MXPA00002907A - Composition preventing polymerisation of ethylenically unsaturated monomers - Google Patents
Composition preventing polymerisation of ethylenically unsaturated monomersInfo
- Publication number
- MXPA00002907A MXPA00002907A MXPA/A/2000/002907A MXPA00002907A MXPA00002907A MX PA00002907 A MXPA00002907 A MX PA00002907A MX PA00002907 A MXPA00002907 A MX PA00002907A MX PA00002907 A MXPA00002907 A MX PA00002907A
- Authority
- MX
- Mexico
- Prior art keywords
- composition according
- composition
- catechol
- tert
- carbon atoms
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 150000008378 aryl ethers Chemical class 0.000 claims abstract description 18
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 16
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-Butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000002401 inhibitory effect Effects 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 230000002194 synthesizing Effects 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- -1 4-isopropoxytechol Chemical compound 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N Catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N Anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- PJZLSMMERMMQBJ-UHFFFAOYSA-N 3,5-ditert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC(O)=C(O)C(C(C)(C)C)=C1 PJZLSMMERMMQBJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N Cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N Piperylene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- PCPYTNCQOSFKGG-ONEGZZNKSA-N (1E)-1-chlorobuta-1,3-diene Chemical compound Cl\C=C\C=C PCPYTNCQOSFKGG-ONEGZZNKSA-N 0.000 claims description 2
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 claims description 2
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 claims description 2
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 claims description 2
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GSYRNBLFBPODTD-UHFFFAOYSA-N 3,6-di(propan-2-yl)benzene-1,2-diol Chemical compound CC(C)C1=CC=C(C(C)C)C(O)=C1O GSYRNBLFBPODTD-UHFFFAOYSA-N 0.000 claims description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-Methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 claims description 2
- LRHCHWXTHWGCKK-UHFFFAOYSA-N 3-butyl-5-methylbenzene-1,2-diol Chemical compound CCCCC1=CC(C)=CC(O)=C1O LRHCHWXTHWGCKK-UHFFFAOYSA-N 0.000 claims description 2
- XLZHGKDRKSKCAU-UHFFFAOYSA-N 3-isopropylcatechol Chemical compound CC(C)C1=CC=CC(O)=C1O XLZHGKDRKSKCAU-UHFFFAOYSA-N 0.000 claims description 2
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-Methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 claims description 2
- APKDDKUIEPOCMZ-UHFFFAOYSA-N 5-methyl-3-octylbenzene-1,2-diol Chemical compound CCCCCCCCC1=CC(C)=CC(O)=C1O APKDDKUIEPOCMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N Methyl vinyl ketone Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 230000000875 corresponding Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000002028 premature Effects 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 claims 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims 1
- 239000008240 homogeneous mixture Substances 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 5
- 230000005712 crystallization Effects 0.000 description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N Isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N Ethyl phenyl ether Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001766 catechin derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention concerns a composition for preventing radical polymerisation of ethylenically unsaturated monomers characterised in that it comprises at least a cathechol derivative and at least an aromatic ether.
Description
COMPOSITION THAT PREVENTS THE POLYMERIZATION OF MONOMERS WITH ETHYLENE INSATURATION
DESCRIPTION OF THE INVENTION
The present invention aims at a liquid composition in a range of temperature ranging from room temperature to -20 ° C, which can be used as an inhibitor of the radical polymerization of ethylenically unsaturated monomers. This relates more particularly to vinyl monomers. The invention also considers the method of preparing the composition. Monomers by ethylenic unsaturation are prone to polymerize spontaneously with the action of heat. However, premature polymerization must be avoided at the time of manufacture, purification and storage of said monomers. In the course of manufacturing or purification, early polymerization is detrimental since it causes a drop in production yields and a clogging of the installations, often making it necessary to temporarily stop production for maintenance reasons. there is an extra cost of production. Due to the exothermicity of the polymerization reaction, explosions and fires are equally to be feared. Now, certain monomers with ethylenic unsaturation are particularly subject to such polymerization reactions. This is mainly the case of the mono- and diolefins and more particularly of the diolefins with conjugated double bonds, for example, isoprene and 1,3-butadiene, as well as the vinyl compounds. In order to prevent the polymerization of the monomers by ethylenic unsaturation, it is known in the art to add one or more polymerization inhibitors or retarders, either preventatively in the course of manufacture, or even directly to said monomers before their utilization. These compounds are generally inhibitors of radical polymerization. It is equally useful in this technical domain to have an urgency inhibitor capable of stopping the polymerization of said monomers in the classical synthesis processes by polymerization, in the case where a technical problem occurs on the installation.
