CA1224811A - Polymerization inhibition process for vinyl aromatic compounds - Google Patents
Polymerization inhibition process for vinyl aromatic compoundsInfo
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- CA1224811A CA1224811A CA000451559A CA451559A CA1224811A CA 1224811 A CA1224811 A CA 1224811A CA 000451559 A CA000451559 A CA 000451559A CA 451559 A CA451559 A CA 451559A CA 1224811 A CA1224811 A CA 1224811A
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- Prior art keywords
- ppm
- vinyl aromatic
- phenylenediamine
- column
- aromatic compound
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Abstract of the Disclosure A compound and a process for utilizing the compound to prevent the polymerization of vinyl aromatic compounds, such as styrene, during heating. The composition includes effective amounts of 2,6-dinitro-p-cresol and either a phenylenediamine or 4-tert-butylcatechol respectively, to act as a polymerization co-inhibitor system in the presence of oxygen.
Description
~ `
12248~1 COS 488 ~-POLYMERIZATION INHIBITION PROCESS FOR VINYL AROMATIC
___ __ _____ COMPOUNDS
Background of the Invention The present invention relates to a polymer inhibiting composition and to a process for inhibiting the polymerization of a readily polymerizable vinyl aromatic compound. F
It is well known that vinyl aromatic compounds F
such as monomeric styrene, lower alkylated styrene such as alpha-methylstyrene and the like, polymerize readily and furthermore, that the rate of polymeriæation increases with increasing temperature. Inasmuch as vinyl aromatic 10 compounds produced by common industrial methods contain L
impurities, these compounds must be subjected to separation and purification processes in order to be suitable for most ~-~
types of further industrial use. Such separation and purification are generally accomplished by distillation. r_ In order to prevent polymerization during storage of vinyl aromatic compounds, various types of known polymerization inhibitors have been employed usually under refrigerated conditions. For example, common inhibitors useful for inhibiting the polymerization of vinyl aromatic compounds during storage conditions include 4-tert-butylcatechol (TBC) and hydroquinone.
F
. ~ ~
~; ~
12248~1 COS 488 ~-POLYMERIZATION INHIBITION PROCESS FOR VINYL AROMATIC
___ __ _____ COMPOUNDS
Background of the Invention The present invention relates to a polymer inhibiting composition and to a process for inhibiting the polymerization of a readily polymerizable vinyl aromatic compound. F
It is well known that vinyl aromatic compounds F
such as monomeric styrene, lower alkylated styrene such as alpha-methylstyrene and the like, polymerize readily and furthermore, that the rate of polymeriæation increases with increasing temperature. Inasmuch as vinyl aromatic 10 compounds produced by common industrial methods contain L
impurities, these compounds must be subjected to separation and purification processes in order to be suitable for most ~-~
types of further industrial use. Such separation and purification are generally accomplished by distillation. r_ In order to prevent polymerization during storage of vinyl aromatic compounds, various types of known polymerization inhibitors have been employed usually under refrigerated conditions. For example, common inhibitors useful for inhibiting the polymerization of vinyl aromatic compounds during storage conditions include 4-tert-butylcatechol (TBC) and hydroquinone.
F
. ~ ~
~; ~
2 ~224811 Sulfur, on the other hand, has been widely employed as a polymerization inhibitor during the distillation of various vinyl aromatic compounds. However, while sulfur provides a reasonably effective inhibitor, its use in such distillation processes results in a highly significant disadvantage namely, there is formed in the reboiler bottom of the distillation column a valueless waste material highly contaminated with sulfur. This waste material, furthermore represents a significant problem of pollution and/or waste removal.
Although many compounds are effective for inhibiting the polymerization of vinyl aromatic compounds under differing conditions such as storage, only some of these compounds have proved to be of any real utility for inhibiting vinyl aromatic polymerization under distillation conditions. One compound found effective for polymerization inhibition is 2, 6-dinitro-p-cresol (DNPC) disclosed in U.S. Patent No. 4,105,506 by Watson. In addition, it has been found that previously known polymerization inhibitors may be combined to achieve an inhibitory effect greater than either inhibitor alone. The synergistic effect of combining two known inhibitors was ~-disclosed in U.S. Patent No. 4,061,545 by Watson, wherein phenothiazine and tert-butylcatechol (TBC) were used together in the presence of oxygen as a polymerization inhibitor. The synergistic effect of N-nitrosodiphenylamine combined with DNPC in inhibiting the polymerization of vinyl toluene under vacuum conditions was disclosed in U.S. Patent No. 4,341,600 by Watson. It has been found, however, that as the distillation temperature
Although many compounds are effective for inhibiting the polymerization of vinyl aromatic compounds under differing conditions such as storage, only some of these compounds have proved to be of any real utility for inhibiting vinyl aromatic polymerization under distillation conditions. One compound found effective for polymerization inhibition is 2, 6-dinitro-p-cresol (DNPC) disclosed in U.S. Patent No. 4,105,506 by Watson. In addition, it has been found that previously known polymerization inhibitors may be combined to achieve an inhibitory effect greater than either inhibitor alone. The synergistic effect of combining two known inhibitors was ~-disclosed in U.S. Patent No. 4,061,545 by Watson, wherein phenothiazine and tert-butylcatechol (TBC) were used together in the presence of oxygen as a polymerization inhibitor. The synergistic effect of N-nitrosodiphenylamine combined with DNPC in inhibiting the polymerization of vinyl toluene under vacuum conditions was disclosed in U.S. Patent No. 4,341,600 by Watson. It has been found, however, that as the distillation temperature
3 ~2248~1 ~.
increases, the eEfectiveness of these inhibitors decreases.
During distillation of vinyl aromatic compounds, higher distillation temperatures are preferred in a distillation apparatus in order to achieve a higher throughput and a more energy efficient distillation. These higher temperatures, however, also result in an increased rate of polymerization which leads to unacceptable levels of polymer in the distillation apparatus. Accordingly, therefore, there exists a strong need for a polymerization inhibitor which will effectively prevent the polymerization of vinyl aromatic compounds during distillation at higher temperatures.
Summary of the Invention It is therefore an object of the present invention to provide both a polymer inhibiting composition and a process for inhibiting the polymerization of vinyl aromatic compounds.
Another object of the invention is to provide both a polymer inhibiting composition and a process for !~;
inhibiting the polymerization of vinyl aromatic compounds at higher temperatures resulting in a higher recovery of high purity, unsaturated vinyl aromatic compounds and in the production of less undesirable by-products.
A still further object of the invention resides in the provision of both a polymer inhibiting composition and a process for inhibiting the polymerization of vinyl aromatic compounds which permits the distillation apparatus to be operated at a higher temperature and an increased - ~224811 ,~
rate of throughput without a reduction in efficiency.
In accomplishing the foregoing and other objects, there has been provided in accordance with the present invention a composition for inhibiting the distillation of a readily polymerizable vinyl aromatic compound in the presence of oxygen when subject to elevated temperature such as in a distillation process, the composition comprising an effective amount of 2,6-dinitro-p-cresol and an effective amount of a phenylene diamine having the formula R~ - N~ 2 wherein R1 and R2 are alkyl, aryl or hydrogen.
In an alternate embodiment, the inhibitor composition comprises an effective amount of 2,6-dinitro-p-cresol and 4-tert-butylcatechol.
The vinyl aromatic compounds covered in the present invention include styrene, substituted styrene, divinylbenzene, vinyltoluene, vinyl naphthalene and the polyvinylbenzenes. This group is also understood to include all structural isomers thereof.
Also, in accomplishing the foregoing other objects, there is provided in accordance with the present invention, a process for inhibiting the polymerization of a readily polymerizable vinyl aromatic compound comprising subjecting the vinyl aromatic compound to heating 30 conditions, such as distillation, in the presence of ~-effective amounts of 2,6-dinitro-p-cresol and the , . _ ~224811 .~
aforementioned phenylenediamine derivatives or
increases, the eEfectiveness of these inhibitors decreases.
