Amine and nitroxide based additive composition for control and inhibition of polymerization of styrene, and method of use thereof.
Abstract
The present invention relates to an additive composition for the control and inhibition of the polymerization of aromatic vinyl monomers, including styrene, comprising (a) one or more nitroxide (ie, nitroxyl) compounds; said composition characterized in that it further comprises one or more of (b) aliphatic amines, wherein said aliphatic amine is selected from the group consisting of tertiary amines, secondary amines and primary amines. In a particular embodiment, the present invention also relates to a method for using the present composition provided. In another embodiment, the present invention also relates to a method for controlling and inhibiting the polymerization of aromatic vinyl monomers, including styrene, using the present composition provided. In still another embodiment, the present invention also relates to a method for the preparation of the present composition provided.

Term
6.2 yearsleft in the term
Expires 21 November 2032.
- Priority
- Filed
- Granted
- Today
- Expires
22 claims: 17 independent, 5 dependent
- 1CLAIMS J p T | ' <' REIVINDICACIONES J p T|‘ < ' INSTITUTO MEXICANO MEXICAN INSTITUTE 1. An additive composition for corfW® yes ^ ± p's ^ gs? 1. Una composición de aditivo para el corfW®sí^± p's^gs? la inhibición de la polimerización de monómoroo idm, νί,ηί,,ΐο aromáticos, incluyendo estireno, que comprende:the inhibition of the polymerization of monomoroo idm, νί, ηί ,, ΐο aromatics, including styrene, comprising: (a) uno o más compuestos de nitróxido (es decir, nitroxilo);y caracterizada en que dicha composición comprende además una o más de (b) aminas, en donde dicha amina es una amina alifática, y en donde la amina alifática es una amina terciaria. one or more composed of nitroxide (it is say, nitroxyl);Y characterized on that said composition further understand one or more than (b) amines, where said amine is a amine aliphatic, and on where the aliphatic amine is a amine tertiary.
- 4La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 1 a 3, en donde dicha amina tratada con óxido de etileno es N,N,Ν',Ν'-Tetrakis(243 hidroxietil)etilen-diamina) (THEED). Four. The additive composition as claimed in any one of claims 1 to 3, wherein said ethylene oxide treated amine is N, N, Ν ', Ν'-Tetrakis (243 hydroxyethyl) ethylene diamine) (THEED). INSTITUTO MEXICANO DE LA PROPIEC'AD INDUSTRIAL MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
- 5The additive composition as claimed in any one of claims 1 to 4, wherein said propylene oxide treated amine is N, N, Ν ', N'-Tetrakis (2-hydroxypropyl) ethylene diamine). 5. La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 1 a 4, en donde dicha amina tratada con óxido de propileno es N,N,Ν',N'-Tetrakis(2 hidroxipropil)etilen-diamina).
- 6The additive composition as claimed in any one of claims 1 to 5, wherein said tertiary alkyl hydroxyl amine is triethanolamine (TEA). 6. La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 1 a 5, en donde dicha amina terciaria de alquilo hidroxilo es trietanolamina (TEA).
- 7The additive composition as claimed in any of the preceding claims 1 to 6, wherein said tertiary alkyl amine is Tris [N-butylamine] (TBA). 7. La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones precedentes 1 a 6, en donde dicha amina de alquilo terciaria es Tris[N-butilamina] (TBA).
- 8An additive composition for the control and inhibition of the polymerization of vinyl aromatic monomers, including styrene, comprising:8. Una composición de aditivo para el control y para la inhibición de la polimerización de monómeros de vinilo aromáticos, incluyendo estireno, que comprende: (a) one or more nitroxide compounds (ie, nitroxyl);and characterized in that said composition further comprises (b) one or more amines, wherein said amine is an aliphatic amine, and wherein the aliphatic amine is selected from the group consisting of primary and secondary amines. (a) uno o más compuestos de nitróxido (es decir, nitroxilo);y caracterizada en que dicha composición comprende además (b) una o más aminas, en donde dicha amina es una amina alifática, y en donde la amina alifática se selecciona del grupo que consiste de aminas primarias y secundarias.
- 9The composition of 9. La composición de IMPIF '. IMPIF'. INSTITUTO MEXICANO additive as it was reeoMámadá ^ INSTITUTO MEXICANO aditivo tal como fue reeoMámadá^ Claim 8, wherein said puima-r ^ ia oo amine is selected from the group consisting of hydroxyl alkyl primary amine and alkyl primary amine. La reivindicación 8, en donde dicha amina puima-r^ia o o selecciona del grupo que consiste de amina primaria de alquilo hidroxilo y amina primaria de alquilo.
- 11La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 8 a 10, en donde dicha amina primaria de alquilo hidroxilo es monoetanolamina (MEA). eleven. The additive composition as claimed in any one of claims 8 to 10, wherein said alkyl hydroxyl primary amine is monoethanolamine (MEA).
- 14The additive composition as claimed in any one of claims 1 to 13, wherein said composition comprises:14. La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 1 a 13, en donde dicha composición comprende: approximates the weight of I) said nitroxyl compounds);aproxima®ai peso de I) dichos compuestos nitroxilo);(b) de aproximadamente 0.25% peso de (b) of about 0.25% weight of II) II) 15. 15. Either about 60% nitroxy in said amines, or additive composition mixtures as claimed in claims 1 thereof. La cualquiera de nitróxi a aproximadamente 60% en dichas aminas, o mezclas de composición de aditivo tal de las reivindicaciones 1 las mismas. as claimed in a 14, wherein said nitroxide compound (i.e. nitroxyl) is selected from the group comprising di-tert-butylnitroxyl, 1-oxyl- como fue reclamada en a 14, en donde dicho compuesto de nitróxido (es decir, nitroxilo) se selecciona del grupo que comprende de di-tert-butilnitroxil, 1-oxil- 2,2,6,6-tetramethylpiperidine, l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (or 4-Hydroxy Tempo or 4-HT), 1-oxyl- 2,2,6,6-tetrametilpiperidina, l-oxil-2,2,6,6tetrametilpiperidin-4-ol (o 4 Hidroxi Tempo o 4-HT), 1-oxil- 2.2.6.6- tetramethylpiperidin-4-one, and derivatives thereof;and di-nitroxides and derivatives comprising bis ( l-oxyl- 2.2.6.6- tetrametilpiperidin-4-ona, y derivados de los mismos;y di-nitróxidos y derivados que comprenden bis(l-oxil- 2.2.6.6- tetramethylpiperidin-4-yl) sebacate, bisj1-oxyl- 2.2.6.6- tetrametilpiperidin-4-il)sebacato, bisj1-oxil- 2.2.6.6- tetramethylpiperidin-4-yl) succinate, bis (1-oxyl- 2.2.6.6- tetrametilpiperidin-4-il)succinato, bis(1-oxil- 2.2.6.6- tetramethylpiperidin-4-yl) adipate, and mixtures thereof. 2.2.6.6- tetrametilpiperidin-4-il)adipato, y mezclas de los mismos.
- 1516. The additive composition as claimed in any one of claims 1 to 15, wherein said composition does not comprise a nitroaromatic compound. 16. La composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones 1 a 15, en donde dicha composición no comprende un compuesto nitroaromático.
- 1617. A method for the control and for the inhibition of the polymerization of vinyl aromatic monomers, ν '. including styrene, by adding the ο®η®ο® · ϊΌ <5ίι -de. 17. Un método para el control y para la inhibición de la polimerización de monómeros de vinilo aromáticos, ν'. incluyendo estireno, mediante la adición de lá ο®η®ο®·ϊΌ<5ίι -de . A jr ζ, · / - '5 ^ Un jr ζ , · /--‘5^ INSTITUTO MEXICANO ' r . .> aditivo tal como fue reclamada en cualquiera^N^^*^ 1¾^¾¾¾^ reivindicaciones precedentes 1 a 16 a 1 de monómeros, en donde dicha composición comprende:MEXICAN INSTITUTE ' r . .> additive as claimed in any ^ N ^^ * ^ 1¾ ^ ¾¾¾ ^ preceding claims 1 to 16 to 1 of monomers, wherein said composition comprises: (a) one or more nitroxide compounds (ie, nitroxyl);and characterized in that said composition further comprises one or more of (b) said amines;and said composition is added to said monomers .. ' (a) uno o más compuestos de nitróxido (es decir, nitroxilo);y caracterizada en que dicha composición comprende además una o más de (b) dichas aminas;y dicha composición es añadida a dichos monómeros..'