The main inhibitor used is 4-tert-butylcatecal, which is added alone or possibly in a mixture with other inhibitors. For this purpose, mention may be made of U.S. patents US 2 478 710 US 3 405 189 and Japanese patent JP 19 633/64, which describe the stabilization of butadiene, isoprene and 1, 3- pentadiene and cyclopentadiene. Similarly, the French patent FR 2 696 17i, the United States patent US 3 390 198 and the European patent 403 672 illustrate the stabilization of the vinyl monomers. More generally, reference may be made to United States patents US 2 925 449 and US 4 487 981. 4-tert-Butylcatechol is a solid compound at room temperature. Its melting point is 54 ° C. In this way, in order to make easily injected at the level of the boilers, deposits, reactors, storage lines and the refluxes of distillation of industrial facilities, this must be previously solubilized, either in the monomer to be stabilized, or in a given organic solvent. Thus, 4-tert-butylcatechol is marketed by the company RHONE-POULENC, in the form of a composition in water, in methanol, in isobutanol, in toluene and in xylene. These compositions do not give entirely satisfaction since they are not liquid. negative temperatures, that is, lower than 0 ° C. In fact, 4- tert-butylcatechol has a crystallization point higher than 0 ° C in methanol, toluene and xylene. On the other hand, under particular conditions and mainly under vibrational or mechanical constraints, a partial crystallization of 4-tert-butylcatechol from the corresponding compositions in water and isobutanol is observed at a temperature above 0 ° C. In this way, in order to avoid a crystallization of 4-tert-butylcatechol, the commercial solutions described above are preheated between 20 ° C and 60 ° C and maintained at these temperatures in order to be injected over the manufacturing processes of the objective monomers , which implies the use of industrial lines with thermostats. The present invention contemplates providing the compositions based on 4-tert-butylcatechol which can be used as the polymerization inhibitor and which do not have the drawbacks of the compositions of the prior art, ie liquids at temperatures ranging from ambient temperature .up to approximately -20 ° C. At these temperatures in effect, the compositions of the invention remain in the liquid form without it being possible to observe the crystallization or the vitrification of 4-tert-butylcatechol. Precisely, the compositions of the invention that are liquid in the range that goes from room temperature to a temperature of
-20 ° C, they compose at least one catechol derivative and at least one aromatic ether. By 'ambient temperature' 'is meant in general, a temperature comprised between a range of temperatures ranging from 15 ° C to 25 ° C. It should be noted that the upper end of the temperature range does not present any critical character. Preferably, the compositions of the invention comprise at least one or more catechol derivatives of the formula (I):
R * (I)
- in said formula: Ri, R2, R3 and R, identical or different, represent a hydrogen atom, an alkyl group or an alkoxy group, at least one substituent between Ri, R2, R3 and R represents a hydrogen atom , • at most three substituents between Ri, R2, R3. and R4 represent a hydrogen atom. By "alkyl" is meant in accordance with the invention a straight or branched hydrocarbon chain such as, for example, methyl, n-butyl, tert-butyl, n-propyl, isopropyl and octyl. "" By 'alkoxy' is meant according to the invention an alkyl-oxy group wherein the alkyl group is as defined above. Preferably, the alkoxy group is an isopropoxy group. In the present text, the expression 'catechol derivative' encompasses the compounds of the formula (I), with the exception of the catechol in which Ri, R2, R3 < - and R represent all one hydrogen atom. Preferred of catechol derivatives is that composed of compounds of the formula (I) in which Ri, R2, R3 and R are identical or different, chosen from a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, preferably, from 1 to 4 carbon atoms and an alkoxy group of 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms Another group of preferred derivatives of catechol consists of the compounds of the formula (I) in which at least three substituents between Ri, R2, R3 and R represent a hydrogen atom, among which those for which the fourth substituent Ri, R2, R3 or R is chosen from an alkyl group of 1 to 12 carbon atoms , preferably, from 1 to 4 carbon atoms and an alkoxy group