During distillation of vinyl aromatic compounds, higher distillation temperatures are preferred in a distillation apparatus in order to achieve a higher throughput and a more energy efficient distillation. These higher temperatures, however, also result in an increased rate of polymerization which leads to unacceptable levels of polymer in the distillation apparatus. Accordingly, therefore, there exists a strong need for a polymerization inhibitor which will effectively prevent the polymerization of vinyl aromatic compounds during distillation at higher temperatures.
Summary of the Invention It is therefore an object of the present invention to provide both a polymer inhibiting composition and a process for inhibiting the polymerization of vinyl aromatic compounds.
Another object of the invention is to provide both a polymer inhibiting composition and a process for !~;
inhibiting the polymerization of vinyl aromatic compounds at higher temperatures resulting in a higher recovery of high purity, unsaturated vinyl aromatic compounds and in the production of less undesirable by-products.
A still further object of the invention resides in the provision of both a polymer inhibiting composition and a process for inhibiting the polymerization of vinyl aromatic compounds which permits the distillation apparatus to be operated at a higher temperature and an increased - ~224811 ,~
rate of throughput without a reduction in efficiency.
In accomplishing the foregoing and other objects, there has been provided in accordance with the present invention a composition for inhibiting the distillation of a readily polymerizable vinyl aromatic compound in the presence of oxygen when subject to elevated temperature such as in a distillation process, the composition comprising an effective amount of 2,6-dinitro-p-cresol and an effective amount of a phenylene diamine having the formula R~ - N~ 2 wherein R1 and R2 are alkyl, aryl or hydrogen.
In an alternate embodiment, the inhibitor composition comprises an effective amount of 2,6-dinitro-p-cresol and 4-tert-butylcatechol.
The vinyl aromatic compounds covered in the present invention include styrene, substituted styrene, divinylbenzene, vinyltoluene, vinyl naphthalene and the polyvinylbenzenes. This group is also understood to include all structural isomers thereof.
Also, in accomplishing the foregoing other objects, there is provided in accordance with the present invention, a process for inhibiting the polymerization of a readily polymerizable vinyl aromatic compound comprising subjecting the vinyl aromatic compound to heating 30 conditions, such as distillation, in the presence of ~-effective amounts of 2,6-dinitro-p-cresol and the , . _ ~224811 .~
aforementioned phenylenediamine derivatives or
4-tert-butylcatechol respectively, and oxygen.
According to the present process, the amount of polymerization occurring within the distillation apparatus
According to the present process, the amount of polymerization occurring within the distillation apparatus
5 at temperatures as high as 150C is significantly reduced in comparison with conventionally employed methods. In ~;
addition, the distillation apparatus may be operated at a higher temperature and pressure than when using conventional inhibitors thereby allowing a higher rate of 10 distillation throughput.
Further objects, features, and advantages of the invention will become apparent from the detailed c description which follows and from the claims.
15 Brief-Description of the Drawings Fig. 1 is a schematic diagram of one embodiment of the process of the present invention utilizing a three column distillation train, and Fig. 2 is a schematic diagram of another 20 embodiment of the process of the present invention ~T
utilizing direct injection of the vinyl aromatic feed into the recycle column. r ~;:
Detailed Desc_ ptlon of the Preferred Embodiment _ _ _ ~ _ The present invention employs 2,6-dinitro-p-cresol, hereinafter referred to as DNPC, and a phenylenediamine derivative in the presence of oxygen, as a polymerization co-inhibitor composition during the heating of vinyl aromatic compounds.
The phenylenediamine of the present invention has , ~
l224all the formula: -R1 - N - ~ - N - R2 wherein R1 is an alkyl group, aryl group or hydrogen, and R2 is an alkyl group, aryl group, or hydrogen. It is ~-preferred that the allcyl groups of R1 and R2 respectively contain from 1 to 12 carbons inclusive.
Examples of such preferred p'nenylenediamine derivatives include p-phenylenediamine, N, N'dimethyl phenylenediamine, N, N'-diethylphenylenediamine, N, N'-Bis~1,4-dimethylpentyl) -p-phenylenediamine, and N-4-methyl-2-pentyl-N'-phenyl-p- ~K' phenylenediamine.
It should be noted that N, N'-Bis (1, 4-dimethylpentyl)-p-phenylenediamine and N-4-methyl-2-pentyl-N'-phenyl-p-phenylenediamine are particularly preferred; however, N, N'-Bis (1, 4-dimethylpentyl)-p-phenylenediamine is the most preferred.
The distillation techniques of the present 20 invention are suitable for use in virtually any type of separation of a readily polymerizable vinyl aromatic compound from a mixture where the compound is subjected to ~-temperatures above room temperature. By polymerization inhibitor it is meant that unwanted polymerization of the vinyl aromatic monomer is prevented at elevated temperatures such as in a distillative apparatus. .' Increasing the temperature in the apparatus has the -advantages of a higher distillation rate, however, this increased temperature can cause a higher rate of polymerization which is counterbalanced by the introduction ~2248~1 -'~
of the inhibitor of the present invention. In its most useful application, the composition is applied to a distillation mixture of vinyl aromatic compounds selected from the group consisting of styrene, substituted styrene 5 such as alpha-methyl styrene, divinylbenzene, vinyl toluene, vinyl naphthalene, and the polyvinylbenzenes.
This group is understood to include all structural isomers of the aforementioned compounds. The preferred application of the present invention relates to the distillation of 10 crude styrene.
The amounts of polymerization inhibitor added may vary over a wide range depending upon the conditions of b~;
distillation. Generally, the degree of stabilization is r proportional to the amount of inhibitor added. In 15 accordance with the present invention, it has been found, based on vinyl aromatic feed to the B-T column 10 or the recycle column 90, that a phenylenediamine concentration generally between about 50 ppm and 2000 ppm and a DNPC
concentration between about 100 ppm and 2000 ppm have 20 generally produced suitable results, depending primarily r-upon the temperature of the distillative mixture and the degree of inhibition desired. Preferably however, the r-phenylenediamine lnhibitor o~ the present invention is used in concentration from about 50 ppm to about 1000 ppm and the DNPC concentration is from about 250 ppm to about 1000 ppm. The preferred ppm ratio of phenylenediamine to DNPC
is 2:3. There is no particular order for mixing the compounds of the present invention. In one particular embodiment tl-ey are added together at atmospheric 30 temperature and pressure outside the distillation train and r 8 ~Z;~481~
injected therein. The distillation technique of the present invention is suitable for use in virtually any type of distillative separation of a readily polymerizable vinyl aromatic compound from a mixture wherein the vinyl aromatic compound is subject to temperatures above room temperature.
Oxygen must be added to the system in order for the phenylenediamine co-inhibitor to work properly. Oxygen is added separately into the system to achieve a greater concentration of oxygen in the required area. The oxygen employed in the present invention may be in the form of oxygen or an oxygen-containing gas. If an oxygen-containing gas is employed, the remaining F-constituents of the gas must be inert to the vinyl aromatic compound under the distillation conditions. The most useful and least expensive source of oxygen is air, which is preferred for the present invention. The amount of oxygen may vary widely, but generally it is desirable to use that amount found in air.
Referring to the drawings, FIG. 1 illustrates a conventional styrene distillation train comprising a benzene-toluene fractionation column 10, referred to in the r industry as a B-T column, an ethylbenzene or recycle column 12, and a styrene or finishing column 14. It should be 25 ~oted that the operational principles of the present distillation method are highly suitable for use, with minor modifications, with other distillation equipment used in the purification of other vinyl aromatic compounds. As shown in FIG. 1, a crude styrene feed is introduced into 30 the intermediate portion of B-T column 10 through feedline r ~, 16. B-T column lO may be of any suitable design known to one skilled in the art and may contain any suitable number of vapor-liquid contacting devices, such as bubble cap trays, perforated trays, etc. Usually, however, column 10 5 contains less than forty distillation trays. Column 10 is also equipped with a suitable reboiler 18 for supplying heat thereto. Temperature of reboiler 18-is generally from about 190F to about 250F.