- 1819. A method for the use of the additive composition as claimed in any of the preceding claims 1 to 16, for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, wherein said composition comprises:19. Un método para la utilización de la composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones precedentes 1 a 16, para el control y para la inhibición de la polimerización de monómeros de vinilo aromáticos, incluyendo estireno, en donde dicha composición comprende: (a) one or more nitroxide compounds (ie, nitroxyl);and characterized in that said composition because it also comprises one or more of (b) said amines, - (a) uno o más compuestos de nitróxido (es decir, nitroxilo);y caracterizada en que dicha composición porque comprende además una o más de (b) dichas aminas, — IMPI & IMPI & and said monomers are treated with said composition y dichos monómeros son tratados con dicha compos INDUSTRIAL • ν '· »» *! »—— _____ INDUSTRIAL • ν'·»»*!»—— _____
- 2021. Un método para la preparación de la composición de aditivo tal como fue reclamada en cualquiera de las reivindicaciones precedentes 1 a 16, para el control y para la inhibición de la polimerización de monómeros de vinilo aromáticos, incluyendo estireno, en donde el método comprende:twenty-one. A method for the preparation of the additive composition as claimed in any of the preceding claims 1 to 16, for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, wherein the method comprises: (a) mezclar uno o más de dichos compuestos de nitróxido (es decir, nitroxilo), caracterizado en que dicho compuesto de nitróxido (es decir, nitroxilo) o mezcla de los mismos, se mezcla además con una o más de (b) dichas aminas. (a) mixing one or more of said nitroxide compounds (i.e. nitroxyl), characterized in that said nitroxide compound (i.e. nitroxyl) or mixture thereof, is further mixed with one or more of (b) said amines.
- 2122. The method such What It was claimed in the claim 21, in where saying one or more compounds from nitroxide, and said a or more amines, I know they add to the monomer stream individually. 22. El método tal como fue reclamado en la reivindicación 21, en donde dicho uno o más compuestos de nitróxido, y dicha una o más aminas, se añaden a la corriente de monómeros individualmente. las the
- 222. 3. The method as it was preceding claims 23. El método tal como fue reivindicaciones precedentes 17 to 20, where said composition is used in a temperature range that varies 17 a 20, en donde dicha composición es utilizada en un rango de temperatura que varia 5 from about 50 ° C to about 180 ° C. 5 de aproximadamente 50°C a aproximadamente 180°C.
Independent claims17
362 paragraphs in 14 sections, as filed
COMPOSITION OF ADDITIVE BASED ON AMINE AND NITRAX ^ Dg Wfo, Φ *
METHOD OF USE OF THE SAME.
FIELD OF THE INVENTION
The present invention relates to an additive composition based on amine and nitroxide for the control and inhibition of the polymerization of aromatic vinyl monomers, wherein the aromatic vinyl monomers include styrene.
In one embodiment, the present invention relates to the use of the amine nitroxide additive composition of the present invention to control and inhibit the polymerization of vinyl aromatic monomers, including styrene.
In another embodiment, the present invention relates to a method of preparing the additive composition based on amine and nitroxide of the present invention for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene.
In yet another embodiment, the present invention relates to a method of controlling and inhibiting the polymerization of vinyl aromatic monomers, including styrene, by employing the amine nitroxide additive composition of the present invention.
/
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BACKGROUND OF THE INVENTION J p
Polymerization of monomers from Vi? I ^ ®la pO¿ &) ¡i- 1NDUSTRI, including styrene, during processing is a cause for concern; because it causes the formation of unwanted polymers and results in the loss of performance of the final product, which makes the process uneconomical.
In the state of the art, the use of inhibitors, retarders and combinations thereof has been reported to overcome the problem of styrene polymerization.
The problem with using the inhibitors alone is that they have to be added continuously or at regular intervals, since once they are consumed, the polymerization will start again.
The problem with using retarders alone is that they are not very effective in reducing styrene polymerization to a substantial level of inhibition or to an acceptable level of inhibition.
In the prior art document US 5,254,760 (referred to as US'760 hereinafter) the inhibition of the polymerization of vinyl monomers using a combination of nitroxide (i.e. nitroxyl compounds) is disclosed, including compound 1-oxyl-2,2,6,6 and nitroaromatic compounds including dinitro-butylphenol [see abstract, column 3, lines 26-32; column 4, lines 1-2, 12 of US'760] as a polymerization inhibitor.
IM PI
Document US'7 60 discloses and teaches
INDUSTRIAL '--a. ·' · · 'Combination of nitroxide compounds (i.e. nitroxyl) and nitroaromatic compounds. US'760 discloses and teaches against the use of any of the nitroxide compounds of nitroaromatic compounds
[See column 5, lines
50-56;
column 6, lines 10-14 and
42-46;
column 7, lines
36-41 of US'760].
However, nitroaromatic compounds including DNBP must be used in higher amounts and / or are also known for their toxic nature to human exposure [see column 1, lines 64-68 of the document
US'760].
Therefore, the industry is targeting an additive composition where nitroaromatic compounds can be avoided. Any effort aimed at avoiding the consumption of nitroaromatic compounds will lessen this problem posed by the industry.
NEED FOR THE INVENTION
Therefore, there is still a need for an effective additive composition and method for its use and preparation, and for a method for controlling and inhibiting the polymerization of monomers of
<img file="MX339245B_D0003.tif" />
aromatic vinyl, by using where the additive composition does not
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r
J de di only
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the substantial control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, but also does not comprise nitroaromatic compounds.
PROBLEM TO BE SOLVED BY THE INVENTION
Therefore, the present invention aims to provide a solution to the existing problem of the industry described above, by proposing an effective additive composition and a method for its use and preparation, and a method for control and for the inhibition of the polymerization of vinyl aromatic monomers, wherein the additive composition is not only suitable for the substantial control and inhibition of polymerization of vinyl aromatic monomers, including styrene, but also does not comprise nitroaromatic compounds.
In addition to the aforementioned objective, the present invention also aims to provide an effective additive composition and a method for its use and preparation, and a method for the control and for the inhibition of the polymerization of aromatic vinyl monomers, in where the additive composition is not only suitable for substantial control and for JlJ ^ Jf ^ .yi (3-i'on., <img file="MX339245B_D0006.tif" /> «NstitutomexicaÑo for the polymerization of vinyl monomers
<img file="MX339245B_D0007.tif" />
including styrene, but also reduced or minimized compounds of nitroxides (ie, nitroxyl) compounds.
OBJECTIVES OF THE INVENTION
Consequently, the main objective of the present invention is to provide an effective additive composition and a method for its use and preparation, and a method for the control and inhibition of the polymerization of aromatic vinyl monomers, wherein the composition of additive is not only suitable for the substantial control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, it also does not comprise nitroaromatic compounds.
Another main objective of the present invention is to provide an effective additive composition and a method for its use and preparation, and a method for the control and inhibition of the polymerization of aromatic vinyl monomers, wherein the additive composition does not it is only suitable for the substantial control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, but also comprises
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a reduction or minimization in the amount ddl ®p ^ pffñS¡tps' ''<sup>:</sup>of lio. X Ji Ápp
INSTITUTO MFXICANO. , nitroxide (i.e. nitroxyl).<sup>Say m</sup>ind ° m'AÍ
It is also an object of the prpconi-o invention, to provide an effective additive composition and a method for its use and preparation, and a method for the control and for the inhibition of the polymerization of aromatic vinyl monomers, wherein the composition of additive comprises a reduction or minimization in the amount of one or more nitroxide compounds (i.e. nitroxyl), and does not comprise nitroaromatic compounds, and is still suitable for the substantial control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, and is still required in a relatively lower dosage in used dosages of compounds compared to those of nitroxides alone (i.e., nitroxyl ) to achieve the same, or a better level of control and inhibition of the polymerization of vinyl aromatic monomers, including styrene.