of 1 at 12 carbon atoms, preferably 1 to 4 carbon atoms, are still more advantageous. A third group of preferred compounds is that composed of 3-methylcatechol, 4-methylcatechol, 3-isopropylcatechol, 3-butyl-5-methylcatechol, 4-tert-butylacecol, 3,5-di-tert-butylcatechol, 4,6- di-tert-butylcatechol, 3-octyl-5-methylcatechol, 4-isopropoxytechol, 3,6-diisopropylcatechol and their mixtures. It will be noted that all catechol derivatives are marketed or easily prepared by an expert in the field. Among these catechol derivatives, 4-tert-butylcatechol is the preferred compound. Another feature of the composition of the invention is that it comprises, as a solvent, an aromatic ether. In the following discussion of the present invention, the term 'aromatic ether' means an aromatic compound in which a hydrogen atom directly linked to the aromatic nucleus is replaced by an ether group and by 'aromatic compound', the classical notion of aromaticity such as it is defined in the literature, mainly by Jerry MARCH, Advanced Organic Chemistry, 4th edition, John Wiley and Sons, 1992, pp. 40 and subsequent. Several criteria preside over the choice of solvent. The catechol derivative must be soluble in the aromatic ether and must not crystallize at the temperature of use.
The aromatic ether must be liquid in the temperature range of use and have a crystallization temperature below 0 ° C, preferably below -20 ° C. For more precise jnanexa, the aromatic ether suitable for the invention can be represented by the general formula (II):
II)
in said formula (II), the different symbols represent: R5 represents a linear or branched alkyl group having from 1 to 4 carbon atoms; And it represents a chlorine or fluorine atom. As examples of groups R5, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups. It is also possible to put into operation a mixture of aromatic ethers.
The aromatic ethers put into operation most preferably in the compositions of the invention are: anisole, phenetol, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 2-fluoxoanisole, 4-fluoroanisole. Anisole is the preferred solvent put into operation in the compositions of the invention. This one presents interesting properties. This is a non-toxic, thermally stable product that has a high boiling point (154 ° C) and a high ignition point (51 ° C). The compositions of the invention comprise at least one or a derivative of catechol and an aromatic ether. The proportions by mass of each constituent are easily determined by the person skilled in the art. The composition obtained should ensure a maximum stability of the catechol derivative that should not solidify or crystallize in the temperature range considered.
Preferred compositions of the invention comprise: from 30 to 60% by weight of catechol derivative (s), from 40 to 70% by weight of aromatic ether (s). In order to obtain a liquid composition at a temperature below -10 ° C, it is preferably operated: - from 30 to 50% by weight of catechin derivative (s), from 50 to 70% by weight of ether ( is) aromatic (s). Reference can be made to the examples they need according to the temperature, the shape of the composition obtained. As far as the method of preparing the compositions of the invention is concerned, this is any where the latter leads to a homogeneous composition. The constituents of the claimed composition can be mixed in any order, at room temperature or at a higher temperature, for example between 50 ° C and 60 ° C.
The compositions of the invention are polymerization inhibiting agents. These can therefore be used as stabilizers of the ethylenically unsaturated monomers which are most susceptible to degradation by polymerization, either by direct addition to said pure monomers or by addition to the monomer solutions. However, according to a preferred embodiment, the compositions of the invention are used as polymerization inhibitors in the course of synthesis of said manomeres. These are added to the reaction medium no matter at what stage of the synthesis procedure. According to other aspects, the invention relates to a method for preventing the polymerization of a monomer with ethylenic unsaturation at the time of the synthesis of said monomer comprising the addition to the reaction medium of a composition of the invention in a any stage of said synthesis process. It is not useful to add a large amount of the polymerization inhibitor. The optimum amount that must be added depends on the nature of the monomer by ethylenic unsaturation to be stabilized.
