MXPA96006243A - Esterification of acid (met) acrylic with an ftaa - Google Patents
Esterification of acid (met) acrylic with an ftaaInfo
- Publication number
- MXPA96006243A MXPA96006243A MXPA/A/1996/006243A MX9606243A MXPA96006243A MX PA96006243 A MXPA96006243 A MX PA96006243A MX 9606243 A MX9606243 A MX 9606243A MX PA96006243 A MXPA96006243 A MX PA96006243A
- Authority
- MX
- Mexico
- Prior art keywords
- acid
- meth
- acrylic
- acrylic acid
- dissociation
- Prior art date
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000004821 distillation Methods 0.000 claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000007858 starting material Substances 0.000 claims abstract description 10
- 239000003377 acid catalyst Substances 0.000 claims abstract description 9
- 238000010494 dissociation reaction Methods 0.000 claims description 41
- 230000005593 dissociations Effects 0.000 claims description 41
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 102000004196 processed proteins & peptides Human genes 0.000 claims 1
- 108090000765 processed proteins & peptides Proteins 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 16
- 239000000047 product Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000003776 cleavage reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N Phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- 229950000688 Phenothiazine Drugs 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-Ethylhexanol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-Hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- KWXICGTUELOLSQ-UHFFFAOYSA-N 4-Dodecylbenzenesulfonic Acid Chemical compound CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229940047670 SODIUM ACRYLATE Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M Sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000001154 acute Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- IKRARXXOLDCMCX-UHFFFAOYSA-N butyl 2-butoxypropanoate Chemical compound CCCCOC(C)C(=O)OCCCC IKRARXXOLDCMCX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VABBJJOSOCPYIT-UHFFFAOYSA-N methyl 2-methoxypropanoate Chemical compound COC(C)C(=O)OC VABBJJOSOCPYIT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Abstract
The present invention relates to: In a process for (meth) acrylic esterification with alkanol in the presence of an esterification catalyst in which unreacted starting compounds and (meth) acrylic ester are separated by distillation and a lower product containing esters oxi is obtained, the lower product is separated and the lower product is directly mixed with oligomeric (meth) acrylic acid and the oxi esters present in the lower product are dissociated at an elevated temperature in the presence of acid catalysts different from the oligomeric (meth) acrylic acid or, The oxy-esters are first separated by distillation from the lower product, the distillate is mixed with oligomeric (meth) acrylic acid and dissociated at an elevated temperature in the presence of different acid catalysts (meth) acrylic oligomer.
Description
ESTERI FICAC ION DE ACIDO (MET) ACRI LICO WITH AN ALCANOL
The invention relates to a process for the esterification of (meth) acrylic acid with an alkanol in the presence of an esterification catalyst, in which the unreacted starting compounds and the (meth) acrylic ester formed are separated by distillation and a lower product comprising oxi esters is obtained. The term (meth) acrylic acid here denotes, as is customary, acrylic or methacrylic acid. The preparation of alkyl esters of (meth) acrylic acid is usually carried out by esterification of (et) acrylic acid with alkanols at elevated temperature in the liquid phase, in the presence or absence of solvent and in the presence of acid as catalyst (DE-A 29 39 519). A disadvantage of this method of preparation is the side reactions that occur under the esterification conditions mentioned above, namely, the unreacted starting alcohol is added to the double bond of alkyl (meth) acrylate already formed (Michael addition) to provide a compound of the general formula I below and the unreacted (meth) acrylic acid is added to the double bond of the ester formed to provide a compound of the general formula II. Multiple addition is also possible. In addition, mixed types may occur. These adducts (aleo xi esters and acyloxy esters) are abbreviated as oxy esters.
