention is described below.
Embodiment 1-9
In thermostatic bath, put into a there-necked flask that 100 gram ethylbenzene are housed,, test their solubleness in ethylbenzene under the differing temps respectively not stopping to stir the following different nitroxyl compound combination that slowly is metered into respectively.
Solubleness under table 1 differing temps (gram)
* nitroxyl compound combination A is the mixture of H-TEMPO and Oxo-TEMPO, and the weight ratio of H-TEMPO and Oxo-TEMPO is 1: 1
Nitroxyl compound combination B is the mixture of H-TEMPO and PH-TEMPO, and the weight ratio of H-TEMPO and PH-TEMPO is 1: 1
Data in the table 1 show, after adding other nitroxyl compound, and 4-hydroxyl-2,2,6, the solubleness of 6-tetramethyl-piperidyl oxygen base in ethylbenzene improves greatly, and is especially obvious at low temperatures.
Embodiment 10-13
Use different nitroxyl compounds ethylbenzene to be configured to 20% solution, in 50 ℃ thermostat container, placed seven days continuously as solvent, the nitroxyl compound content of testing total, the result who obtains is as shown in table 2.
50 ℃ of following stability datas of the different nitroxyl compounds of table 2
* nitroxyl compound combination C is the mixture of Oxo-TEMP and OH-TEMPO, and the weight ratio of Oxo-TEMPO and H-TEMPO is 1: 1
Nitroxyl compound combination D is the mixture of Oxo-TEMPO and PH-TEMPO, and the weight ratio of Oxo-TEMPO and PH-TEMPO is 1: 1
Nitroxyl compound combination E is the mixture of Oxo-TEMPO and SE-TEMPO, and the weight ratio of Oxo-TEMPO and SE-TEMPO is 1: 1
The data of table 2 show that behind other nitroxyl compound of adding, the fall off rate of oxynitrides content is starkly lower than pure Oxo-TEMPO among the OXO-TEMPO.
Embodiment 14-25
On 250 milliliters there-necked flask, load onto TM, return line and stirring rake; Toward the interior vinylbenzene that has removed stablizer that adds 100 grams of flask; Add the oxygen content in 15 minutes minimizing systems of logical nitrogen behind the following material, closed system is placed on whole flask in 120 ℃ the constant temperature oil bath then; Continuously stirring is tested the content of the polymkeric substance in the vinylbenzene after two hours, the result who obtains sees table 3.
The different additives of table 3 are to cinnamic polymerization inhibition effect
* nitroxyl compound combination F is the mixture of H-TEMPO and Oxo-TEMPO, and the weight ratio of H-TEMPO and Oxo-TEMPO is 1: 1
Nitroxyl compound combination B is the mixture of H-TEMPO and SE-TEMPO, and the weight ratio of H-TEMPO and SE-TEMPO is 1: 1
Table 3 explanation, nitroxyl compound combination of the present invention is suitable for the effect of cinnamic polymerization inhibition effect and single nitroxyl compound.The difference of nitroxyl compound combination, polymerization inhibition effect is also different.
Claims (11)
1. a nitroxyl compound combination is characterized in that comprising two kinds or two or more nitroxyl compounds.
2. the nitroxyl compound of claim 1 is selected from:
2,2,6,6-tetramethyl-piperidyl oxygen base;
4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base;
4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base;
1-oxygen-2,2,6,6-tetramethyl piperidine-4 carbamate;
1-oxygen-2,2,6,6-tetramethyl piperidine-4 yl acetate;
1-oxygen-2,2,6, the basic 2-ethylhexanoate of 6-tetramethyl piperidine-4;
1-oxygen-2,2,6, the basic stearate of 6-tetramethyl piperidine-4;
1-oxygen-2,2,6,6-tetramethyl piperidine-4 yl benzoic acid ester;
1-oxygen-2,2,6, the basic 4-p t butylbenzoic acid of 6-tetramethyl piperidine-4 ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) succinate;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) adipic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) sebate;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) n-butylmalonic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) phthalic ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) isophthalic acid ester;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) terephthalate;
Two (1-oxygen-2,2,6,6-tetramethyl piperidine-4 bases) are to the cyclohexyl dicarboxylic acid ester;
Three (1-oxygen-2,2,6,6-tetramethyl piperidine-4 base) phosphorous acid ester.
3. the nitroxyl compound of claim 1 combination is characterized in that having at least the weight ratio of a kind of nitroxyl compound in compsn to surpass 1%.
Claim 1 nitroxyl compound combination, it is characterized in that having at least a kind of nitroxyl compound is 4-hydroxyl-2,2,6,6-tetramethyl-piperidyl oxygen base or 4-oxo-2,2,6,6-tetramethyl-piperidyl oxygen base.
5. the combination of the nitroxyl compound of claim 1 is used for the vinyl-arene treating process.