Thus, the ideal amount of the inhibitor should be evaluated on a case-by-case basis. In general, the composition of the invention is added in an amount such that the concentration of the catechol derivative (s) is between 10 and 300 ppm, preferably between 50 and 120 ppm. The compositions of the invention are particularly suitable in the case where the ethylenically unsaturated monomer is chosen from vinyl monomers, cyclopentadiene and dicyclopentadiene. According to the invention, the expression
"vinyl monomers" encompasses all compounds that have at least one vinyl group, among which are styrene and its derivatives of the α-methylstyrene type, vinyltoluene and divinylbenzene, acrylic acid and its esters such as acrylate, methyl, ethyl acrylate, butyl acrylate, esters of methacrylic acid such as methyl methacrylate, methyl vinyl ketone, acrylonitrile, isoprene, 2,3-dimethylbuta-l, 3-diene, chloroprene, bromoprene, 1-chlorobutadiene, vinyl chloride and 1,3-pentadiene.
The process of the invention is particularly effective when the monomer with ethylenic unsaturation is 1,3-butadiene or isoprene. It is also useable at the time of the isolation and purification of the hydrocarbon mixtures of 4 carbon atoms resulting from the steam disintegration of the petroleum cuts, and more particularly when they contain at least 43% of 1,3-butadiene. The composition of the invention is advantageously used as an emergency inhibitor during the synthesis of polymers from
monomers with ethylenic unsaturation, preferably styrene and its derivatives. The following examples are given by way of illustration and refer to the preferred embodiments of the invention. In the examples, the percentages expressed are percentages by weight.
EXAMPLES 1 TO 8:
In these examples, the compositions based on 4-tert-butylcatechol and anisole are prepared by mixing, at room temperature, two constituents, in the proportions indicated in Table I below. Said compositions are studied by differential calorimetric analysis with the aid of the Mettier® DSC 30 apparatus, between -150 ° C and 100 ° C in order to highlight the solid / liquid transitions • The compositions comprising 20%, 40% and 60% % of 4-tert-butylcatechol are studied by DSC. The results show that for 20% 40% and 60% of 4-tert-butylcatechol, the solid / liquid transition is not seen and the glass transition temperature is lower than -80 ° C. All the mixtures are stored at different temperatures, either at room temperature, either in the refrigerator or in the freezer. The results observed in storage are summarized in the following table:
Table (I)
The results show that the numexous compositions remain liquid over a wide range of temperatures. In this way, it can be considered to use them directly in the industrial units, such as without previous overheating.
EXAMPLES 9 TO 13:
In the following examples, the compositions based on 4-tert-butylcatechol and fenetol are prepared by mixing at room temperature of 2 constituents in the proportions indicated in table (II). All the mixtures are stored 8 days at different temperatures and the observed results are summarized in the following table:
Table (II
In these examples, numerous compositions remain liquid at very low temperature.
Claims (20)
1. Liquid composition in the range from room temperature to a temperature of -20 ° C, comprising at least one catechol derivative and at least one aromatic ether.
2 ^ Composition according to claim 1, characterized in that it comprises at least one or more catechol derivatives of the formula (I): OH \? 7 R / 1 R3 (I) in said formula: Ri, R2, R3 and 4, identical or different, represent a hydrogen atom, an alkyl group or an alkoxy group; at least one substituent between Ri, R2, R3 and R4 represents a hydrogen atom; at most three substituents between Ri, R2, R3 and R4 represent a hydrogen atom.
3. Composition according to claim 2, characterized in that the catechol derivative corresponding to formula (I) in which Ri, R2, R3 and R4, identical or different, are chosen from a hydrogen atom, a gxupo alkyl of 1 to 12 carbon atoms, preferably of 1 to 4 carbon atoms and an alkoxy group of 1 to 12 carbon atoms, preferably of 1 to 4 carbon atoms.