It is also an object of the present invention to provide an effective additive composition and a method for its use and preparation, and a method for the control and inhibition of the polymerization of aromatic vinyl monomers, wherein the additive composition comprises one or more amines and a reduction or minimization in the amount of one or more compounds of
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nitroxide (i.e. nitroxyl), and does not comprise ^ qoíti ^ lu es tos
IVí .1 nitroaromatics, and is still adequate pá
Substantial INDUSTRIAL and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, and is still required in a relatively lower dosage compared to the used dosages of nitroxide compounds alone (i.e., nitroxyl) to achieve the same, or a better level of control and inhibition of the polymerization of aromatic vinyl monomers, including styrene and wherein the amine is an aliphatic amine.
The present invention has a particular object to provide an effective additive composition and a method for its use and preparation, and a method for the control and inhibition of the polymerization of aromatic vinyl monomers, wherein the additive composition comprises one or plus amines and reduced or minimized amounts of one or more nitroxide compounds (i.e. nitroxyl), and does not comprise nitroaromatic compounds, and is still suitable for the substantial control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, and is still required in a relatively lower dosage compared to the used dosages of nitroxide compounds alone (i.e., nitroxyl ) to achieve the same, or a better level of aromatic ^ polymerization inhibition control and vinyl monomers, including msft '
DS THE industrial PROPERTY
<img file="MX339245B_D0012.tif" />
where the amine is an aliphatic amine, which is selected from the group comprising tertiary amines, secondary amines and primary amines, preferably, the amine is a tertiary amine, and therefore, the composition of the present invention is not only inexpensive, It is also environmentally friendly.
The present invention also aims to improve the performance of nitroxide (i.e. nitroxyl) compounds over a wide range of temperatures, inclusive, at high temperatures and in the presence of air, wherein the composition of the present invention further comprises a or more aliphatic amines.
Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, particularly when read in conjunction with the exemplary embodiments, which are in no way intended to be limiting of the scope of the invention. present invention.
DETAILED DESCRIPTION AND PREFERRED IMPLEMENTATION MODALITIES
OF THE PRESENT INVENTION
In order to overcome the problems of the state of as well as to
T 'P'ÍX' -, .......
preserve
INSTITUTO MEXICANO 5 DE LA PROPERTY INDUSTRIAL that when a
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• il
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consists of compounds the technique described above, achieving the described objectives of the present inventor has found aliphatic amine to the composition that of nitroxide (that is, nitroxyl), inclusive, without nitroaromatic compounds, then, not only the control is substantially improved of the polymerization and the efficiency of the inhibition of nitroxide compounds, but rather the polymerization of vinyl aromatic monomers, including styrene, surprisingly and unexpectedly, the composition comprising one or more nitroxide compounds and one or more aliphatic amine compounds is also controlled and inhibited to an acceptable level at substantially reduced dosages, which makes the composition of the present invention economical, as well as friendly to the environment.
In order to overcome the problems of the state of the art described above, as well as to achieve the described objectives of the present invention, the inventor has found that when one or more aliphatic tertiary amines or aliphatic tertiary amines containing one or more groups hydroxyl or one or more secondary amines or one or more primary amines or mixtures thereof, are added to the composition consisting of one or more nitroxide compounds (i.e. nitroxyl) without compounds is substantially improved £ and the: INSTITUTO MEXICANO X
OF THE Γ-ROPíEJao 'nitroxide, s'ÍWeP ^ K
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nitroaromatics, then, not only is the control of polymerization inhibition of the polymerization compounds of vinyl aromatic PJ monomers, iiiu'luyuiidu styrene, surprisingly and unexpectedly, it is also controlled and inhibited to an acceptable level in substantially reduced dosages of the composition that comprises nitroxide compounds and aliphatic amine compounds, which makes the composition of the present invention economical, as well as friendly to the environment.
Accordingly, the present invention relates to an additive composition for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, comprising:
(a) one or more nitroxide compounds (i.e. nitroxyl), said composition characterized in that it further comprises one or more:
(b) Aliphatic amines selected from the group consisting of tertiary amines, secondary amines and primary amines, preferably the amine is a tertiary amine.
Consequently, in an embodiment, the present invention relates to an additive composition for the control and for the inhibition of the polymerization of aromatic vinyl monomers, comprising:
(a) one or more lp compounds. .
including 'premiere ,?
INSTITUTO MEXICANO DE LZ PE'C'P '^ IVJ · »INDUSTRIAL nitroxide (that is, nitroxilos), characterized in that said composition also comprises one or (b) tertiary amines.
Consequently, in another embodiment, the present invention relates to an additive composition for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, comprising:
(a) one or more nitroxide compounds (i.e. nitroxyl), said composition characterized in that it further comprises one or more:
(b) amines which are selected from the group consisting of primary amines and secondary amines.
According to the present invention, the aliphatic amine is an aliphatic tertiary amine, which contains one or more hydroxyl groups in the alkyl chain of the tertiary amine, preferably, it contains three hydroxyl groups in the alkyl chain of the tertiary amine, plus preferably the hydroxyl groups are hydroxyalgyl groups.
Accordingly, in accordance with a more preferred embodiment.
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FROM THE IS'L'L'iT invention, the amine is a tertiary amine of alkyl hydroxyalkyl.
<td>Therefore, of</td><td>accordance</td><td>with</td><td>a</td><td>from</td><td>the</td>
<td>execution modalities</td><td>preferred</td><td>from</td><td>the</td><td colspan="2">Present</td>
<td>invention, amine is a</td><td colspan="2">treated amine</td><td>with</td><td>oxide</td><td>from</td>
<td>ethylene.</td><td></td><td></td><td></td><td></td><td></td>
<td>Therefore, of</td><td>accordance</td><td>with</td><td>a</td><td>from</td><td>the</td>
<td>execution modalities</td><td>preferred</td><td>from</td><td>the</td><td colspan="2">Present</td>
<td>invention, amine is a</td><td colspan="2">treated amine</td><td>with</td><td>oxide</td><td>from</td>
<td>propylene.</td><td></td><td></td><td></td><td></td><td></td>
<td>Therefore, of</td><td>accordance</td><td>with</td><td>a</td><td>from</td><td>the</td>
<td>execution modalities</td><td>preferred</td><td>from</td><td>the</td><td colspan="2">Present</td>
<td colspan="2">invention, the amine is an alkyl amine</td><td colspan="2">tertiary</td><td>to.</td><td></td>
<td>Therefore, of</td><td>accordance</td><td>with</td><td>a</td><td>from</td><td>the</td>
<td>execution modalities</td><td>preferred</td><td>from</td><td>the</td><td colspan="2">Present</td>
<td>invention, amine is a</td><td>mix of</td><td>a</td><td colspan="3">or more amines</td>
with hydroxyl alkyl tertiary oxide, ethylene treated amines, propylene oxide treated amines, and tertiary alkyl amines.
Accordingly, in accordance with the most preferred embodiments of the present invention, the hydroxyl alkyl tertiary amine is tris (2-hydroxypropyl) amine (TIPA).
In accordance with a preferred mode of the present 1 i dad'esjd ^ y ^^ J. pation invention, the amif ^ SE ^^ gg ^ cja ¿a
INÜUS'I MAL ^ ¿^ 1223 * ^ Ethylene is N, N, Ν ', N'-Tetrakis (2-hydroxyethyl) ethylenediamine) (THEED).
According to one of the preferred embodiments of the present invention, the amine treated with propylene oxide is N, N, Ν ', N'-Tetrakis (2-hydroxypropyl) ethylenediamine) (Quadrol).
According to one of the preferred embodiments of the present invention, the hydroxyl alkyl tertiary amine is triethanolamine (TEA).
According to one of the preferred embodiments of the present invention, the tertiary alkyl amine is Tris [N-butylamine] (TBA).
According to one of the embodiments of the present invention, the primary amine is selected from the group comprising alkyl hydroxyl primary amine and alkyl primary amine.
According to one of the embodiments of the present invention, the secondary amine is alkyl secondary amine.
According to one of the embodiments of the present invention, the alkyl hydroxyl primary amine is monoethanolamine (MEA).
In accordance with one of the modalities of realization
Κ
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In accordance with one embodiment of the present invention, the alkyl secondary amine is dibutylamine (DBA).
It has been found that when the composition of the present invention comprises one or more of the amines described above, the efficiency of nitroxide compounds to control and inhibit the polymerization of aromatic vinyl monomers, including styrene, surprisingly and unexpectedly, is substantially improved. at an acceptable level this occurs also at substantially reduced dosages of nitroxide compounds and occurs also without aromatic nitro compounds, which makes the composition of the present invention relatively more economical and ecological.