6. the vinyl-arene of claim 5 is selected from vinylbenzene, alpha-methyl styrene, Vinyl toluene, Vinylstyrene.
7. the vinyl-arene treating process of claim 5 is characterized in that the nitroxyl compound combination directly joins in the vinyl-arene.
8. the vinyl-arene treating process of claim 5 is characterized in that nitroxyl compound combination water, toluene, and ethylbenzene etc. are produced involved raw material in the vinyl-arene process, and product joins in the vinyl-arene after solvent or the impurity dissolving again.
9. the vinyl-arene treating process of claim 5 is characterized in that the concentration that nitroxyl compound is combined in the vinyl-arene is 1～2000ppm.
10. the vinyl-arene treating process of claim 5 is characterized in that nitroxyl compound combination and at least a retarder combination use, and wherein retarder is selected from:
2,2, 4-dinitrophenol;
2-nitro-4-methyl phenol;
2,6-dinitrobenzene-4-methylphenol;
2,4-dinitrobenzene-6-sec-butyl phenol;
4-phenylmethylene-2,6-di-t-butyl-2,5-cyclohexadiene-1-ketone.
11. the combination of combination of the nitroxyl compound of claim 10 and retarder is used, and it is characterized in that the weight ratio of nitroxyl compound combination and retarder is 1: 99～99: 1.
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| CN2011103739469A CN102516005A (en) | 2011-11-21 | 2011-11-21 | Combination for nitroxyl compounds and application of combination |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2993164A1 (en) | 2014-09-08 | 2016-03-09 | Evonik Degussa GmbH | Phenolic (thio) acetals as inhibitors of the polymerisation of olefinically unsaturated monomers |
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| US5254760A (en) * | 1992-07-29 | 1993-10-19 | Ciba-Geigy Corporation | Inhibiting polymerization of vinyl aromatic monomers |
| WO2000036052A1 (en) * | 1998-12-17 | 2000-06-22 | Nalco/Exxon Energy Chemicals, L.P. | Inhibiting polymerization of vinyl aromatic monomers using synergistic mixtures containing nitroxide stabilizers |
| CN1259114A (en) * | 1997-06-13 | 2000-07-05 | 西巴特殊化学品控股有限公司 | Polymerization inhibition of acrylates using blends of nitroxides |
| WO2001040404A1 (en) * | 1999-12-03 | 2001-06-07 | Uniroyal Chemical Company, Inc. | Composition and method for inhibiting polymerization and polymer growth |
| WO2002033026A1 (en) * | 2000-10-16 | 2002-04-25 | Uniroyal Chemical Company, Inc. | Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors |
| US20060122341A1 (en) * | 2004-12-03 | 2006-06-08 | Vilan Kosover | Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors |
| US20090114878A1 (en) * | 2007-11-02 | 2009-05-07 | Evonik Degussa Gmbh | Process for stabilizing olefinically unsaturated monomers |
| US20100168434A1 (en) * | 2005-10-20 | 2010-07-01 | A H Marks And Company Limited | Inhibition of polymerisation |
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2011
- 2011-11-21 CN CN2011103739469A patent/CN102516005A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254760A (en) * | 1992-07-29 | 1993-10-19 | Ciba-Geigy Corporation | Inhibiting polymerization of vinyl aromatic monomers |
| CN1259114A (en) * | 1997-06-13 | 2000-07-05 | 西巴特殊化学品控股有限公司 | Polymerization inhibition of acrylates using blends of nitroxides |
| WO2000036052A1 (en) * | 1998-12-17 | 2000-06-22 | Nalco/Exxon Energy Chemicals, L.P. | Inhibiting polymerization of vinyl aromatic monomers using synergistic mixtures containing nitroxide stabilizers |
| WO2001040404A1 (en) * | 1999-12-03 | 2001-06-07 | Uniroyal Chemical Company, Inc. | Composition and method for inhibiting polymerization and polymer growth |
| WO2002033026A1 (en) * | 2000-10-16 | 2002-04-25 | Uniroyal Chemical Company, Inc. | Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors |
| US20060122341A1 (en) * | 2004-12-03 | 2006-06-08 | Vilan Kosover | Aromatic sulfonic acids, amines, and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosanilines as polymerization inhibitors |
| US20100168434A1 (en) * | 2005-10-20 | 2010-07-01 | A H Marks And Company Limited | Inhibition of polymerisation |
| US20090114878A1 (en) * | 2007-11-02 | 2009-05-07 | Evonik Degussa Gmbh | Process for stabilizing olefinically unsaturated monomers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2993164A1 (en) | 2014-09-08 | 2016-03-09 | Evonik Degussa GmbH | Phenolic (thio) acetals as inhibitors of the polymerisation of olefinically unsaturated monomers |
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Application publication date: 20120627 |