W'nile most of the polymer is formed in the 10 ethylbenzene or recycle column 12, a small but significant amount of the total polymer formed during distillation is formed in the B-T column 10. Accordingly, a polymerization inhibitor is desirable within this column. To prevent polymerization in the B-T column 10, 2, 6-dinitro-p-cresol 15 hereinafter referred to as DNPC, is introduced into the B-T
column 10 as a separate stream through line 20, or it may be incorporated into the crude styrene feed flowing through line 16. To facilitate the process, the phenylenediamine inhibitor may also be introduced into the B-T column 10 20 through line 20 or it may be incorporated into the crude ~-styrene feed flowing through line 16. Although the ?
phenylenediamine inhibitor provides little or no inhibition ~' in B-T column 10 due to lack of oxygen, it is transported with the B-T bottoms through line 24 to the recycle column 25 12 where it acts as the primary inhibitor therein. When the DNPC and/or phenylenediamine polymerization inhibitor are added to the B-T column 10 as a separate stream they -are preferably dissolved in a volatile aromatic hydrocarbon diluent such as ethylbenzene. The position of the 30 inhibitor feedline 20 will normally be intermediate to B-T
' ~22481~
column 10 in order to achieve an inhibitor distribution which is nearly coincident with the distribution of the readily polymerizable vinyl aromatic compound within the column 10.
Under the distillation conditions imposed in column 10, an overhead stream comprising benzene and toluene is removed via line 22. These low boiling aromatic hydrocarbons are subsequently condensed and passed to storage for further use. The bottoms product in the B-T
column comprising styrene, ethylbenzene, inhibitor and tar, serves as a charge to the recycle or ethylbenzene column 12. The bottoms product is introduced into the intermediate portion of ethylbenzene column 12 by means of line 24 and pump 26. The recycle column 12 may be of any suitable design known to those skilled in the art and may contain from 40 to 100 trays. Preferably, however, the recycle column is of the parallel path design.
Additionally, it is also preferable that the recycle column contain a large number of trays, as many as 72, in order to achieve a proper separation between the similar boiling styrene and ethylbenzene. The B-T bottoms are preferably introduced into the intermediate portion of the recycle column 12.
A certain amount of inhibitor protection within the ethylbenzene column 12 is provided by the phenylenediamine composition introduced intermediate to column 12 through line 2~, together with the B-T bottoms fraction through line 30, or with the DNPC into the B-T
column through line 20. It is necessary to add air only to 30 recycle column 12 due to DNPC protection in the rest of the ~r~
.
distillation train. In the recycle column 12 a more effective polymerization inhibitor is necessary due to the high temperatures up to 150C therein which are desirable in that column for a more energy efficient distillation.
5 By obtaining temperatures of at least 118C and preferably 130C or more, low pressure steam may bè recovered from an overhead condensor (not shown) on recycle column 12.
Oxygen is introduced into reboilers 32 through air purge lines 36 and 38 respectively. Alternatively, 10 oxygen may be introduced into reboilers 32 through sump or boot 40 via line 42 if there is sufficient air pressure/volume to reach the reboilers through line 43.
For the phenylenediamine to be effective, an equilibrium amount of oxygen is dissolved in the liquid phase of the 15 column 12; however, the amount of oxygen introduced should not exceed that amount which could cause explosion therein.
The oxygen is dispersed throughout the column 12 where it works in conjunction with the phenylenediamine to inhibit polymerization therein. The amount of oxygen necessary 20 will depend on the number and spacing of oxygen inlets around column 12, and how efficiently oxygen and liquid hydrocarbon are mixed therein. Therefore in practical application, the oxygen flow is increased as long as polymer yields are reduced, limited by the amount of oxygen 25 which would yield an explosive mixture. Complete dispersion of air throughout column 12 does not generally ;~
occur, therefore the presence of DNPC therein works as a r co-inhibitor at those locations where the effectiveness of the phenylenediamine is diminished due to the absence of 30 air. Therefore, the DNPC continues providing ~224~
.
-~..
polymerization inhibition in those areas of recycle column 12 where there is an absence of air thereby providing an overall higher polymerization inhibition effectiveness than would have been achieved if only phenylenediamine had been present by itself or in combination with other oxygen - activated inhibitors.
Surprisingly, it has been found that not only is DNPC compatible with the phenylenediamine, DNPC also works as a polymerization inhibitor in the presence of air as 10 well as in its ~bsence. DNPC therefore also provides inhibitor protection in addition to that provided by phenylenediamine in those areas of the recycle column where there is effective air dispersion. It has been found, however, that when DNPC alone is used as an inhibitor in 15 the presence of air, the DNPC is exhausted more rapidly.
This may be due to the fact that more polymer free radicals are generated in the presence of air. Therefore, to maintain effective DNPC/oxygen polymerization inhibition f over an extended period of time it is necessa~y to add more 20 DNPC inhibitor. Additional DNPC and phenylenediamine protection may be obtained by the recycle of tar conl:~ining DNPC/phenylenediamine back into recycle column 12 as explained in U.S. Patent No. 4,272,344.
Alternatively, the phenylenediamine inhibitor may 25 be introduced with the DNPC inhibitor into the B-T column 10 through line 20 as a DNPC/phenylenediamine mixture.
There is no preferred order of mixing these together. A
random order of mixing at ambient temperature and pressure will achieve suitable results. A portion of the DNPC/phenylenediamine inhibitor travels through the B-T
column to the recycle column 12 together with the B-T
bottoms product.
The bottoms portion from recycle column 12 comprisinq styrene inhibitor and tar is withdrawn from the reboiler area of recycle column 12 through line 60. The recycle bottoms is then fed by pump 62 into the intermediate portion of the styrene or finishing column 14 through line 64. Optionally, the bottoms material may be introduced into the lower portion of the styrene column 14 through line 66.
The finishing column 14 may be of any suitable ~;
design known to those skilled in the art. A typical column will contain for example, about 24 distillation trays.
Reboilers 68 are connected to sump 76 through line 78 and pump 80. Reboiler 68 is generally operated at a temperature from about 82C to about 121C. Generally, inhibitor protection is adequately provided in this column by the DNPC and phenylenediamine inhibitor present in the 20 bottoms feed. A portion of the tar from column 14 may be r-recycled at least back into the ethylbenzene column 12 through line 88 in order to further supplement the DNPC
within the system. ?`
The high purity styrene overhead product is withdrawn through line 74 from styrene column 14. The styrene column bottoms product, composed of polystyrene, undistilled styrene, heavy by-products and the DNPC/
phenylenediamine co-inhibitor, is withdrawn off the reboiler recirculating line 78 and directed to a flash pot 30 54 via line 85 for further processing. In the flash pot 84 r ~224811 ,~, residual styrene is removed from the bottoms of the styrene column and recycled back thereto through line 86. The tar produced in the flash pot 84 is withdrawn from the system on a continuous bas-s through line 83 or recycled back to the recycle column 12 or B-T column 10 through line 88.
FIG. 2 illustrates the application of the distillation method of the present invention to another typical distillation train. A styrene feed is introduced through line 91 into the intermediate portion of recycle 10 column 90, which is preferably of the parallel distillation path design. Line 92 supplies the phenylenediamine inhibitor to the recycle column 90. Heat is supplied to the bottoms of column 90 by means of reboilers 94. Oxygen r is introduced into reboilers 94 through air purge lines 96 15 and 98. Oxygen may be introduced directly into reboilers 94 through sump or boot 100 and line 101 if there is sufficient oxygen pressure and volume to reach the ~-reboilers through lines 97. In B-T column 122, benzene and toluene are withdrawn as an overhead fraction through line 20 123 and are subsequently condensed for further use. An ethylbenzene bottoms product is withdrawn through line 124 i, and is recycled for further use. Reboiler 126 provides B-T rb column 122 with the necessary heat for distillation.
The recycle bottoms product comprising 25 polystyrene, undistilled styrene, heavy by-products, phenylenediamine and DNPC is withdrawn from recycle column 1-90 through line 128. The impure styrene fraction is then charged to the upper portion of the styrene column 130 by means of pump 132 and line 133. Optionally, impure styrene 30 may be introduced into the lower region of styrene column ~:
12~481~
100 through line 134. A reboiler circuit comprising reboiler 136 and pump 138 is attached to the styrene or finishing column 130 for supplying the necessary heat thereto. DNPC is preferably introduced with the 5 phenylenediamine into recycle column 90 through line 92.