RO- (CH, CH-C02)? - (I)
R 'R' CH2 = C-C02- (CH2-CH-C02) -R (II) where x, y = 1-5 R = alkyl R '= H or CH3 When R' = H, the esterification is of acrylic acid, when R '= CH3, the esterification is methacrylic acid. The problem of oxy-ester formation is particularly acute in the preparation of acrylic acid esters, with the principal oxy-esters formed being alkoxypropionic esters and acrylic loxipropionic esters, wherein 2, y = 1. In the preparation of alcoholic acid esters methacrylic, the formation of oxi ester occurs to a lesser degree. The formation of oxy esters is disclosed in DE-A 23 39 529. This indicates that the formation of oxy esters occurs essentially independently of the specific esterification conditions. Of particular importance is the formation of oxy ester in the preparation of C.sub..C0 alkanoyl acrylates, in particular C.sub.G-alkanoles, very particularly in the preparation of n-butyl acrylate and sodium acrylate. 2-eti lhexi lo. It is a characteristic of the oxy esters that their boiling point is above the boiling point of the starting acid, partic alcohol, meta ester formed and any organic solvent also used. The work of any esterification reaction mixture of these is usually carried out by separating unreacted starting compounds and the meta ester from the reaction mixture by distillation, with the acid catalyst used so that the esterification is capable to be removed with antipathy, if appropriate, by extraction with water and / or aqueous alkali (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, Vol. Al, 5th ed. VCH, p. 167 ff). The lower product remaining in said distillation work contains the oxy esters which results in a considerable loss in yield. Due to this reason, several additional methods have been examined in order to solve the problems that result from the formation of oxy esters. Thus, JP-A-82/62229 describes the alkaline saponification of the high boiling esterification residues. In this way, part of the used alcohol, acrylic and beta-hydroxypropionic acid or its salts are recovered, a simple and economical return of the products, the esterification reaction, therefore, is not possible. JP-B-72/15936 describes the preparation of acrylic esters with beta-alkoxypropionic esters reaction with acrylic acid in the presence of strong acids (transesterification). Nevertheless, this forms as equimolar amounts of beta-alkoxypropionic acid by-product that can not be returned to the transesterification reaction and, therefore, represent waste material. JP-A-93/25086 describes the dissociation of the addition product of Michael butyl beta-butoxypropionate (see formula I, x = 1, R = butyl) at elevated temperature and in the presence of sulfuric acid and an excess of water. However, the yield is only about 30%. Finally, JP-A-94/62149 discloses the dissociation of Michael addition products I and II (see above, x = y = 1) in the presence of alkoxides of tj_ tanium. In this reaction, the conversion is also low (c 60%) and large amounts of titanate are necessary. This procedure, therefore, is not economically and environmentally unfriendly due to the large amounts of titanate that must be discarded. GB 923 595 describes the recovery of monomers from the residue of the esterification of acrylic acid with alkanes in the absence of molecular oxygen. It recommends, among others, the removal of all volatile monomers before dissociation, the dissociation in the presence of sulfuric acid and the removal of the dissociation products by means of a stream of inert gas. According to the examples, dissociation is always carried out at least 300eC Coke is formed as waste (17-40%) and this has to be removed from the reaction. This procedure, therefore, is not economical and can not be carried out. out on an industrial scale. A further disadvantage is the need to exclude oxygen. CN-A 1,063,678 discloses the dissociation of the alkoxy propionic ester present in the cleavage residue in the presence of sulfuric acid in a cascade, with temperature and catalyst concentration (0.8-1.5% being different in each reactor) Coupled with the dissociation is a Distillation to separate alkanol and acrylate The process is very troublesome and does not achieve high conversions Finally, CN-A 1,058,390 describes the dissociation of alkoxypropionic esters in the presence of sulfuric acid, etc., in alcohols and acrylic esters. The dissociation is first carried out under reflux and the reaction products are subsequently distilled.The dissociation of ester residues containing acrylic acid from the preparation of ethyl / methyl acrylate (ethyl ethoxypropionate, methyl methoxypropionate) is carried out in the presence of eta nol or methanol, and here too, the procedure is complicated and it does not convert One object of the present invention is to carry out the redissociation of the oxy esters present in this lower product and to reuse the starting acid, starting alcohol and the goal ether obtained therefor for the purposes of This rification without the disadvantages of the procedures of the previous technique. It has been found that this object is achieved by a process for esterifying (meth) acrylic acid with an alkane in the presence of an esterification catalyst in which the unreacted starting compounds and the (meth) acrylic ester formed are Separate by distillation and! a lower product containing oxi esters is obtained, wherein the lower product is separated and either (a) the lower product is mixed directly with oligomeric (meth) acrylic acid and the oxy esters present in the lower product dissociate a high temperature in the presence of acid catalysts other than oligomeric (meth) acrylic acid, or (b) the oxy esters are first separated by distillation from the lower product, the distillate is mixed with oligomeric (meth) acrylic acid and it is dissociated at an elevated temperature in the presence of acid catalysts different from oligomeric (meth) acrylic acid. The alcohol is preferably n-butanol or 2-ethylhexanol. In general, from 10 to 50% by weight, preferably from 10 to 40% by weight, based on the quantity d product lower in (a) or distilled in (b), of (meth) ac acid oligomeric is added. The oligomeric acrylic acid is normally used in a manner known per se, it is stabilized by means of polymerization inhibitors. Advantageously, the oligomeric (et) acrylic acid used for this purpose is the lower product obtained in the purification of crude acrylic acid distillation, this lower product comprises mainly compounds of formula III below (see, for example, example, DE 22 35 326):
CH2 = CH-C02- (CH2CH2C02) -H (III) x = 1-5 The oligomers of (meth) acrylic acid can be added to the mixture to be dissociated before dissociation. They can also be fed separately to the dissociation reactor
These: olomers are not free-radical oligomers, eg Michael's adducts of the acid with itself, as they are obtained as by-products, for example, in the distillation of (meth) acrylic acid. These oligomers are usually burned as non-recyclable by-products from the production of (meth) acrylic acid. Under the conditions of redissociation, these oligomeric (meth) acrylic acids are also redissolved, continuously generating free (meth) acrylic acid in statu nascend
Compared with a previous addition of (meth) acrylic acid, this has the advantage that the added (meth) acrylic acid is not distilled immediately together with the dissociation products, but that the dissociation proceeds continuously in the presence of acid (et) acrylic, resulting in reduced formation of secondary products (dialkyl ethers, olefins). In accordance with an advantageous embodiment of the invention, the process of or sociation is carried out in the presence of molecular oxygen. According to a further advantageous embodiment of the invention, the product to be dissociated has added, in addition to the acid esterification catalyst which is different from the oligomeric (meth) acrylic acid and additional acids may already be present. selected from the group consisting of mineral acids such as sulfuric acid or phosphoric acid, and organic acids other than oligomeric (meth) acrylic acid, for example alkyl or aryl sulfonic acids, such as methanesulfonic acid or p-acid. -toluenesulfonic. The total amount of different acid of the oligomeric (meth) acrylic acid which is then present may be from 1 to 20% by weight, preferably from 5 to 15% by weight, based on the amount of the lower product in ( a) or distilled in (b). It is particularly useful if a scrubbing gas containing preferably molecular oxygen is passed through the lower product in (a) or the distillate in (b) as a trap for the cleavage products. The air or mixtures of air with inert gas (eg nitrogen) are advantageously used as a purification gas. The advantages of the process of the present invention in particular are that the dissociation proceeds more rapidly and that a smaller amount of side products such as ethers or olefins is formed. In this way, among other things, minor losses of starting materials, particularly alcohols, occur in known processes. In addition, the dissociation yields high. The direct return of the dissociation mixture does not adversely affect the purity of the (meth) acrylic ester and leads to a low ether content. Due to this reason, complicated separation of the ether from the easily polymerizable (meth) acrylic ester is not necessary. In total, this also means reduced environmental pollution, since smaller amounts of waste are obtained. In the distillative separation of the oxy esters from the lower product, the distillation conditions depend on the type of alcohol component used in the esterification. In general, a temperature of 100 to 300eC and a pressure of 1 to 50 mbar are used. Any conventional distillation apparatus is suitable for the distillation process. Since only a simple separation task is going to be performed, a simple splash guard is usually sufficient ie a column is not normally required. For the dissociation of the oxy-esters separated by distillation or present in the lower product, a simple stirred, heatable reactor, with a heating jacket or heating coil, or a flushed circulation evaporator can be used., for example, a falling film evaporator or flash evaporator, coupled with a residence time container. In order to achieve better separation of the dissociation products, it may be advantageous to use a grinding fixation superimposed on the dissociation apparatus, for example, a packed or tray column. This fixation fixation is generally operated using stabilization by polymerization inhibitors (e.g., phenothiazine, hydroquinone monomethyl ether, etc.). The conditions for carrying out the process of the present invention to dissociate oxy esters formed in the lower product in the esterification or separated from the lower-product are as follows: Catalyst: at least one acid selected from the group consisting of Minor acids, for example sulfuric acid and phosphoric acid, and organic acids other than oligomeric (meth) acrylic acid, for example alkyl- or arylsulfonic acids such as methanesulfonic acid or p-to-luenesulfonic acid. Catalyst amount 1-20% by weight, preferably 5-15% by weight, based on the amount of the lower product in (a) or the oxy-ester distillate separated from the lower product in (b)