In accordance with one of the embodiments of the present invention, the composition of the present invention comprises:
a) from about 40% to about 99.75% by weight of i) said nitroxide (ie, nitroxyl) compounds; Y
b) from about 0.25% to about 60% by weight of II) said amines or a mixture thereof.
<img file="MX339245B_D0018.tif" />
The present invention monomers are added to the stream containing the vinyl aromatics, including styrene, in an amount ranging from about 0.01 ppm to about 2000 ppm, preferably from about 1 ppm to about 2000 ppm by weight of the monomer stream that includes styrene.
According to the present invention, the nitroxide (or nitroxyl) compounds are selected from the group comprising di-tert-butylnitroxyl, l-oxyl-2,2,6,6 tetramethylpiperidine, l-oxyl-2,2,6, 6-tetramethylpiperidin-4ol, l-oxyl-2,2,6,6-tetramethylpiperidin-4-one, and derivatives thereof; and di-nitroxides and derivatives comprising bis (loxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-oxyl-
2.2.6.6- tetramethylpiperidin-4-yl) succinate, bis (1-oxyl-
2.2.6.6- tetramethylpiperidin-4-yl) adipate, and mixtures thereof.
According to the preferred embodiment of the present invention, the nitroxide (or nitroxyl) compound is selected from the group comprising bis (l-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl) sebacate and l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol or 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl (or 4 Hydroxy Tempo or 4-HT), and mixtures thereof.
<img file="MX339245B_D0019.tif" />
According to the most preferred embodiment of the present invention, the compound d¿Jrc ^ J & x'í-do ^ ST.jIJTO MEXICANO ln 'JA IN DL · i TRί \!.
nitroxyl) is l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (or 4
Hydroxy Tempo or 4-HT).
According to one of the preferred embodiments of the present invention, the composition of the present invention does not comprise a nitroaromatic compound.
Consequently, in another embodiment, the present invention also refers to a method for using the additive composition based on amine and nitroxide of the present invention that is described in the present patent application, a reference that in its The entirety is directed at controlling and inhibiting the polymerization of vinyl aromatic monomers, including styrene, wherein the stream comprising the vinyl aromatic monomer
<td>including styrene,</td><td>I know</td><td>treats</td><td>with</td><td>bliss</td><td>composition of</td>
<td>additive comprising</td><td>one</td><td>or more</td><td>from</td><td>sayings</td><td>composed of</td>
<td>nitroxide (i.e.</td><td colspan="2">nitroxyls)</td><td>Y</td><td>one or</td><td>more of said</td>
<td>amines.</td><td></td><td></td><td></td><td></td><td></td>
<td>In particular, in</td><td>a</td><td>second</td><td colspan="2">modality</td><td>of realization,</td>
The present invention also refers to a method for the use of the additive composition of the present invention described in the present patent application, a reference that in its entirety is directed to the control and inhibition of the polymerization of vinyl monomers aromatics, including styrene, comprises:
(a) one or more compounds wherein said composition I iw r I („tNST'TIj-rr; Μ<sub>2</sub>χ:<sub>(</sub>-<sub>ν</sub>.;<sub>ο</sub> ,
FROM THE PROPERTY \ TO INDI'STR! ' Nitroxyls), said composition characterized in that it also comprises one or more:
(b) aliphatic amines selected from the group consisting of tertiary amines, secondary amines and primary amines, preferably the amine is a tertiary amine;
and said monomers are treated with said composition.
Consequently, in this second embodiment, the present invention particularly relates to a method for using the additive composition of the present invention described in the present patent application, a reference that in its entirety is directed to the control and inhibition of the polymerization of vinyl aromatic monomers, including styrene, wherein said composition comprises:
(a) one or more nitroxide compounds (i.e. nitroxyl), said composition characterized in that it further comprises one or more:
(b) tertiary amines; and said monomers are treated with said composition.
Consequently, in this second embodiment, the present invention is also sj
INSTiT'JTC MEXICAN V composition of d <.
method for the use of the present invention described in patent, reference that in its control vinyl
<img file="MX339245B_D0020.tif" />
<img file="MX339245B_D0021.tif" />
the nrpspntp application for totality is directed, to the inhibition of the polymerization of aromatics, including styrene, in composition comprising:
(a) one or more nitroxyl nitroxide compounds), said composition characterized in that it comprises monomers of which said in addition one or (b) amines that are selected from the group consisting of primary amines and secondary amines;
said monomers are treated with said composition.
It should be noted that the stream comprising vinyl aromatic monomers, including styrene, may be referred to in the present patent application as stream, or stream of monomers, or stream of vinyl aromatic monomers.
According to one of the embodiments of the present invention, the method for using said additive composition of the present invention comprises treating said stream of monomers with approximately 0.01 ppm to approximately 2000 ppm, preferably approximately 1 ppm to approximately
2000 ppm of said monomer.
composition based on weight
IMPI
INSTITUTO MEXICANO de la pro; ¡f. ;; ad INDUSTRIAL del
<img file="MX339245B_D0022.tif" />
It should be noted, composition of which all the characteristics of the present invention described in this patent application, reference that in its entirety is directed, to consider that they have been included in the present method for the use of said additive composition of the present invention.
Consequently, in a third embodiment, the present invention also relates to a method for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, by using the amine-based additive composition and nitroxide of the present invention, described in the present patent application, reference that in its entirety is directed, to when the stream comprising aromatic vinyl monomers, including styrene, it is treated with an additive composition comprising one or more nitroxide compounds (ie, nitroxyl) and one or more amines.
In particular, in the third embodiment, the present invention relates to a method for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, by using the additive composition of the present invention, described in the present patent application, referehc '
<img file="MX339245B_D0023.tif" />
totality is directed, when the composition bought ^ j<sub>p</sub>M «: can (a) one or more nitroxide compounds (that is, nitroxyl), said composition characterized in that it also comprises one or more:
(b) aliphatic amines selected from the group consisting of tertiary amines, secondary amines and primary amines, preferably the amine is a tertiary amine; and said composition is added to said monomers.
Consequently, in this third embodiment, the present invention particularly relates to a method for controlling and inhibiting the polymerization of vinyl aromatic monomers, including styrene, by using the additive composition of the present invention. , described in the present patent application, reference that in its entirety is directed, when the composition comprises:
(a) one or more nitroxide compounds (i.e. nitroxyl), said composition characterized in that it further comprises one or more:
(b) tertiary amines; and and said composition is added to said monomers.
Consequently, in this third embodiment, method for the present invention also teéJr ^^ e ^ fya ^ -μρ the control and for the inhibTaSMiRCHE ^ ÍS '<The industrial polymerization of aromatic vinyl monomers, including styrene, by using of the additive composition of the present invention, described in the present patent application, reference that in its entirety is addressed, when the composition comprises:
(a) one or more nitroxide compounds (i.e. nitroxyl), said composition characterized in that it further comprises one or more:
(b) amines which are selected from the group consisting of primary amines and secondary amines; and and said composition is added to said monomers.
It should be noted that the stream comprising vinyl aromatic monomers, including styrene, may be referred to in the present patent application as stream, or stream of monomers, or stream of vinyl aromatic monomers.
According to one of the embodiments of the present invention, the method for controlling and inhibiting the polymerization of aromatic vinyl monomers, including styrene, by using the additive composition of the present invention, comprises the following: addition of about 0.01 ppm to about 2000 ppm, preferably about
<img file="MX339245B_D0024.tif" />
approximately 2000 ppm of said composition of vinyl aromatic monomers, including styrene, based on the weight of the monomer.
It should be noted that all the characteristics of the composition of the present invention, described in this patent application, a reference that in its entirety is directed, to be considered as having been included in the present method for the control and inhibition of polymerization of aromatic vinyl monomers, including styrene, by employing said additive composition of the present invention.
According to one embodiment of the present invention, the composition of the present invention can be mixed with, or added to, the monomer stream containing vinyl aromatic monomers, including styrene, either before the stream enters the processing system, or after the stream has entered the processing system, but preferably, the composition is added to the stream containing vinyl aromatic monomers, before processing begins so as to avoid polymerization of vinyl aromatic monomers.