The purified styrene overhead product is withdrawn through line 144.
Reboilers 148 are connected to finishing column sump 136 through recirculating line 145 and pump 150. The 10 finishing column bottoms produce is withdrawn off reboiler recirculating line 145 for further processing in flash pot 146. Flash pot 146 recycles back into finishing column 14 ~;
through line 149. The tar produced during the distillation r process is withdrawn through line 152 or recycled back to 15 the distillation train through line 154.
In another embodiment of the present invention, an effective amount of 4-tert-butylcatechol is introduced into the aforementioned distillation trains through recycle columns 12, 90 in place of the phenylenediamine to act as a 20 co-inhibitor with DNPC. It has been found that DNPC and 4-tert-butylcatechol, hereinafter referred to as TBC, is an efficient co-inhibitor system in the presence of air at 2 temperatures up to 140C. An effective amount of TBC, based on vinyl aromatic feed to the B-T column 10 or the recycle column 90, is from about 50 ppm to about 2000 ppm;
a preferred amount of TBC is from about 200 ppm to about 1000 ppm. The preferred ppm ratio of TBC to DNPC iS 2 to 3.
Use of the compositions and methods of the present invention enables a distillation apparatus to operate , . .
r :.:
,~, with an increased throughput rate as opposed to conventional prior art processes since higher temperatures are permitted in the recycle column due to introduction of effective amounts of DNPC/phenylenediamine or DNPC/TBC inhibitor composition. In addition, the DNPC inhibitor may be used in the remaining fractionation columns to insure effective polymerization inhibition where lower temperatures and absence of air are encountered. Therefore, higher distillation temperatures and higher pressure may be utilized without the formation of objectionable amounts of polymer. In this manner, the rate of distillation may be increased without increasing the amount of polymerization --which was previously experienced in the conventional distillation procedures.
In addition by optimizing the distribution of the DNPC/phenylenediamine or DNPC/TBC inhibitor within the recycle column and by optimizing the distribution of DNPC
inhibitor in the remaining fractionation columns of the ~~
distillation train, greater temperatures may be achieved in the recycle column than in conventional distillation procedures to permit more efficient energy recovery therefrom. ,-In order to more fully describe the present invention, the following examples are presented which are intended to be illustrative and not in any sense limitative of the invention.
Example 1 Two 100 ml reaction flasks were prepared. A
30 first (1) was charged with 25 grams styrene to which was i~-12248~
added lO0 ppm DNPC and 50 ppm Flexone 4L, (a trademark of Uniroyal Chemical, Flexone 4L having the chemical formula N, N'-Bis (1,4-dimethylpentyl)-p-phenylenediamine as discussed in the Uniroyal Material Safety Sheet covering Flexone 4L). A second (2) flask was charged with 25 grams styrene to which was added 200 ppm DNPC. The flasks were fitted with magnetic stirrers and septum closures and heated in a stirred oil bath to 138C plus or minus 2C. The first flask was purged with approximately 3 ml/min air run beneath the liquid surface during the period of distillation. The second flask was run under a nitrogen blanket. After two hours the samples were tested for the degree of styrene polymerization as a check, by measuring the changes in refractive index. As a check, occasionally the monomer was stripped off and the remaining polymer weighed. A final polymer yield of 14.94% resulted in the first flask, ~~
whereas a final polymer yield of 18.24% resulted in Flask 2, indicating the superior inhibitory effectiveness at high temperature of the phenylenediamine/DNPC co-inhibitor system over the DNPC alone.
Example 2 A 100 ml reaction flask was charged with 25 grams styrene to which was added 100 ppm DNPC and 90 ppm TBC.
The flask was fitted with a magnetic stirrer and septum ,;
closure and heated in a stirred oil bath to 1t8C plus or minus 2C. The flask was purged with 1-2 ml/minute of air run beneath the liquid surface during the period of 30 heating. The following results were obtained: ~
r t , ",, 1~
~.' time (minutes) % polymerization _______ O O
0.34 120 0.42 5 150 0.58 180 0.75 210 1.23 -Comparison Exampl'e 2A
__ __ _ 10A 100 ml flask was charged with 25 grams styrene to which was added 100 ppm DNl?C. The procedure of Example 2 was followed and the following results were obtained:
time (minutes) % polymerization O O
1560 0.50 120 12.52 (DNPC
consumed) ~,.
Comparison Example 2B
20A 100 ml flask was charged with 25 grams styrene ,~.
to which was added 90 ppm TBC. The procedure of Example 2 ~:-was followed and the following results were obt~ained:
time (minutes) _polymerization O O
2560 1.15 120 1.71 ,~
150 1.71 1~30 2.60 210 9.29 30 The results of Example 2 and Comparison Examples 2A and 2B
l9 :~224811 indicate the increased effectiveness of the DNPC/TBC
co-inhibitor composition at lower temperatures over DNPC or TBC alone.
S Example 3 A 12" diameter pilot plant fractionation column packed with Norton Intalox Packing was utilized to distill a 1:1 mixture of ethylbenzene and styrene. The column had a continuous feed and overhead draw to simulate a 10 conventional recycle column. 300 ppm of DNPC (based on styrene content) and 200 ppm of Flexzone 4L (based on styrene content) was introduced into the column. Air was S
introduced into the column at a rate of 1.2 liters/minute.
The reboiler temperature was maintained at 118C. sOttoms 15 were drawn off every 30 to 60 minutes to maintain a constant reboiler level. At hourly intervals, the feed rate, overhead rate, column temperature profile, reflux ratio and overhead pressure were recorded. At 2 hour intervals, bottom and overhead samples were collected. At 20 6 to 8 hour intervals, aldehyde and peroxide content in the overhead were determined. The percent polymer in the fL~
bottoms was determined by vacuum evaporating a portion of the bottoms to dryness, placing a portion of tne bottoms product in a flask, heating the flask to drive off the 25 monomer, and then weighing the remaining amount which comprises polymer.
The following results were obtained:
Polymer Yield: 0-0.21%
Aldehydes: 181-427 ppm Peroxides: 13-25 ppm i224811 As a further test, the oxygen rate was decreased from 0.50 to 0.25 liters/minutes, then to 0.10 liters/minutes; the polymer yield ranged from 0.24 to 0.36%.
. 5 P:
Rxample 4 _ The procedure of Example 3 was followed utilizing 300 ppm DNPC and 200 ppm TBC. The reboiler temperature was maintained at 118C.
The following results were obtained:
Polymer Yield: 0.80-1.22%
Aldehydes: 220-420 ppm Peroxides: 25-141 ppm As a further test, the oxygen flow rate was 15 decreased from 0.50 to 0.25 liter/min then to 0.10 liter/min; the polymer yield steadily increased from 1.29 to 2.09%. E
.~
Comparison Example 3/4 ___ . . ...
The procedure oE Example 3 was followed except no air was introduced to the column and 500 ppm DNPC alone was utilized as an inhibitor. The reboiler was maintained at 118C. The polymer yield ranged from 3.97 to 4.25%.
Example 5 The procedure of Example 3 was followed utilizing 300 ppm DNPC and 200 ppm Flexzone 4L (the same concentrations used at 118C in Example 3). The reboiler temperature was maintained at 132C.
The following results were obtained:
` 21 i224811 Polymer Yield: 0.80-1.22%
Aldehydes: 280-346 ppm Peroxides: 48-80 ppm As a further test, the oxygen flow rate was decreased from 0.50 to 0.25 liter/min, then to 0.10 liter/min; as a result the polymer yield increased slightly from 1.24 to 1.47%.
Example 6 ._ The procedure of Example 3 was followed utilizing 600 ppm DNPC and 400 ppm TBC. (Double the concentrations used at 118C in Example 4.) Reboiler temperature was ~
maintained at 132C. r The following results were obtained:
Polymer Yield: 1.01-1.36~
Aldehydes: 310-440 ppm Peroxides: 107-167 ppm As a further test, the oxygen flow rate was decreased from 0.50 to 0.25 liter/min, then to 0.10 20 liter/min; as a result the polymer yield steadily increased .
from 1.57 to 2.92%.