Amount of acid 5-50% by weight, preferably 10-40% in (meth) acrylic 1 oligomer weight, based on the amount of lower -rich product in (a) or of the oxy-distillate separated from the lower product in (b) Temperature: 150-2509C, preferably 180-230eC Pressure: preferably atmospheric pressure or under reduced pressure (so that the dissociation products vaporize immediately) - 1 atm) Purification gas, if quantity is used: 1 -100 1 / h Reaction time: 1-10 hours Conversion: 90% The reaction is carried out, for example, by the lower product to be dissociated which is continuously taken from the distillation work of the esterification mixture and is fed together with the dissociation catalyst to the dissociation reactor. However, the reaction can also be carried out batchwise. It is also possible to use a semi-continuous reaction process in which the product to be dissociated is continuously fed to the dissociation reactor (containing the dissociation catalyst), and the lower product is batch-removed from the dissociation reactor only. after the dissociation is completed. The cleavage products are continuously removed by distillation. The applicability of the described dissociation process is not restricted to a specific type of esterification process from which the oxy-esters, that is, addition compounds I and II, are obtained as by-products. In general, esters are prepared by customary methods (see Ull ann's Encyclopedia of Industrial Chemistry, Vol. Al, ta.Ed., VCH, p.167 ff.). A typical example of the conditions under which the esterification preceding the dissociation of the oxi esters may occur may briefly be as follows: Alcohol: (meth) acrylic acid 1: 0.7-1.2 (molar) Catalyst: acid sulfuric or sulfonic acids Quantity of catalyst- 0.1-10% by weight (preferably 0.5-5% by weight) based on the starting material
Stabilization: 200-2,000 ppm phenothiazine (based on - the weight of the starting materials) Reaction temperature: 80-160eC, preferably 90-130 ^ 0 Reaction time: 1-10 hours, preferably 1-6 hours If desired, a trap (e.g., cyclohexane or toluene) can be used to remove the esterification water. The esterification can be carried out at atmospheric pressure, under superatmospheric pressure or subatmospheric pressure, either continuously or batchwise. In the acid catalyzed esterification of acrylic acid with alkanols, the lower product obtained after removing the acid esterification catalyst, the unreacted starting materials and the acrylic ester generally has the following composition: 1-20 % by weight of acrylic ester 50-80% by weight of alkoxypropionates (see formula I) 5-30% by weight of acyloxypropionates (see formula II) remainder: mainly stabilizers (phenotiazione) and polymers Additional details and advantages of the process of the present invention can be taken from the examples described below.
First, a result achieved using a process not in accordance with the present invention will be described by means of a comparison example.
EXAMPLE OF COMPARISON A glass circulation reactor (volume: 1 l) heated by a heating plug was charged with 50 g of an Oxy distillate obtained from an esteri cation residue from n-buty production. lacrylate which had been liberated from the acid esterification catalyst, together with 40 gd p-toluenesulfonic acid. The oxy-ester distillate comprised: 11.0% by weight of buty lacrylate 64.8% by weight of butoxy ester I (R = C4Hg) 20.5% by weight of acyloxy ester II (R = C4Hg) The dissociation temperature was 195 SC and the Operation pressure was 1 atm. During the dissociation, the esterification residue to be dissociated was continuously fed to the digestion reactor, regulated by the level in the reactor. The cleavage products were removed in vapor form and condensed on the top of the column 950 cm x 2.8 cm, empty) superimposed on the dissociation reactor. During a period of 119.5 hours, 7.401 g of mixture were fed to the dissociation reactor and 7,080 g were condensed. of di-sociation products.
According to analysis by gas chromatography, the condensate comprised: 72.0% by weight of butyl alcohol 13.9% by weight of butanol 4.8% by weight of acrylic acid 1.4% by weight of dibutyl ether 6.6% by weight of butenes 0.2% by weight of butyl butoxypropionate Conversion: 96% by weight based on oxy esters. The lower cleavage products were still easily manageable (pumpable) at 25 ° C and had no solids.
EXAMPLE OF THE PROCESS OF THE PRESENT INVENTION A glass circulation reactor (volume: 11) calibrated by means of a heating plug was charged with 500 g of the oxy distillate from the Comparison Example, with the addition of 40 g. of p-toluenesulfonic acid and 10 g of a distillation residue obtained in the production of pure acrylic acid distillate and having the following composition: 5.5% by weight of acrylic acid 54.0% by weight of diacrylic acid 14.5% by weight of acid dodecyl benzene sulfonic acid: mainly polymers of acrylic acid and phenothiazine
The dissociation temperature was 195 d C and the operating pressure was 1 atm.