According to one of the embodiments of the present invention, the nitroxide compounds and the amine compounds can be mixed «
the stream of mixed monomers.
According to one of the modalities individually
<img file="MX339245B_D0025.tif" />
INDUSTRIAL implementation of the present invention, the composition can be used in, or used with, a wide range approximately
60 ° C to 180 ° C.
or added to, the monomer stream in de
50 ° C
The composition at temperatures which vary to 180 ° C, preferably in the range of preparing any compositions.
Accordingly, embodiment, the method for the amine base and in the present of the present invention can be known way in a fourth present invention also to prepare modality refers preparation of the nitroxide additive composition entire application is directed, the polymerization including styrene, from of the present invention described patent, reference that in its for the control and of monomers of for the inhibition of vinyl aromatics, wherein the nitroxide and amine compounds are added individually or after being mixed.
In particular, the present invention in the fourth embodiment also refers to an embodiment, a method for the preparation of the additive composition of the present invention described in the present reference application which in its entirety is directed, to
<img file="MX339245B_D0026.tif" />
for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, wherein the method comprises:
(a) mixing one or more of said nitroxide compounds (i.e., nitroxyl), characterized in that said nitroxide compound or mixture thereof, is further mixed with one or more:
(b) Aliphatic amines selected from the group consisting of tertiary amines, secondary amines and primary amines, preferably the tertiary amines.
Consequently, in this fourth embodiment, the present invention particularly relates to a method for the preparation of the additive composition of the present invention described in the present patent application, a reference that in its entirety is directed to the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, wherein the method comprises:
(a) mixing one or more of said nitroxide compounds (i.e., nitroxyl), characterized in that said nitroxide compound or mixture thereof, is further mixed with one or more:
(b) tertiary amines.
modality additive
I Ο pT Ji se PedrareMiSicAia) OF INDUSTRIAL PROPERTY
<img file="MX339245B_D0027.tif" />
Consequently, in this fourth embodiment, the present invention is also a method for the preparation of the present invention composition described in the present patent application, a reference that in its entirety is directed to the control and inhibition of the polymerization of monomers aromatic vinyl, including styrene, wherein the method comprises:
(a) mixing one or more of said nitroxide (i.e. nitroxyl) compounds, characterized in that said nitroxide compound or mixture thereof is further mixed with one or more:
(b) amines selected from the group consisting of primary amines and secondary amines.
It should be noted that the stream comprising the vinyl aromatic monomers, including styrene, can be referred to as a stream, or as a stream of monomers, or as a stream of vinyl aromatic monomers.
It should be noted that all the characteristics of the composition of the present invention described in the present patent application, reference that in its entirety is directed to, is considered to have been included in the present method to prepare said additive composition of the present invention. .
In one of the embodiments of the present invention, the inventor has found that when the
<img file="MX339245B_D0028.tif" />
composition of the present invention compIeAíí Rr (a.of
INSTITUTO MEXICANO i DE LA PROPIEDAD any of the amines selected from Ν, Ν, N ', N'-Tetrakis (2-hydroxyethyl) ethylenediamine) (THEeD) and
N, N, Ν ', Ν'-Tetrakis (2-hydroxypropyl) ethylenediamine) (Quadrol), then the efficiency for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, of the nitroxides is substantially improved , inclusive, the improvement of said efficiency is not as substantial as for the composition comprising tris (2-hydroxypropyl) amine (TIPA). Therefore, according to the most preferred embodiment of the present invention, hydroxypropyl) amine (TIPA) is the most preferred amine.
In another embodiment of the present invention, the inventor has found that when the composition of the present invention comprises one of any of the amines selected from the group consisting of triethanolamine (TEA), tris [N-butylamine] (TBA), monoethanolamine (MEA), octylamine (OA), dibutylamine (DBA), then the efficiency for the control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, of the nitroxides is improved, however, the improvement in said efficiency is not as substantial as for the composition comprising Ν, Ν, Ν ', Ν'Tetrakis (2-hydroxyethyl) ethylenediamine) (THEED) or Ν, Ν, Ν', Ν'27
Tetrakis (2-hydroxypropyl) ethylenediamine) (QuadroíL) ^ Therefore, according to a more preferred modality of
INDUSTRIAL invention, N, N, Ν ', Ν'-Tetrakis (2-hydroxyethyl) ethylenediamine) (THEED) and N, N, Ν', Ν'-Tetrakis (2-hydroxypropyl) ethylenediamine) (Quadrol), are amines most preferred. Dibutiiamine (DBA) has surprisingly and unexpectedly been found to show better efficiency when used in compositions at a dosage of about 200 ppm or more.
In still another embodiment of the present invention, the inventor has found that when the composition of the present invention comprises one of any of the amines selected from the group consisting of N, N, dissec-butyl-para-phenylene diamine (UOP5 ), ethylenediamine (EDA), tetraethylenepentamine (ΤΕΡΑ), dipropylamine (DPA), or diethanolamine (DEA), then the efficiency for the control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, of the nitroxides it is not improved. Therefore, in one embodiment, the composition of the present invention does not comprise any of the amines selected from the group consisting of N, N, dissect-butyl-para-phenylene diamine (UOP5), ethylenediamine (EDA), tetraethylenepentamine ( ), dipropylamine (DPA), or diethanolamine (DEA). It should be noted that some of these amines result in a very marginal improvement in nitroxide efficiency, but this is not commercially viable.
Y ·... '-\<sub>x</sub>.
More advantages and additional modalities of
OF THE INDUSTRIAL PROPERTY raar · the present invention, will be apparent from the following embodiments.
The present invention is now described with the aid of the following examples, which are not intended to limit the scope of the present invention, however, they have been incorporated by way of illustration in order to exemplify the best way of carrying out the present invention .
EXPERIMENTS
Main Experiment
In the following experiments, a weighed amount of distilled styrene and additives were brought into a reactor (tubular reactor or round bottom reactor) equipped with a thermometer and with a nitrogen inlet and outlet. In these experiments, a tubular reactor without a mechanical stirrer was used, so that a sufficient flow of N2 was maintained to ensure adequate stirring. The reactions were carried out at a temperature of approximately 120 ° C for approximately 2 hours. After the selected duration, the reactor was cooled below 10 ° C by immersion in crushed ice. The contents of the reactor were then poured into a beaker. In this same beaker, approximately a precipitate obtained was filtered, dried to remove methanol, and weighed.
The weight of the precipitate was reported as percentage (%) of polymer formed in the following tables.
It should be noted that styrene was purified prior to use to remove stabilizers.
In the following examples, the additive of the state of the art is a nitroxide, which is l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (or 4-Hydroxy Tempo or 4-HT), which is taken in an amount of about 100 ppm, 200 ppm, 300 ppm, 500 ppm, or 1000 ppm by weight of styrene.
In the following examples, the additive of the present invention is a composition comprising nitroxide which is 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (or 4-Hydroxy Tempo or 4-HT), and the Aliphatic tertiary amine is tri-isopropanoamine (TIPA) containing three hydroxyl groups, where from about 1 ppm to about 20 ppm of TIPA is added to a weighed amount of nitroxide.
Experiment 1
The results of the Main Experiment described above, when it is carried out with 10 g of distilled styrene, with a heating of 120 ° C, are provided in Table I.