;.
Comparison Example 5/6 ________ The procedure of Example 3 was followed utilizing 1000 ppm DNPC alone as an inhibitor. (Double the concentration of DNPC used at 118C in Comparison Example 3/4.) The following results were obtained:
Polymer Yield: 2.70-3.00%
r .~, Aldehydes: 220-260 ppm Peroxides: 49-96 ppm While the present invention has been described in various preferred embodiments and illustrated by numerous examples, a skilled artist will appreciate that various modifications, substitutions, omissions and changes may be made without departing from the spirit thereof.
addition, the distillation apparatus may be operated at a higher temperature and pressure than when using conventional inhibitors thereby allowing a higher rate of 10 distillation throughput.
Further objects, features, and advantages of the invention will become apparent from the detailed c description which follows and from the claims.
15 Brief-Description of the Drawings Fig. 1 is a schematic diagram of one embodiment of the process of the present invention utilizing a three column distillation train, and Fig. 2 is a schematic diagram of another 20 embodiment of the process of the present invention ~T
utilizing direct injection of the vinyl aromatic feed into the recycle column. r ~;:
Detailed Desc_ ptlon of the Preferred Embodiment _ _ _ ~ _ The present invention employs 2,6-dinitro-p-cresol, hereinafter referred to as DNPC, and a phenylenediamine derivative in the presence of oxygen, as a polymerization co-inhibitor composition during the heating of vinyl aromatic compounds.
The phenylenediamine of the present invention has , ~
l224all the formula: -R1 - N - ~ - N - R2 wherein R1 is an alkyl group, aryl group or hydrogen, and R2 is an alkyl group, aryl group, or hydrogen. It is ~-preferred that the allcyl groups of R1 and R2 respectively contain from 1 to 12 carbons inclusive.
Examples of such preferred p'nenylenediamine derivatives include p-phenylenediamine, N, N'dimethyl phenylenediamine, N, N'-diethylphenylenediamine, N, N'-Bis~1,4-dimethylpentyl) -p-phenylenediamine, and N-4-methyl-2-pentyl-N'-phenyl-p- ~K' phenylenediamine.
It should be noted that N, N'-Bis (1, 4-dimethylpentyl)-p-phenylenediamine and N-4-methyl-2-pentyl-N'-phenyl-p-phenylenediamine are particularly preferred; however, N, N'-Bis (1, 4-dimethylpentyl)-p-phenylenediamine is the most preferred.
The distillation techniques of the present 20 invention are suitable for use in virtually any type of separation of a readily polymerizable vinyl aromatic compound from a mixture where the compound is subjected to ~-temperatures above room temperature. By polymerization inhibitor it is meant that unwanted polymerization of the vinyl aromatic monomer is prevented at elevated temperatures such as in a distillative apparatus. .' Increasing the temperature in the apparatus has the -advantages of a higher distillation rate, however, this increased temperature can cause a higher rate of polymerization which is counterbalanced by the introduction ~2248~1 -'~
of the inhibitor of the present invention. In its most useful application, the composition is applied to a distillation mixture of vinyl aromatic compounds selected from the group consisting of styrene, substituted styrene 5 such as alpha-methyl styrene, divinylbenzene, vinyl toluene, vinyl naphthalene, and the polyvinylbenzenes.
This group is understood to include all structural isomers of the aforementioned compounds. The preferred application of the present invention relates to the distillation of 10 crude styrene.
The amounts of polymerization inhibitor added may vary over a wide range depending upon the conditions of b~;
distillation. Generally, the degree of stabilization is r proportional to the amount of inhibitor added. In 15 accordance with the present invention, it has been found, based on vinyl aromatic feed to the B-T column 10 or the recycle column 90, that a phenylenediamine concentration generally between about 50 ppm and 2000 ppm and a DNPC
concentration between about 100 ppm and 2000 ppm have 20 generally produced suitable results, depending primarily r-upon the temperature of the distillative mixture and the degree of inhibition desired. Preferably however, the r-phenylenediamine lnhibitor o~ the present invention is used in concentration from about 50 ppm to about 1000 ppm and the DNPC concentration is from about 250 ppm to about 1000 ppm. The preferred ppm ratio of phenylenediamine to DNPC
is 2:3. There is no particular order for mixing the compounds of the present invention. In one particular embodiment tl-ey are added together at atmospheric 30 temperature and pressure outside the distillation train and r 8 ~Z;~481~
injected therein. The distillation technique of the present invention is suitable for use in virtually any type of distillative separation of a readily polymerizable vinyl aromatic compound from a mixture wherein the vinyl aromatic compound is subject to temperatures above room temperature.
Oxygen must be added to the system in order for the phenylenediamine co-inhibitor to work properly. Oxygen is added separately into the system to achieve a greater concentration of oxygen in the required area. The oxygen employed in the present invention may be in the form of oxygen or an oxygen-containing gas. If an oxygen-containing gas is employed, the remaining F-constituents of the gas must be inert to the vinyl aromatic compound under the distillation conditions. The most useful and least expensive source of oxygen is air, which is preferred for the present invention. The amount of oxygen may vary widely, but generally it is desirable to use that amount found in air.
Referring to the drawings, FIG. 1 illustrates a conventional styrene distillation train comprising a benzene-toluene fractionation column 10, referred to in the r industry as a B-T column, an ethylbenzene or recycle column 12, and a styrene or finishing column 14. It should be 25 ~oted that the operational principles of the present distillation method are highly suitable for use, with minor modifications, with other distillation equipment used in the purification of other vinyl aromatic compounds. As shown in FIG. 1, a crude styrene feed is introduced into 30 the intermediate portion of B-T column 10 through feedline r ~, 16. B-T column lO may be of any suitable design known to one skilled in the art and may contain any suitable number of vapor-liquid contacting devices, such as bubble cap trays, perforated trays, etc. Usually, however, column 10 5 contains less than forty distillation trays. Column 10 is also equipped with a suitable reboiler 18 for supplying heat thereto. Temperature of reboiler 18-is generally from about 190F to about 250F.
W'nile most of the polymer is formed in the 10 ethylbenzene or recycle column 12, a small but significant amount of the total polymer formed during distillation is formed in the B-T column 10. Accordingly, a polymerization inhibitor is desirable within this column. To prevent polymerization in the B-T column 10, 2, 6-dinitro-p-cresol 15 hereinafter referred to as DNPC, is introduced into the B-T
column 10 as a separate stream through line 20, or it may be incorporated into the crude styrene feed flowing through line 16. To facilitate the process, the phenylenediamine inhibitor may also be introduced into the B-T column 10 20 through line 20 or it may be incorporated into the crude ~-styrene feed flowing through line 16. Although the ?
phenylenediamine inhibitor provides little or no inhibition ~' in B-T column 10 due to lack of oxygen, it is transported with the B-T bottoms through line 24 to the recycle column 25 12 where it acts as the primary inhibitor therein. When the DNPC and/or phenylenediamine polymerization inhibitor are added to the B-T column 10 as a separate stream they -are preferably dissolved in a volatile aromatic hydrocarbon diluent such as ethylbenzene. The position of the 30 inhibitor feedline 20 will normally be intermediate to B-T
' ~22481~
column 10 in order to achieve an inhibitor distribution which is nearly coincident with the distribution of the readily polymerizable vinyl aromatic compound within the column 10.
Under the distillation conditions imposed in column 10, an overhead stream comprising benzene and toluene is removed via line 22. These low boiling aromatic hydrocarbons are subsequently condensed and passed to storage for further use. The bottoms product in the B-T
column comprising styrene, ethylbenzene, inhibitor and tar, serves as a charge to the recycle or ethylbenzene column 12. The bottoms product is introduced into the intermediate portion of ethylbenzene column 12 by means of line 24 and pump 26. The recycle column 12 may be of any suitable design known to those skilled in the art and may contain from 40 to 100 trays. Preferably, however, the recycle column is of the parallel path design.