The oxy-ester distillate and the corresponding amount of acrylic acid distillation residue (20% by weight) were continuously fed to the reactor, regulated by the reactor level. 10% by weight of the feed stream was continuously removed from the reactor. Over a period of 302 hours, 23,985 g of the mixture of oxy ester distillate and acrylic acid distillation residue was fed to the dissociation reactor and 21.580 g of product mixture condensed. According to the analysis by gas chromatography, the condensate comprised: 69.5% by weight of butyl acrylate 6.1% by weight of butanol 19.5% by weight of acrylic acid 1% 0.6% by weight of dibutyl ether 3.1% by weight of butenes Conversion: 96% by weight based on oxy esters. It can be seen from the previous example of the process of the present invention that this process is capable of achieving higher conversions and results in lower losses of starting material than the known processes.
Claims (10)
1. - A process for esterifying (meth) acrylic acid with an alkanol in the presence of an esterification catalyst in which the unreacted starting compounds and the formed (meth) acrylic ester are separated by distillation and a lower product containing oxy esters, where the lower product is separated and either a) the lower product is directly mixed with oligomeric (meth) acrylic acid and the oxy esters present in the lower product dissociate at a temperature high in the presence of acid catalysts other than (meth) acrylic or gomeric acid, or b) the oxy esters are first removed by distillation of the lower product, the distillate is mixed with oligomeric (meth) acrylic acid and it is dissociated at an elevated temperature in the presence of acid catalysts other than oligomeric (meth) -acrylic acid
2. A process according to claim 1 wherein the amount of (meth) acrylic acid The added oligomeric ion is from 5 to 50% by weight, preferably from 10 to 40% by weight, based on the amount of product lower in (a) or distilled in (b).
3. A process according to claim 1 or 2, wherein the dissociation process is carried out in the presence of molecular oxygen.
4. - A process as claimed in any of clauses 1 to 3, wherein the dissociation process is carried out from 150 to 250 ° C, preferably from 180 to 2305C 5.- A process in accordance with any of the re vindicators 1 to 4, wherein the added acid catalyst is an acid selected from the group consisting of mineral acids such as sulfuric acid or phosphoric acid, and organic acids other than oligomeric (meth) acrylic acid, per axle Peptides, alkyl or aryl sulphonic acids such as methanesulfonic acid or p-toluenesulfonic acid. 6. A process according to claim 5 wherein the added amount of acid catalyst is from 1 to 20% by weight, preferably from 5 to 15% by weight, based on the amount of the lower product in (a) or distilled in (b). 7. A process according to any of the claims 1 to 6, where the dissociation is carried out under reduced pressure (1 atm). 8. A process according to any of the claims 1 to 7, wherein a purification gas is passed through the inferior product in (a) or distilled in (b) in order to eliminate the dissociation products. 9. A process as claimed in clause 8, where the purification gas used is a gas containing oxigen. 10. A process according to any of the preceding claims, wherein the dissociation products obtained are returned directly to the esterification.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19547485A DE19547485A1 (en) | 1995-12-19 | 1995-12-19 | Methacrylic] acid esterification with alkanol for alkyl methacrylate] |
| DE19547485.6 | 1995-12-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA96006243A true MXPA96006243A (en) | 1998-04-01 |
| MX9606243A MX9606243A (en) | 1998-04-30 |
Family
ID=7780594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9606243A MX9606243A (en) | 1995-12-19 | 1996-12-09 | (meth)acrylic acid esterification with an alkanol. |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0780359B1 (en) |
| JP (1) | JP3830595B2 (en) |
| KR (1) | KR100460248B1 (en) |
| CN (1) | CN1095827C (en) |
| BR (1) | BR9703408A (en) |
| CA (1) | CA2193408A1 (en) |
| CZ (1) | CZ369096A3 (en) |
| DE (2) | DE19547485A1 (en) |
| DK (1) | DK0780359T3 (en) |
| ES (1) | ES2145371T3 (en) |
| MX (1) | MX9606243A (en) |
| MY (1) | MY118758A (en) |
| SG (1) | SG79928A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19536191A1 (en) * | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| DE19536183A1 (en) * | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the preparation of alkyl esters of (meth) acrylic acid |
| DE19536184A1 (en) * | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| SG81213A1 (en) * | 1995-12-15 | 2001-06-19 | Rohm & Haas | Process for producing butyle acrylate |
| DE19701737A1 (en) * | 1997-01-20 | 1998-07-23 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| US5877345A (en) | 1997-02-07 | 1999-03-02 | Rohm And Haas Company | Process for producing butyl acrylate |
| MY120051A (en) | 1997-07-30 | 2005-08-30 | Mitsubishi Rayon Co | Process for purification of (meth)acrylic acid |
| DE19814387A1 (en) * | 1998-03-31 | 1999-10-07 | Basf Ag | Process for the production of acrylic acid and acrylic acid esters |
| DE19851984A1 (en) * | 1998-11-11 | 2000-05-18 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| DE19851983A1 (en) | 1998-11-11 | 2000-05-18 | Basf Ag | Process for the continuous production of alkyl esters of (meth) acrylic acid |
| DE19922722A1 (en) | 1999-05-18 | 2000-11-23 | Basf Ag | Process for the preparation of (meth) acrylic acid esters |
| DE10007213A1 (en) * | 2000-02-17 | 2001-08-23 | Basf Ag | Process for the preparation of esters of alpha, beta-unsaturated carboxylic acids |
| DE10127941A1 (en) | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters by transesterification comprises recycling by-product alcohol to the production of the starting (meth)acrylate |
| WO2005007609A1 (en) | 2003-07-11 | 2005-01-27 | Basf Aktiengesellschaft | Thermal separation method for separating at least one (meth)acrylmonomer-enriched material flow |
| EP4015498B1 (en) | 2020-12-18 | 2024-04-24 | Basf Se | Method for the continuous production of acrylic acid n-butylester |
| CN117299040B (en) * | 2023-11-30 | 2024-03-12 | 万华化学集团股份有限公司 | Device system and method for simultaneously preparing butyl acetate and butyl acrylate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB923595A (en) | 1960-12-03 | 1963-04-18 | Distillers Co Yeast Ltd | Improvements in and relating to the production of acrylic esters |
| US3868410A (en) * | 1972-08-03 | 1975-02-25 | Celanese Corp | Conversion of oligomeric acrylates to acrylate monomers |
| DE2339529A1 (en) | 1973-08-03 | 1975-02-13 | Ardie Werk Gmbh | Accelerator linkage for heavy vehicle with fuel injection pump - has hydraulic servo to alter linkage length when changing gear |
| JPS5762229A (en) | 1980-10-02 | 1982-04-15 | Mitsubishi Petrochem Co Ltd | Recovery of useful component from heavy substance obtained as by-product in preparation of acrylic ester |
| CN1058390A (en) | 1990-07-13 | 1992-02-05 | 梁效成 | The treatment process of waste liquid containing alkoxyl propionic ester |
| JPH0768168B2 (en) | 1991-07-12 | 1995-07-26 | 東亞合成株式会社 | Decomposition method of Michael adduct of acrylic acid ester |
| CN1026104C (en) | 1992-03-17 | 1994-10-05 | 侯玉里 | Waste oil reproducing process for acrylate ester |
| JP2943523B2 (en) | 1992-08-12 | 1999-08-30 | 東亞合成株式会社 | Method for producing useful compound from Michael adduct of acrylic acid ester |
-
1995
- 1995-12-19 DE DE19547485A patent/DE19547485A1/en not_active Withdrawn
-
1996
- 1996-12-09 MY MYPI96005168A patent/MY118758A/en unknown
- 1996-12-09 MX MX9606243A patent/MX9606243A/en unknown
- 1996-12-13 DE DE59605038T patent/DE59605038D1/en not_active Expired - Lifetime
- 1996-12-13 EP EP96120074A patent/EP0780359B1/en not_active Expired - Lifetime
- 1996-12-13 ES ES96120074T patent/ES2145371T3/en not_active Expired - Lifetime
- 1996-12-13 DK DK96120074T patent/DK0780359T3/en active
- 1996-12-16 JP JP33583696A patent/JP3830595B2/en not_active Expired - Lifetime
- 1996-12-16 CZ CZ963690A patent/CZ369096A3/en unknown
- 1996-12-17 SG SG9611746A patent/SG79928A1/en unknown
- 1996-12-18 CA CA002193408A patent/CA2193408A1/en not_active Abandoned
- 1996-12-18 KR KR1019960067283A patent/KR100460248B1/en not_active IP Right Cessation
- 1996-12-18 CN CN96121570A patent/CN1095827C/en not_active Expired - Lifetime
-
1997
- 1997-05-27 BR BR9703408A patent/BR9703408A/en not_active IP Right Cessation
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