<img file="MX339245B_D0029.tif" />
<img file="MX339245B_D0030.tif" />
Table I
<td>Active Dosage of the Prior Art Additive Composition (ppm);</td><td>% of polymer formed with the Prior Art Additive</td><td>Dosage Active of the Present Additive Composition (ppm) i</td><td>% of polymer formed with the Present Composition</td><td>Technical Effects of the Present Composition</td>
<td rowspan="4">100 ppm</td><td rowspan="4"> 13.19</td><td>100 + 4 TYPE</td><td> 11.22</td><td rowspan="7">The efficiency of nitroxide polymerization inhibition is improved, and the% polymer formed is substantially reduced with the addition of the aliphatic tertiary amine in the nitroxide.</td>
<td>100 + 10 TYPE</td><td> 10.9</td>
<td>100 + 15 TYPE</td><td> 6.28</td>
<td>100 + 20 TYPE</td><td> 4.3</td>
<td rowspan="2">200 ppm</td><td rowspan="2"> 9.38</td><td>100 + 15 TYPE</td><td> 6.28</td>
<td>100 + 20 TYPE</td><td> 4.3</td>
<td>300 ppm</td><td> 5.1</td><td>100 + 20 TYPE</td><td> 4.3</td>
It is understood from Table I above, that when only 4 ppm to 20 ppm of TIPA are added to 100 ppm of 4-HT (additive of the state of the art), the
<td>efficiency of</td><td>4-HT</td><td>to control and</td><td>to inhibit</td><td>the</td>
<td>polymerization</td><td>from</td><td>styrene is,</td><td>surprising</td><td>and</td>
<td>10 unexpectedly</td><td colspan="2">, substantially improved.</td><td></td><td></td>
<td>I also know</td><td>can</td><td>observe from</td><td>Table I, which</td><td>the</td>
<td>polymerization</td><td>of</td><td>styrene is,</td><td>surprising</td><td>and</td>
<td>unexpectedly</td><td colspan="2">, substantially reduced;</td><td colspan="2">only with the addition</td>
<td>from 4 ppm to 20</td><td>ppm of</td><td>TIPA at 100 ppm</td><td>4-HT (additive</td><td>of</td>
state of the art).
the percentage. (%) of polymer alone, it is reduced Ji ^^ n ^ 'a¡jiníeñté INSTITUTO M EXICANO DELA PROPERTY 6.28%, and 4
10.9%, a added 4
<img file="MX339245B_D0031.tif" />
It can be seen that formed with 100 ppm of 4-HT from 13.19% to 11.22%, respectively, when total composition), 10 ppm (9.09% of the total composition), 15 ppm (13.04% of the total composition) and 20 ppm (16.67% of the total composition) of TIPA at 100 ppm of 4-HT.
It can also be seen from Table I, that for the composition comprising 100 ppm of 4-HT and 15 ppm of TIPA (13.04% of TIPA of the total composition), the percentage (%) of polymer formed is, surprising and unexpectedly, substantially less than the percentage (%) of polymer formed with the composition consisting of 200 ppm of 4-HT, which means that, the present composition results in a saving of half the dosage of 4-HT, and therefore it is economical and environmentally friendly.
It can also be seen from Table I, that for the composition comprising 100 ppm of 4-HT and 20 ppm of TIPA (16.67% of TIPA of the total composition), the percentage (%) of polymer formed is, surprisingly and unexpectedly, substantially less than the percentage (%) of polymer formed with the composition consisting of 300 ppm of 4-HT, which means that, the present composition results in a saving of two thirds of the 4HT dosage, and therefore therefore, it is economical and environmentally friendly.
Experiment 2
The results of the Main Experiment described above, when carried out with 10 g of distilled styrene, with heating at 135 ° C, for 2 hours, are provided in Table II.
<img file="MX339245B_D0032.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Table II
<td>Active Dosage of Prior Art Additive Composition (ppm) i</td><td>% polymer formed with Prior Art Additive</td><td>Active Dosage of the Present Additive Composition (ppm) i</td><td>% of polymer formed with the Present Composition</td><td>Technical Effects of the Present Composition</td>
<td rowspan="4">500 ppm</td><td rowspan="4"> 16.7</td><td>500 + 5 TYPE</td><td> 6.45</td><td rowspan="7">The efficiency of nitroxide polymerization inhibition is improved, and the% polymer formed is substantially reduced with the addition of the aliphatic tertiary amine to the nitroxide.</td>
<td>500 + 10 TYPE</td><td> 6.05</td>
<td>500 + 15 TYPE</td><td> 5.72</td>
<td>500 + 20 TYPE</td><td> 4.9</td>
<td rowspan="3">1000 ppm</td><td rowspan="3"> 6.13</td><td>500 + 10 TYPE</td><td> 6.05</td>
<td>500 + 15 TYPE</td><td> 5.72</td>
<td>500 + 20 TYPE</td><td> 4.9</td>
It is understood from the Table
II previously mentioned, that
Even TIPA (with styrene additive when only state of the art are added), the additive is treated from ppm to 2 0 ppm of
500 ppm of 4-HT the current of even at a higher temperature of 135 ° C, the efficiency of 4-HT to control and
<img file="MX339245B_D0033.tif" />
unexpectedly, substantially improved.
to inhibit the polymerization of styrene ^. · It is, surprising and
IMPig /
INSTITUTO MEXICANO Vt-ífe DE LA PROPERTY 'INDUSTRIAL Table II, that the
It can also be seen from styrene polymerization is unexpectedly substantially reduced only with the addition of 5 ppm to 20 ppm of TIPA in 500 ppm of 4-HT (state of the art additive).
It should be noted that the percentage (%) of polymer formed with 500 ppm of 4-HT alone is substantially reduced, even at a higher temperature of approximately 135 ° C from 16.7% to 6.45%, to 6.05%, to 5.72%. , and to 4.9%, respectively, when 5 ppm (only 0.99% of the total composition), 10 ppm (only 1.96% of the total composition), 15 ppm (only 2.91% of the total composition) and 20 ppm (only 3.85% of the total composition) of TIPA at 500 ppm of 4-HT. The reduction achieved is even greater than about 3 times.
It can also be seen from Table II, that for the composition comprising 500 ppm of 4-HT and 10 ppm of TIPA (only 1.96% of TIPA of the total composition), the percentage (%) of polymer formed is surprising and unexpectedly, less than the percentage (%) of polymer formed with the composition consisting of 1000 ppm of 4-HT, which means that, the present composition results in a saving of half the dosage of 4-HT , and therefore it is economical and favorable
<img file="MX339245B_D0034.tif" />
INSTITUTE Μ Γ.λ íf / * NO De LA? SO?; FDAD INDUS1 R.IAL
<img file="MX339245B_D0035.tif" />
Experiment 3 to 5
In the following examples, for the Experiment
Mainly mentioned above, the additive composition of the state of the art is 4-HT, which is taken in an amount of approximately
100 ppm, 200 ppm, and 300 ppm, and the additive composition of the present invention is a composition comprising
4-HT as nitroxide, which further comprises
TIPA, THEED, Quadrol, TEA,
TBA, MEA,
OA,
DBA as the amines of the present invention, which are taken in a weight ratio of 99: 1, 98: 2, 95: 5, 90:10,
85:15, 80:20, 70:30 and 50:50, the composition is made at 100 ppm, 200 ppm and 300 ppm.
The inventor has further compared the results of the present compositions with additive compositions comprising 4-HT and an amine selected from a group consisting of UOP5, EDA, *, DPA, or DEA, for comparative purposes.
As can be seen from the data in the Tables
III, IV and V, with the addition of about 1 ppm to about 150 ppm of TIPA, THEED, Quadrol, TEA, TBA,
4-HT MEA, OA or DBA to make a total of 100 ppm, 200 ppm and 300 ppm of the composition in order to have a 4-HT: amine weight ratio of 99: 1, 98: 2, 95: 5, 90:10, 85:15, 80:20,
<img file="MX339245B_D0036.tif" />
70:30 and 50:50, the composition efficiency ajptf £ yg of the
MEXICAN INSTITUTE
<img file="MX339245B_D0037.tif" />
state of the art consisting of 4-HT peace ^ A ^^^ oi ^^^^ r to inhibit styrene polymerization ps .-- snrprpnriente and unexpectedly, generally improved.
As can be seen, when the composition of the present invention comprises any one of the amines selected from the group consisting of N, N, N ', N'-Tetrakis (2-hydroxyethyl) ethylenediamine) (THEED) and N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine) (Quadrol), then the efficiency for the control and for the inhibition of the polymerization of aromatic vinyl monomers, including styrene, of the nitroxides is substantially improved, however, the improvement is not as substantial as for the composition comprising tris (2-hydroxypropyl) amine (TIPA). Therefore, according to the most preferred embodiment of the present invention, tris (2-hydroxypropyl) amine (TIPA) is the most preferred amine.