Additionally, it is also preferable that the recycle column contain a large number of trays, as many as 72, in order to achieve a proper separation between the similar boiling styrene and ethylbenzene. The B-T bottoms are preferably introduced into the intermediate portion of the recycle column 12.
A certain amount of inhibitor protection within the ethylbenzene column 12 is provided by the phenylenediamine composition introduced intermediate to column 12 through line 2~, together with the B-T bottoms fraction through line 30, or with the DNPC into the B-T
column through line 20. It is necessary to add air only to 30 recycle column 12 due to DNPC protection in the rest of the ~r~
.
distillation train. In the recycle column 12 a more effective polymerization inhibitor is necessary due to the high temperatures up to 150C therein which are desirable in that column for a more energy efficient distillation.
5 By obtaining temperatures of at least 118C and preferably 130C or more, low pressure steam may bè recovered from an overhead condensor (not shown) on recycle column 12.
Oxygen is introduced into reboilers 32 through air purge lines 36 and 38 respectively. Alternatively, 10 oxygen may be introduced into reboilers 32 through sump or boot 40 via line 42 if there is sufficient air pressure/volume to reach the reboilers through line 43.
For the phenylenediamine to be effective, an equilibrium amount of oxygen is dissolved in the liquid phase of the 15 column 12; however, the amount of oxygen introduced should not exceed that amount which could cause explosion therein.
The oxygen is dispersed throughout the column 12 where it works in conjunction with the phenylenediamine to inhibit polymerization therein. The amount of oxygen necessary 20 will depend on the number and spacing of oxygen inlets around column 12, and how efficiently oxygen and liquid hydrocarbon are mixed therein. Therefore in practical application, the oxygen flow is increased as long as polymer yields are reduced, limited by the amount of oxygen 25 which would yield an explosive mixture. Complete dispersion of air throughout column 12 does not generally ;~
occur, therefore the presence of DNPC therein works as a r co-inhibitor at those locations where the effectiveness of the phenylenediamine is diminished due to the absence of 30 air. Therefore, the DNPC continues providing ~224~
.
-~..
polymerization inhibition in those areas of recycle column 12 where there is an absence of air thereby providing an overall higher polymerization inhibition effectiveness than would have been achieved if only phenylenediamine had been present by itself or in combination with other oxygen - activated inhibitors.
Surprisingly, it has been found that not only is DNPC compatible with the phenylenediamine, DNPC also works as a polymerization inhibitor in the presence of air as 10 well as in its ~bsence. DNPC therefore also provides inhibitor protection in addition to that provided by phenylenediamine in those areas of the recycle column where there is effective air dispersion. It has been found, however, that when DNPC alone is used as an inhibitor in 15 the presence of air, the DNPC is exhausted more rapidly.
This may be due to the fact that more polymer free radicals are generated in the presence of air. Therefore, to maintain effective DNPC/oxygen polymerization inhibition f over an extended period of time it is necessa~y to add more 20 DNPC inhibitor. Additional DNPC and phenylenediamine protection may be obtained by the recycle of tar conl:~ining DNPC/phenylenediamine back into recycle column 12 as explained in U.S. Patent No. 4,272,344.
Alternatively, the phenylenediamine inhibitor may 25 be introduced with the DNPC inhibitor into the B-T column 10 through line 20 as a DNPC/phenylenediamine mixture.
There is no preferred order of mixing these together. A
random order of mixing at ambient temperature and pressure will achieve suitable results. A portion of the DNPC/phenylenediamine inhibitor travels through the B-T
column to the recycle column 12 together with the B-T
bottoms product.
The bottoms portion from recycle column 12 comprisinq styrene inhibitor and tar is withdrawn from the reboiler area of recycle column 12 through line 60. The recycle bottoms is then fed by pump 62 into the intermediate portion of the styrene or finishing column 14 through line 64. Optionally, the bottoms material may be introduced into the lower portion of the styrene column 14 through line 66.
The finishing column 14 may be of any suitable ~;
design known to those skilled in the art. A typical column will contain for example, about 24 distillation trays.
Reboilers 68 are connected to sump 76 through line 78 and pump 80. Reboiler 68 is generally operated at a temperature from about 82C to about 121C. Generally, inhibitor protection is adequately provided in this column by the DNPC and phenylenediamine inhibitor present in the 20 bottoms feed. A portion of the tar from column 14 may be r-recycled at least back into the ethylbenzene column 12 through line 88 in order to further supplement the DNPC
within the system. ?`
The high purity styrene overhead product is withdrawn through line 74 from styrene column 14. The styrene column bottoms product, composed of polystyrene, undistilled styrene, heavy by-products and the DNPC/
phenylenediamine co-inhibitor, is withdrawn off the reboiler recirculating line 78 and directed to a flash pot 30 54 via line 85 for further processing. In the flash pot 84 r ~224811 ,~, residual styrene is removed from the bottoms of the styrene column and recycled back thereto through line 86. The tar produced in the flash pot 84 is withdrawn from the system on a continuous bas-s through line 83 or recycled back to the recycle column 12 or B-T column 10 through line 88.
FIG. 2 illustrates the application of the distillation method of the present invention to another typical distillation train. A styrene feed is introduced through line 91 into the intermediate portion of recycle 10 column 90, which is preferably of the parallel distillation path design. Line 92 supplies the phenylenediamine inhibitor to the recycle column 90. Heat is supplied to the bottoms of column 90 by means of reboilers 94. Oxygen r is introduced into reboilers 94 through air purge lines 96 15 and 98. Oxygen may be introduced directly into reboilers 94 through sump or boot 100 and line 101 if there is sufficient oxygen pressure and volume to reach the ~-reboilers through lines 97. In B-T column 122, benzene and toluene are withdrawn as an overhead fraction through line 20 123 and are subsequently condensed for further use. An ethylbenzene bottoms product is withdrawn through line 124 i, and is recycled for further use. Reboiler 126 provides B-T rb column 122 with the necessary heat for distillation.
The recycle bottoms product comprising 25 polystyrene, undistilled styrene, heavy by-products, phenylenediamine and DNPC is withdrawn from recycle column 1-90 through line 128. The impure styrene fraction is then charged to the upper portion of the styrene column 130 by means of pump 132 and line 133. Optionally, impure styrene 30 may be introduced into the lower region of styrene column ~:
12~481~
100 through line 134. A reboiler circuit comprising reboiler 136 and pump 138 is attached to the styrene or finishing column 130 for supplying the necessary heat thereto. DNPC is preferably introduced with the 5 phenylenediamine into recycle column 90 through line 92.
The purified styrene overhead product is withdrawn through line 144.
Reboilers 148 are connected to finishing column sump 136 through recirculating line 145 and pump 150. The 10 finishing column bottoms produce is withdrawn off reboiler recirculating line 145 for further processing in flash pot 146. Flash pot 146 recycles back into finishing column 14 ~;
through line 149. The tar produced during the distillation r process is withdrawn through line 152 or recycled back to 15 the distillation train through line 154.
In another embodiment of the present invention, an effective amount of 4-tert-butylcatechol is introduced into the aforementioned distillation trains through recycle columns 12, 90 in place of the phenylenediamine to act as a 20 co-inhibitor with DNPC. It has been found that DNPC and 4-tert-butylcatechol, hereinafter referred to as TBC, is an efficient co-inhibitor system in the presence of air at 2 temperatures up to 140C. An effective amount of TBC, based on vinyl aromatic feed to the B-T column 10 or the recycle column 90, is from about 50 ppm to about 2000 ppm;
a preferred amount of TBC is from about 200 ppm to about 1000 ppm. The preferred ppm ratio of TBC to DNPC iS 2 to 3.
Use of the compositions and methods of the present invention enables a distillation apparatus to operate , . .
r :.:
,~, with an increased throughput rate as opposed to conventional prior art processes since higher temperatures are permitted in the recycle column due to introduction of effective amounts of DNPC/phenylenediamine or DNPC/TBC inhibitor composition. In addition, the DNPC inhibitor may be used in the remaining fractionation columns to insure effective polymerization inhibition where lower temperatures and absence of air are encountered. Therefore, higher distillation temperatures and higher pressure may be utilized without the formation of objectionable amounts of polymer. In this manner, the rate of distillation may be increased without increasing the amount of polymerization --which was previously experienced in the conventional distillation procedures.