4. Composition of confounding with any of claims 2 and 3, characterized in that the catechol derivative corresponds to the formula (I) in which at least three substituents between Ri, R2, R3 and R4 represent a hydrogen atom.
5. Composition according to any of claims 2 to 4, characterized in that it comprises one or more catechol derivatives chosen from 3-methylcatechol, 4-methylcatechol, 3-isopropylcatechol, 3-butyl-5- methylcatechol, 4-tert-butylcatechol, 3, 5-di-tert-butylcatechol, 4,6-di-tert-butylcatechol, 3-octyl-5-methylcatechol, 4-isopropoxytechol, 3,6- diisopropylcatechol and its mixtures.
6. Composition of confounding with claim 5, characterized in that it comprises 4-tert-butylcatechol.
7. Composition according to any of claims 2 to 6, characterized in that it comprises an aromatic ether of general formula (II): (ID in the formula (II), the different symbols represent: R5 represents a linear or branched alkyl group having from 1 to 4 carbon atoms; And it represents a chlorine or fluorine atom.
8. Composition according to claim 7, characterized in that the aromatic ether xesponde to the genexal formula (II) in which the gxupo R5 represents a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl group, sec-butyl, tert-butyl.
9. The composition according to any of claims 7 and 8, characterized in that it comprises an aromatic ether selected from: anisole, phenethol, 2-chloroanisole, 3-chloroanisole, 4-chloroanisole, 2-fluoroanisole, 4-fluoroanisole.
10. Composition according to any of claims 7 to 9, characterized in that it comprises anisole and / or phenethol.
11. Composition according to any of claims 1 to 10, characterized in that it comprises: from 30 to 60% by weight of catechol derivative (s); from 40 to 70% by weight of aromatic ether (s).
12. Composition according to claim 11, characterized in that it comprises: from 30 to 50% by weight of catechol derivative (s); 50 to 70% by weight of aromatic ether (s).
13. Composition according to any of claims 1 to 12, characterized in that it is used as an inhibitor of the polymerization of monomers with ethylenic unsaturation.
14. Process for preparing a composition described in any of claims 1 to 13, characterized in that it consists of preparing a homogeneous mixture of at least one or more derivatives of catechol and one or more aromatic ethers.
15. Process for preventing the radical polymerization of a monomer with ethylenic unsaturation, at the time of the synthesis of said monomer, comprising the addition to the reaction medium of a composition according to any of claims 1 to 12, in any one step of said synthesis procedure.
16. Process according to claim 15, characterized in that the amount of additional composition is such that the concentration in derivative (s) of catechol is between 10 and 300 ppm, preferably between 50 and 120 ppm relative to the weight Total monomer.
17. Process according to any of claims 15 and 16, characterized in that the monomer with ethylenic unsaturation is chosen from vinyl monomers such as styrene and its derivatives, preferably a-methylstyrene, vinyltoluene and divinylbenzene; acrylic acid and its esters preferably, methyl acrylate, ethyl acrylate, butyl acrylate; esters of methacrylic acid, preferably methyl methacrylate; methyl vinyl ketone; acrylonitrile; isoprene; 2, 3-dimethylbuta-1, 3-diene; Chloraprene; bromopene; 1-chlorobutadiene; vinyl chloride and 1,3-pentadiene; cyclopentadiene and dicyclopentadiene.
18. Process according to claim 17, characterized in that the monomer with ethylenic unsaturation is 1,3-butadiene and isoprene.
19. Process for preventing premature polymerization at the time of isolation and purification of hydrocarbon mixtures of 4 carbon atoms, originating from the steam disintegration of petroleum cuts containing one or more monomers with ethylenic unsaturation, such as 1, 3-butadiene and isopxene, which comprises the addition of a confounding composition with any of the claims 1 to 12.
20. Use of the liquid composition declines in any of the claims 1 to 12, as an emergency inhibitor during the synthesis of polymers from monomers with ethylenic unsaturation, preferably styrene and its derivatives.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR97/11890 | 1997-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA00002907A true MXPA00002907A (en) | 2001-05-17 |
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