As can also be seen, when the composition of the present invention comprises one of any of the amines selected from the group consisting of triethanolamine (TEA), Tris [N-butylamine] (TBA), monoethanolamine (MEA), octylamine (OA) , dibutylamine (DBA), then the efficiency for the control and for the inhibition of the polymerization of vinyl aromatic monomers, including styrene, of the nitroxides is improved, however, the improvement is not as substantial as for the composition than οοιρρι ^ Γ> ^^ Ι ^ Ι- | Ν t, .. N 'tetrakis (2-hydroxyethyl) ethylenediamine) tetrakis (2-hydroxypropyl) ethylenediamine) (Quadrol). Therefore, according to a more preferred embodiment of the present invention, N, N, NN'-tetrakis (2-hydroxyethyl) ethylenediamine) (THEED) and N, N, N ', N'-tetraqks (2-hydroxypropyl ) ethylenediamine) (Quadrol), are more preferred amines.
As can be seen, dibutylamine (DBA) surprisingly and unexpectedly shows better efficiency when used in compositions of dosages of about 200 ppm or more.
As has also been observed, when the composition comprises any of the comparative amines selected from the group consisting of N, N, dissec-butyl-para-phenylene diamine (UOP5), ethylenediamine (EDA), tetraethylenepentamine (ΤΕΡΑ), dipropylamine (DPA ), or diethanolamine (DEA), then the efficiency for the control and for the inhibition of the polymerization of aromatic vinyl monomers including styrene of the nitroxides, is not improved. Therefore, in one embodiment, the present composition does not comprise any of the amines selected from a group consisting of N, N, disec-butyl-para-phenylene diamine (UOP5), ethylenediamine (EDA), tetraethylenepentamine (ΤΕΡΑ ), dipropylamine (DPA), or diethanolamine (DEA). It should be noted, that some of these amines result in a very marginal improvement in efficiency.
<img file="MX339245B_D0038.tif" />
it is commercially viable.
It should be noted that, surprisingly and unexpectedly, with increasing amine concentration, that is, when about 20% or more of the amine is added to 4-HT, the polymerization inhibition efficiency of the present composition of additive is marginally reduced, due to reasons that are not currently known.
Therefore, in view of the above-mentioned experimental data as well as their analysis, it can be concluded that only the additive compositions of the present invention comprising 4-HT an amine selected from the group consisting of TIPA, THEED, Quadrol,
TEA, TBA, MEA, OA and DBA surprisingly and unexpectedly result in improved polymerization control and inhibition efficiency of the state of the art additive composition consisting of 4-HT, and these Results confirm the synergistic effect of the compositions of the present invention.
Experiment 6
The above Main Experiment was also carried out with a round bottom reactor for the additive composition of the state of the art consisting of 4-HT; and the additive composition of that comprising 4-HT and TIPA, and it was found that of the amine additives of the present
<img file="MX339245B_D0039.tif" />
The efficiency of the state of the art additive composition to control and inhibit styrene polymerization is surprisingly and unexpectedly generally improved, even in a round bottom reactor.
Table VI
<td>Composition</td><td>Active dosage, ppm</td><td>% Polymer</td>
<td>4HT</td><td> 100</td><td> 13.27</td>
<td>4HT</td><td> 200</td><td> 9.11</td>
<td>4HT</td><td> 300</td><td> 6.79</td>
<td>4HT</td><td> 400</td><td> 2.32</td>
<td>4HT + TIPA (90:10)</td><td> 100</td><td> 10.17</td>
<td>4HT + TIPA (90:10)</td><td> 200</td><td> 4.42</td>
<td>4HT + TIPA (95: 5)</td><td> 200</td><td> 5.15</td>
The above-mentioned experimental data confirms the surprising and unexpected synergistic effects and technical effects as well as the advantages of the additive composition of the present invention compared to the additive composition of the state of the art and the comparative compositions.
All the above results confirm the synergistic, surprising and unexpected effects of the composition of the present invention, both at lower temperatures, as well as at higher temperatures.
All results above indiria ^ i ^ x -. ^ Also
I ΐ Í. Do they confirm that there is a successive increase in the<sup>NS</sup>é ^^ i®n .. 'GiR ^ Tea]<sub>t</sub>,. ^ υ industrial additive of this of the art to control and inhibit the polymerization of styrene.
All the aforementioned results also confirm that the composition of the present invention is capable of achieving a much better efficiency to control and inhibit styrene polymerization with the same dose of additive of the state of the art, which means that the present The invention also results in economic and environmental benefits.
The previous experimental results confirm that the composition proposed by the present invention is much superior than the additive of the state of the art, and therefore, it has surprising technical advantages and effects over the additive of the state of the art.
It should be noted that the term, approximately, as used in the present patent application, is not intended to broaden the scope of the claimed invention, but has only been incorporated to include any experimental margin of error that is admissible within the scope of the invention. the technique to which the present invention belongs.
<img file="MX339245B_D0040.tif" />
Table III
<td>Η Οι ® Ρ Η</td><td>lD 00 CO 1—1</td><td>CN CN <—1</td><td>CO or t — l</td><td>LD «ÑT rH</td><td>rLO • ñT r — 1</td><td>LO r- mr rH</td><td>LD LD rH</td><td>rCN LO t — 1</td>
<td> “ §</td><td>LO LO cn rH</td><td>t — l σ> cn T — l</td><td>r — 1 t — l</td><td>CN 'tr t-l</td><td>mr rH</td><td>t — l LO t — l</td><td>LD 00 'ñT t — l</td><td>LO σ \ lD t — 1</td>
<td>ga 5 8</td><td>cn cn cn i — l</td><td>Com cn t — l</td><td>00 Γ- ΓΟ rH</td><td>t — l O ñT t — I</td><td>LO CN vf <—1</td><td>• ñt rH</td><td>ÑT IT Ό * t — l</td><td>t — 1 t — l LD rH</td>
<td>ιη fe ® Ο Μ<sup>1</sup> Ο</td><td>OR cn r — 1</td><td>CN CN cn 1—1</td><td>LO Lf) cn r — l</td><td>cn LO co t — I</td><td>CN or \ m rH</td><td>t — 1 CN ñT t — I</td><td>00 LD 'd' rH</td><td>cn lD LD rH</td>
<td>g Yes</td><td>cn oo CN 1—1</td><td>CN cn CN rH</td><td>CN LD CN t — l</td><td>cn CN t — 1</td><td>LD m cn i — 1</td><td>OR • ÑT i — 1</td><td>LD LD t — 1</td><td>00 IT</td>
<td>Μ «4 g Λ 5 ο</td><td>rCN CN i — 1</td><td>Mad i — I t — l</td><td>CO LD i — lt — l</td><td>00 LD r — lr — 1</td><td>«Γ r — 1 rH</td><td>Or LD CN i — 1</td><td>CN cn r — 1</td><td>LD LD ñJ * t — l</td>
<td>4ΗΤ / Octyl amine</td><td>CN 00 CN i — l</td><td>a cn CN t — l</td><td>LD cn t — lt — l</td><td>LD CN rH t — 1</td><td>IT 00 Or rH</td><td>LO LD i — 1 i — 1</td><td>LD r — 1 CN t — 1</td><td>Rh cn i — 1</td>
<td>4ΗΤ / ΤΒΑ</td><td>m σι CN i — 1</td><td>i — l LD CN rH</td><td>CN oo t — l rH</td><td>LD t — l rH</td><td>OR ! —1 t — 1</td><td>CN t — 1 t — l</td><td>00 LD t — lt — l</td><td>LO or cn 1—1</td>
<td>4ΗΤ / MEA</td><td>OR WHAT CN t — l</td><td>CO t — 1 CN i — l</td><td>00 or CN t — l</td><td>cn 00 rH t — 1</td><td>LD CN t — 1 t — 1</td><td>LD O t — tt — I</td><td>Or CN t — lt — l</td><td>00 Οϊ rH rH</td>
<td>-χ. Η S »Β *3</td><td>MAD CN rH</td><td>LO CN CN t — l</td><td>IT OR t — li — 1</td><td>OO CO Or rH</td><td>! —1 cn cn</td><td>LD O cn</td><td>rcn cn</td><td>ΓΟΟ O t — l</td>
<td>rH ° Ί</td><td>rin 1—1 τ — 1</td><td>cn CN t — l</td><td>LO cn cn</td><td>LD CN cn</td><td>or 00 oo</td><td>cn sr 00</td><td>LD rH cn</td><td>CN 03 cn</td>
<td>ΒΗ Q m Η 5 «</td><td>LO LO t — l ι — 1</td><td>LO t — l 1—1 i — l</td><td>t — l 00 cn</td><td>LD t — l cn</td><td>cn co 00</td><td>LD co</td><td>LO CN cn</td><td>CN cn cn</td>
<td>η á ® Η Η</td><td>LD t — 1 t — l t — l</td><td>i — l LO O t — l</td><td> 00 00</td><td>CN LT) r-</td><td>«ÑT co r-</td><td>Γ-</td><td>or i — 1 co</td><td>or cn 00</td>
<td>t < 8Β 'f</td><td>0 » cn i — 1</td><td>σ> cn T — l</td><td>σι cn rH</td><td>Ώ cn t — l</td><td>σι cn Rh</td><td>(Λ cn rH</td><td>to cn rH</td><td>Ώ cn r4</td>
<td>Dose Active 4ΗΤ + Amine</td><td>t — l + σ> <T></td><td>CN + 00 cn</td><td>LD + LD cn</td><td>O t — l + O cn</td><td>LD i — l + LD co</td><td>O CN + O 00</td><td>Or cn + or r-</td><td>Or ID + Or LD</td>
<td>Dose Total (ppm)</td><td>oo rH</td><td>co ot — l</td><td>ooi — l</td><td>oo rH</td><td>OO t — 1</td><td>oo rH</td><td>oot — 1</td><td>OO t — 1</td>
<td rowspan="2">Dose Active Ratio of 4HT: Amine</td><td>i — 1</td><td>CN</td><td>LD</td><td>O ι-H</td><td>ID t — l</td><td>OR CN</td><td>or cn</td><td>or LD</td>
<td>cn cn</td><td>00 cn</td><td>LD cn</td><td>Or cn</td><td>ID 00</td><td>O 03</td><td>or r-</td><td>Or LD</td>
<img file="MX339245B_D0041.tif" />
ιβ
Η
<img file="MX339245B_D0042.tif" />
Table
<td>a <E- «CU SC M H</td><td>in m</td><td>LD Γ LD</td><td> 6.17 |</td><td>a «T co</td><td> 6.62 |</td><td> 7.09 |</td><td>co cn 03</td><td> 10.05 |</td>
<td>g | M</td><td>CN LD</td><td>1X641</td><td> | 6.08 |</td><td>1X201</td><td><sup>6</sup>-<sup>34</sup></td><td> 1 <sup>6</sup>·<sup>91</sup> 1</td><td>oo CO</td><td> 1 <sup>9</sup>·<sup>26</sup> 1</td>
<td>> · <»Q</td><td> 4.91</td><td> 4.63</td><td> 4.23</td><td>ld o 'S'</td><td>LO cn • tr</td><td> 4.65</td><td> 5.26</td><td>LO LO CO</td>
<td>ga 5 8</td><td>1X061</td><td> 1 <sup>4</sup>·<sup>95</sup> 1</td><td>| 5.56 I</td><td> 1 <sup>5</sup>·<sup>77</sup> 1</td><td><sup>6</sup>-<sup>10</sup></td><td>LO r-</td><td>CO co</td><td> 1 <sup>9</sup>·<sup>7</sup> 1</td>
<td>LD t <CU ffi O Ί £</td><td>Γ <sup>5</sup>·<sup>05</sup> 1</td><td> 5.24</td><td> 5.62</td><td> 5.90</td><td> 1 7-51</td><td>rr-</td><td>σι 00</td><td>6'6 j</td>
<td>glsi 5 | Ql</td><td>1X151</td><td> ¡ 3-<sup>5</sup>3 1</td><td>i 3-30 |</td><td>1 3.15 I</td><td>Π3.04 1</td><td> 3-41</td><td>cn cn</td><td> | 4.55 |</td>
<td>4HT / Octyl amine</td><td> 4.53</td><td>CN cn cn</td><td>OO cn</td><td> 3.29 |</td><td> 2.92</td><td>CN cn</td><td> 3.56</td><td><sup>4</sup> ·<sup>33</sup> 1</td>
<td>gá s ε ti</td><td>OT «ΝΤ *</td><td> 4.09 |</td><td>| 3.78 I</td><td>LO cn</td><td>Γ CN</td><td> 3.25 |</td><td> 3.68 |</td><td>4X6 |</td>
<td>'4HT / 1 MEA</td><td> 3.95 |</td><td>CN cn</td><td>Γ 3.08 Π</td><td> 2.84 |</td><td> 3.04 |</td><td> 3.55 |</td><td> 4.22 |</td><td> 4.82 |</td>
<td>I KNOW</td><td>* 3 Γ-</td><td> 1 4-05 1</td><td> | 3.22 |</td><td>I <sup>2</sup>·<sup>44</sup> 1</td><td>cn CN CN</td><td> 1 3·<sup>95</sup> 1</td><td> 1 2-55 |</td><td> | 3.22 |</td>
<td>4HT / Quadrol</td><td> | 2.23</td><td> | 1.55</td><td>1 l<sup>44</sup></td><td>tO CN t — 1</td><td> 1 1--02</td><td>cn 00 or</td><td>CN t — 1 i — 1</td><td>CO CO T—)</td>
<td>4HT / THEED</td><td> 2.28</td><td> 1.50</td><td> 1.41</td><td> 1.17</td><td> 0.95</td><td> 0.79</td><td> 1-09</td><td> 1.70</td>
<td>4HT / TIPA</td><td>1 1X51</td><td>Γ or Rh</td><td> | 88’0 !</td><td> | 0.77 |</td><td>CN CO or</td><td> ¡ 0-31 1</td><td> | 0.68 1</td><td> 1 °·<sup>75</sup> 1</td>
<td>ffl</td><td>H Ul</td><td>H m</td><td>rH in</td><td>H in</td><td>rH in</td><td>Rh in</td><td>ΓχΐΊ</td><td> 1 5·<sup>1</sup></td>
<td>Active Dose (ppm) of 4HT + Amine</td><td>I 297 + 3 I</td><td>CO 4-tr oí CN</td><td>I 285 + 15]</td><td>I 270 + 30 I</td><td>| 255 + 45 I</td><td> | 240+60 1</td><td>I 210 + 90</td><td> | 150+150</td>
<td>Dose Total (ppm)</td><td>I 300</td><td>I 300</td><td> 00£ |</td><td>I 300</td><td>Γ ooo</td><td>I 300 1</td><td> 1 <sup>300</sup></td><td> 1 300</td>
<td rowspan="2">Dose Active Proportion of 4HT: Amine</td><td>I — í</td><td>CN</td><td>IT</td><td>Or rH</td><td>LO rH</td><td>Or CN</td><td>Or cn</td><td>Or LD</td>
<td>Ch 01</td><td>00 OI</td><td>i heard</td><td>or OI</td><td>IT CO</td><td>I 80:</td><td>or r-</td><td> | 50:</td>
<img file="MX339245B_D0043.tif" />
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
Contents14
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70 members in 25 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 3383MUM2011 | India | – | |
| 3383MU2011 | India | A | |
| 2012000758 | India | W | |
| 3383MUM2011 | – | – | – |
| IN1200758 | – | – | – |
| IN2011MUM3383 | – | – | – |
| WO2012IN00758 | – | – | – |
Members70
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| CA2857087A1 | Canada | A1 | |
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| WO2013105113A1 | World Intellectual Property Organization (WIPO) | A1 | |
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1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 339245
- Publication, DOCDB
- 339245
- Publication, EPODOC
- MX339245
- Application
- 2014006406
- Application, DOCDB
- 2014006406
- Application, EPODOC
- MX20140006406
Titles2
- Spanish
- COMPOSICION DE ADITIVO A BASE DE AMINA Y NITROXIDO PARA EL CONTROL Y LA INHIBICION DE LA POLIMERIZACION DE ESTIRENO, Y METODO DE USO DE LA MISMA.
- English
- COMPOSITION OF ADDITIVE BASED ON AMINE AND NITROXIDE FOR THE CONTROL AND INHIBITION OF THE POLYMERIZATION OF STYRENE, AND METHOD OF USE OF THE SAME.
Classification
- CPC, 9
- C07C7/20
- C08F2/38
- C09K15/20
- C08F2/40
- C08F2438/02
- C08K5/17
- C08K5/32
- C07B63/04
- C08F12/08
- IPC, 2
- C08K5 17
- C08K5 32