In addition by optimizing the distribution of the DNPC/phenylenediamine or DNPC/TBC inhibitor within the recycle column and by optimizing the distribution of DNPC
inhibitor in the remaining fractionation columns of the ~~
distillation train, greater temperatures may be achieved in the recycle column than in conventional distillation procedures to permit more efficient energy recovery therefrom. ,-In order to more fully describe the present invention, the following examples are presented which are intended to be illustrative and not in any sense limitative of the invention.
Example 1 Two 100 ml reaction flasks were prepared. A
30 first (1) was charged with 25 grams styrene to which was i~-12248~
added lO0 ppm DNPC and 50 ppm Flexone 4L, (a trademark of Uniroyal Chemical, Flexone 4L having the chemical formula N, N'-Bis (1,4-dimethylpentyl)-p-phenylenediamine as discussed in the Uniroyal Material Safety Sheet covering Flexone 4L). A second (2) flask was charged with 25 grams styrene to which was added 200 ppm DNPC. The flasks were fitted with magnetic stirrers and septum closures and heated in a stirred oil bath to 138C plus or minus 2C. The first flask was purged with approximately 3 ml/min air run beneath the liquid surface during the period of distillation. The second flask was run under a nitrogen blanket. After two hours the samples were tested for the degree of styrene polymerization as a check, by measuring the changes in refractive index. As a check, occasionally the monomer was stripped off and the remaining polymer weighed. A final polymer yield of 14.94% resulted in the first flask, ~~
whereas a final polymer yield of 18.24% resulted in Flask 2, indicating the superior inhibitory effectiveness at high temperature of the phenylenediamine/DNPC co-inhibitor system over the DNPC alone.
Example 2 A 100 ml reaction flask was charged with 25 grams styrene to which was added 100 ppm DNPC and 90 ppm TBC.
The flask was fitted with a magnetic stirrer and septum ,;
closure and heated in a stirred oil bath to 1t8C plus or minus 2C. The flask was purged with 1-2 ml/minute of air run beneath the liquid surface during the period of 30 heating. The following results were obtained: ~
r t , ",, 1~
~.' time (minutes) % polymerization _______ O O
0.34 120 0.42 5 150 0.58 180 0.75 210 1.23 -Comparison Exampl'e 2A
__ __ _ 10A 100 ml flask was charged with 25 grams styrene to which was added 100 ppm DNl?C. The procedure of Example 2 was followed and the following results were obtained:
time (minutes) % polymerization O O
1560 0.50 120 12.52 (DNPC
consumed) ~,.
Comparison Example 2B
20A 100 ml flask was charged with 25 grams styrene ,~.
to which was added 90 ppm TBC. The procedure of Example 2 ~:-was followed and the following results were obt~ained:
time (minutes) _polymerization O O
2560 1.15 120 1.71 ,~
150 1.71 1~30 2.60 210 9.29 30 The results of Example 2 and Comparison Examples 2A and 2B
l9 :~224811 indicate the increased effectiveness of the DNPC/TBC
co-inhibitor composition at lower temperatures over DNPC or TBC alone.
S Example 3 A 12" diameter pilot plant fractionation column packed with Norton Intalox Packing was utilized to distill a 1:1 mixture of ethylbenzene and styrene. The column had a continuous feed and overhead draw to simulate a 10 conventional recycle column. 300 ppm of DNPC (based on styrene content) and 200 ppm of Flexzone 4L (based on styrene content) was introduced into the column. Air was S
introduced into the column at a rate of 1.2 liters/minute.
The reboiler temperature was maintained at 118C. sOttoms 15 were drawn off every 30 to 60 minutes to maintain a constant reboiler level. At hourly intervals, the feed rate, overhead rate, column temperature profile, reflux ratio and overhead pressure were recorded. At 2 hour intervals, bottom and overhead samples were collected. At 20 6 to 8 hour intervals, aldehyde and peroxide content in the overhead were determined. The percent polymer in the fL~
bottoms was determined by vacuum evaporating a portion of the bottoms to dryness, placing a portion of tne bottoms product in a flask, heating the flask to drive off the 25 monomer, and then weighing the remaining amount which comprises polymer.
The following results were obtained:
Polymer Yield: 0-0.21%
Aldehydes: 181-427 ppm Peroxides: 13-25 ppm i224811 As a further test, the oxygen rate was decreased from 0.50 to 0.25 liters/minutes, then to 0.10 liters/minutes; the polymer yield ranged from 0.24 to 0.36%.
. 5 P:
Rxample 4 _ The procedure of Example 3 was followed utilizing 300 ppm DNPC and 200 ppm TBC. The reboiler temperature was maintained at 118C.
The following results were obtained:
Polymer Yield: 0.80-1.22%
Aldehydes: 220-420 ppm Peroxides: 25-141 ppm As a further test, the oxygen flow rate was 15 decreased from 0.50 to 0.25 liter/min then to 0.10 liter/min; the polymer yield steadily increased from 1.29 to 2.09%. E
.~
Comparison Example 3/4 ___ . . ...
The procedure oE Example 3 was followed except no air was introduced to the column and 500 ppm DNPC alone was utilized as an inhibitor. The reboiler was maintained at 118C. The polymer yield ranged from 3.97 to 4.25%.
Example 5 The procedure of Example 3 was followed utilizing 300 ppm DNPC and 200 ppm Flexzone 4L (the same concentrations used at 118C in Example 3). The reboiler temperature was maintained at 132C.
The following results were obtained:
` 21 i224811 Polymer Yield: 0.80-1.22%
Aldehydes: 280-346 ppm Peroxides: 48-80 ppm As a further test, the oxygen flow rate was decreased from 0.50 to 0.25 liter/min, then to 0.10 liter/min; as a result the polymer yield increased slightly from 1.24 to 1.47%.
Example 6 ._ The procedure of Example 3 was followed utilizing 600 ppm DNPC and 400 ppm TBC. (Double the concentrations used at 118C in Example 4.) Reboiler temperature was ~
maintained at 132C. r The following results were obtained:
Polymer Yield: 1.01-1.36~
Aldehydes: 310-440 ppm Peroxides: 107-167 ppm As a further test, the oxygen flow rate was decreased from 0.50 to 0.25 liter/min, then to 0.10 20 liter/min; as a result the polymer yield steadily increased .
from 1.57 to 2.92%.
;.
Comparison Example 5/6 ________ The procedure of Example 3 was followed utilizing 1000 ppm DNPC alone as an inhibitor. (Double the concentration of DNPC used at 118C in Comparison Example 3/4.) The following results were obtained:
Polymer Yield: 2.70-3.00%
r .~, Aldehydes: 220-260 ppm Peroxides: 49-96 ppm While the present invention has been described in various preferred embodiments and illustrated by numerous examples, a skilled artist will appreciate that various modifications, substitutions, omissions and changes may be made without departing from the spirit thereof.
Claims (19)
1) A process for inhibiting the polymerization of a vinyl aromatic compound, comprising subjecting the vinyl aromatic compound when heated to effective amounts of 2,6-dinitro-p-cresol and a phenylenediamine, respectively, in the presence of oxygen, the phenylenediamine having the formula wherein R1 and R2 are alkyl, aryl or hydrogen.
2) The process of Claim 1 wherein the vinyl aromatic compound is selected from the group consisting of styrene, substituted styrene, divinylbenzene, vinyl toluene, vinyl naphthalene, the polyvinylbenzenes, and structural isomers thereof.
3) The process of Claim 1 wherein the alkyl groups contain from 1 to 12 carbons respectively.
4) The process of Claim 1 wherein the vinyl aromatic compound is heated to a temperature up to 150°C
5) The process of Claim 1 wherein a) the effective amount of 2,6-dinitro-p-cresol is from about 100 ppm to about 2000 ppm; and b) the effective amount of phenylenediamine is from about 50 ppm to about 2000 ppm.
6) The process of Claim 1 wherein the heating of the vinyl aromatic compound occurs during distillation of said compound.
7) A process for inhibiting the polymerization of a vinyl aromatic compound, comprising subjecting the vinyl aromatic compound when heated to effective amounts of 2,6-dinitro-p-cresol and 4-tert-butylcatechol respectively, in the presence of oxygen.
8) The process of Claim 7 wherein the vinyl aromatic compound is selected from the group consisting of styrene, substituted styrene, divinylbenzene, vinyl toluene, vinyl naphthalene, the polyvinylbenzenes, and structural isomers thereof.
9) The process of Claim 7 wherein the vinyl aromatic compound is heated to a temperature up to of 140°C.
10) The process of Claim 7 wherein a) the effective amounts of 2,6-dinitro-p-cresol is from about 100 ppm to about 2000 ppm based on vinyl aromatic going to purification; and b) the effective amount of 4-tert-butylcatechol is from about 50 ppm to about 2000 ppm based on vinyl aromatic feed.
11) A composition for inhibiting polymerization of a vinyl aromatic compound in the presence of oxygen, comprising a) an effective amount of 2,6-dinitro-p-cresol; and b) an effective amount of a phenylenediamine having the formula wherein R1 and R2 are alkyl, aryl or hydrogen.
12) The composition of Claim ll wherein the vinyl aromatic compound is selected from the group consisting of styrene, substituted styrene, divinylbenzene, vinyl toluene, vinyl naphthalene, the polyvinylbenzenes, and structural isomers thereof.
13) The composition of Claim 11 wherein the alkyl groups contain from 1 to 12 carbons respectively.
14) The composition of Claim 11 wherein:
a) the 2,6-dinitro-p-cresol is present in the amount from about 100 ppm to about 2000 ppm, and b) the phenylenediamine is present in the amount from about 50 ppm to about 2000 ppm.
a) the 2,6-dinitro-p-cresol is present in the amount from about 100 ppm to about 2000 ppm, and b) the phenylenediamine is present in the amount from about 50 ppm to about 2000 ppm.
15) A composition for inhibiting polymerization of a vinyl aromatic compound in the presence of oxygen, comprising a) an effective amount of 2,6-dinitro-p-cresol; and b) an effective amount of 4-tert-butylcatechol.
16) The composition of Claim 15 wherein the vinyl aromatic compound is selected from the group consisting of styrene, substituted styrene, divinylbenzene, vinyltoluene, vinyl naphthalene, the polyvinylbenzenes, and structural isomers thereof.
17) The composition of Claim 15 wherein:
a) the 2,6-dinitro-p-cresol is present in the amount from about 100 ppm to about 2000 ppm; and b) the 4-tert-butylcatechol is present in the amount from about 50 ppm to about 2000 ppm.
a) the 2,6-dinitro-p-cresol is present in the amount from about 100 ppm to about 2000 ppm; and b) the 4-tert-butylcatechol is present in the amount from about 50 ppm to about 2000 ppm.
18) A process for inhibiting the polymerization of a vinyl aromatic compound when heated to effective amounts of 2,6-dinitro-p-cresol and a compound selected from the group 4-tert-butylcatechol, and a phenylenediamine, respectively, in the presence of oxygen, said phenylenediamine having the formula wherein Rl and R2 are alkyl, aryl or hydrogen.
19) A composition for inhibiting polymerization of a vinyl aromatic compound in the presence of oxygen, comprising a) an effective amount of 2,6-dinitro-p-cresol; and b) an effective amount of a compound selected from the group 4-tert-butylcatechol and a phenylene-diamine, said phenylenediamine having the formula wherein R1 and R2 are alkyl, aryl or hydrogen.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US483,978 | 1983-04-11 | ||
| US483,976 | 1983-04-11 | ||
| US06/483,976 US4468343A (en) | 1983-04-11 | 1983-04-11 | Polymerization co-inhibitors for vinyl aromatic compounds |
| US06/483,978 US4466905A (en) | 1983-04-11 | 1983-04-11 | Polymerization inhibition process for vinyl aromatic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224811A true CA1224811A (en) | 1987-07-28 |
Family
ID=27047805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451559A Expired CA1224811A (en) | 1983-04-11 | 1984-04-09 | Polymerization inhibition process for vinyl aromatic compounds |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0680085B2 (en) |
| CA (1) | CA1224811A (en) |
| DE (1) | DE3413642C2 (en) |
| FR (1) | FR2543944B1 (en) |
| GB (1) | GB2138010B (en) |
| IT (1) | IT1196078B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4774374A (en) * | 1987-06-12 | 1988-09-27 | Uniroyal Chemical Company, Inc. | Stabilized vinyl aromatic composition |
| US4915873A (en) * | 1988-01-22 | 1990-04-10 | Uniroyal Chemical Company, Inc. | Polymerization inhibitor composition for vinyl aromatic compounds |
| AU658376B2 (en) * | 1990-10-18 | 1995-04-13 | Uniroyal Chemical Company, Inc. | Benzoquinoneimines as vinyl aromatic polymerization inhibitors |
| US6342648B1 (en) * | 1999-09-30 | 2002-01-29 | Baker Hughes Incorporated | Methods and compositions for inhibiting vinyl aromatic monomer polymerization |
| JP2006176417A (en) * | 2004-12-21 | 2006-07-06 | Hakuto Co Ltd | Method for controlling polymerization of aromatic vinyl compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE932487C (en) * | 1937-09-11 | 1955-09-01 | Int Standard Electric Corp | Process for the temporary stabilization of styrene against polymerization with the addition of stabilizers |
| US2867672A (en) * | 1955-08-29 | 1959-01-06 | Shell Dev | Method of minimizing styrene polymerization during storage |
| JPS4972219A (en) * | 1972-11-18 | 1974-07-12 | ||
| JPS5729692B2 (en) * | 1974-09-17 | 1982-06-24 | ||
| US3988212A (en) * | 1975-03-21 | 1976-10-26 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| US4061545A (en) * | 1976-02-19 | 1977-12-06 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| US4105506A (en) * | 1977-02-24 | 1978-08-08 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| US4132601A (en) * | 1977-11-23 | 1979-01-02 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| US4132602A (en) * | 1977-11-23 | 1979-01-02 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| US4252615A (en) * | 1978-07-18 | 1981-02-24 | Cosden Technology, Inc. | Polymerization inhibitor for vinyl aromatic compounds |
| GB2069523B (en) * | 1979-04-03 | 1983-03-23 | Cosden Technology | Distillation of vinyl aromatic compounds |
| DE2931553A1 (en) * | 1979-08-03 | 1981-02-26 | Basf Ag | METHOD FOR STABILIZING MONOMERIC ACRYLIC ACID ESTERS AGAINST EARLY POLYMERIZATION |
| US4343956A (en) * | 1980-03-13 | 1982-08-10 | Ethyl Corporation | Stabilization dibromostyrene |
| US4341600A (en) * | 1981-04-06 | 1982-07-27 | Cosden Technology, Inc. | Polymerization inhibitor for vinyltoluene |
-
1984
- 1984-04-09 CA CA000451559A patent/CA1224811A/en not_active Expired
- 1984-04-10 FR FR8405644A patent/FR2543944B1/en not_active Expired
- 1984-04-10 JP JP59070176A patent/JPH0680085B2/en not_active Expired - Lifetime
- 1984-04-11 GB GB08409407A patent/GB2138010B/en not_active Expired
- 1984-04-11 DE DE3413642A patent/DE3413642C2/en not_active Expired - Lifetime
- 1984-04-11 IT IT20487/84A patent/IT1196078B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE3413642C2 (en) | 1999-09-09 |
| IT8420487A0 (en) | 1984-04-11 |
| JPH0680085B2 (en) | 1994-10-12 |
| FR2543944B1 (en) | 1987-02-13 |
| GB2138010A (en) | 1984-10-17 |
| FR2543944A1 (en) | 1984-10-12 |
| IT1196078B (en) | 1988-11-10 |
| GB2138010B (en) | 1986-09-10 |
| GB8409407D0 (en) | 1984-05-23 |
| JPS59206419A (en) | 1984-11-22 |
| DE3413642A1 (en) | 1984-10-11 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |