EP4337633A1

EP4337633A1 - Unsaturated esters containing an additive for reducing and stabilising the yellowness index value

Info

Publication number: EP4337633A1
Application number: EP22727014.7A
Authority: EP
Inventors: Florian Zschunke; Andrea Wittkowski; Belaid AIT AISSA; Rudolf Burghardt; Daniel Helmut König; Steffen Krill; Andreas RÜHLING; Sven Balk; Bruno Keller
Original assignee: Roehm GmbH Darmstadt
Current assignee: Roehm GmbH Darmstadt
Priority date: 2021-05-10
Filing date: 2022-04-29
Publication date: 2024-03-20
Also published as: WO2022238144A1; BR112023023281A2; KR20240006654A; CN117279885A; JP2024518080A; TW202311223A

Abstract

The present invention relates to a new method for reducing the yellowness index value of alkyl (meth)acrylates, in particular MMA, and of polymers which were produced from these alkyl (meth)acrylates. The new method develops this effect even after the monomers have been stored for a longer period. The method relates to the addition of specific aldehydes into the monomer composition. This can take place irrespective of the particular process for producing the alkyl (meth)acrylates, and is thus simple and cost effective to achieve. Furthermore, the corresponding monomer compositions form part of the present invention.

Description

1

Unsaturated ester containing an additive to reduce and stabilize the yellow value

field of invention

The present invention relates to a novel process for reducing the yellowness index of alkyl (meth)acrylates, in particular of MMA, and of polymers produced from these alkyl (meth)acrylates. The novel process also develops this effect after the monomers have been stored for a long period of time. The process involves the addition of specific aldehydes into the monomer composition. This can be done independently of the respective manufacturing process for the alkyl (meth)acrylates and is therefore easy and inexpensive to implement.

Furthermore, the corresponding monomer compositions are part of the present invention.

State of the art

Today, methyl methacrylate (MMA) is produced using various processes that start from C2, C3 or C4 building blocks, still predominantly starting from hydrocyanic acid and acetone via the resulting acetone cyanohydrin (ACH) as the central intermediate. This process has the disadvantage that very large amounts of ammonium sulfate are obtained, the processing of which is associated with very high costs. Other processes that use a raw material basis other than ACH are described in the relevant patent literature and have meanwhile been implemented on a production scale. Another disadvantage is that the C3-based MMA produced does not have optimal yellowness values. Although these are relatively small, they still lead to troublesome slight yellowing, particularly in the production of PMMA sheets, films or molded parts which are used in optically relevant applications.

In a process based on C-4 raw materials for the production of MMA, starting materials such as isobutylene or tert-butanol are used, which are converted into the desired methacrylic acid derivatives over several process stages. These are oxidized in a first stage to methacrolein and in a second stage to methacrylic acid. Finally, an esterification takes place to give the desired alkyl ester, in particular with methanol to give MMA. More details on this method are, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry 2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Methacrylic Acid and Derivatives, DOI: 10.1002/14356007. a16_441.pub2 and in Krill and Rühling et. al. "Many ways 2 lead to methyl methacrylate”, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, doi.org/10.1002/ciuz.201900869.

In this process, isobutylene or tert-butanol is generally oxidized to form methacrolein in a first stage, which is then reacted with oxygen to form methacrylic acid. The methacrylic acid obtained is subsequently converted into MMA with methanol. Further details on this method are available in Ullmann's Encyclopedia of Industrial Chemistry 2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Methacrylic Acid and Derivatives, DOI:

10.1002/14356007. a16_441.pub2.

In detail, a distinction is made between three processes for the production of MMA on this basis. Raw materials used include, for example, tert-butanol, which is converted to isobutene by eliminating water, alternatively methyl tert-butyl ether, which is converted to isobutene by eliminating methanol, or isobutene itself, which is available as a raw material from a cracker, for example . In summary, this results in the following three routes:

Process A, "Tandem C Direct Oxidation" process, without intermediate isolation of methacrolein: Here, in a first step, isobutene is used to produce methacrolein, which is oxidized to methacrylic acid in step 2, before finally esterifying it with methanol in step 3 to form MMA becomes.

Method B, "Separate C Direct Oxidation" method: Here, in a first step, methacrolein is produced from isobutene, which is first isolated and intermediately purified in step 2, before it is converted into methacrylic acid in step 3 and this finally in step 4 with it methanol is esterified to MMA.

Method C, "Direct Metha Process" or direct oxidative esterification process: Here, too, methacrolein is produced in a first step from isobutene, which is first isolated and intermediately cleaned in step 2 before it is mixed with methanol and air in step 3 is directly oxidatively esterified to MMA.

All methods presented are well documented in the prior art, including in (i) IHS Chemical Process Economics Program, Review 2015-05, R.J. Chang, Syed Naqvi (ii) Vapor Phase Catalytic Oxidation of Isobutene to Methacrylic Acid, Stud. Surf. Be. Catal. 1981 , 7 , 755-767

Even if the educt and by-product profile of the C4-based MMA differs significantly from those obtained from C3 building blocks, C4-based MMA without a very complex multi-stage purification with loss of product is also easy to achieve, but still optical yellowing in end-use applications. Basically, and even if disturbing, the yellowing of C4-based products tends to be somewhat less than that of C3-based products. This yellowing could persist somewhat, though 3 cannot be sufficiently reduced by providing an alternative C4-based method.

In this alternative C4-based process, MMA is obtained by oxidizing isobutylene or tert-butanol with atmospheric oxygen in the gas phase at heterogeneous contact to form methacrolein and subsequent oxidative esterification reaction of methacrolein using methanol. This method, developed by ASAHI, is described, inter alia, in the publications US Pat. No. 5,969,178 and US Pat. No. 7,012,039. A disadvantage of this method is in particular a very high energy requirement. In a further development of the process, the methacrolein is obtained from propanal and formaldehyde in the first stage. Such a method is described in WO 2014/170223. However, even with this optimization, it is often found that C4-based MMA also often has relevant residual yellow values.

As an alternative to this process, US Pat. No. 5,969,178 discloses working up in just one column, with the feed necessarily being above the bottom. Low-boiling constituents are removed from the reactor discharge at the top of this column. A mixture of crude MMA and water remains in the sump and is to be sent for further processing. A mixture of methacrolein and methanol, intended for recycling into the reactor, is finally removed from the column via a side stream, the exact position of which must first be determined and which can be adjusted by adding various boiling trays. US Pat. No. 5,969,178 itself points out that such a method is difficult to carry out because of various azeotropes. In addition, methacrylic acid in particular, which is always present as a by-product, plays a major role. According to this process, even if US Pat. No. 5,969,178 is silent about this, the methacrylic acid would be separated off in such a way that it remained in a phase to be disposed of and isolation would only be worthwhile to a limited extent. However, this reduces the overall yield of methacrylic products from this process.

US Pat. No. 7,012,039 discloses a somewhat different work-up of the reactor effluent from the oxidative esterification. Here, in a first distillation stage, methacrolein is distilled off overhead via sieve trays and the aqueous, MMA-containing mixture is passed from the bottom into a phase separator. In this, the mixture is adjusted to a pH of about 2 to 3 by adding sulfuric acid. The sulfuric acid water is then separated from the organic or oil phase by means of centrifugation. In a further distillation, this oil phase is separated into high-boiling components and a phase containing MMA, which is drawn off overhead. The MMA-containing phase is then separated from low-boiling components in a third distillation. This is followed by a fourth distillation for final purification.

The problem with this process is the sulfuric acid, which has to be added in large quantities and can have a corrosive effect on parts of the system. Accordingly, these parts, such as in particular the phase separator or the second distillation column, have to be 4 suitable materials to be made. Furthermore, US Pat. No. 7,012,039 is also silent about the handling of the methacrylic acid that is produced or the remaining methanol in the product. However, it can be assumed that the former is also separated in the distillation stages, while the methanol can only be partially recovered and recycled with the methacrolein, while the remainder is probably lost in the third distillation stage.

WO 2014/170223 describes a similar method to US 7,012,039. The only difference is that in the actual reaction, the pH value is adjusted by adding a methanolic sodium hydroxide solution in a circuit. This serves, among other things, to protect the catalytic converter. Furthermore, the separation of the aqueous phase in the phase separation is easier due to the salt content. However, it also means that some of the methacrylic acid formed is present as the sodium salt and is later separated off with the aqueous phase and discarded. In the case of the variant of adding sulfuric acid in the phase separation, the free acid is indeed recovered. However, sodium (hydrogen) sulfate accumulates, which can lead to other problems during disposal.

Finally, WO 2017/046110 teaches an optimized processing of the crude MMA obtained from an oxidative esterification by first separating it from a heavy phase and then distilling off an alcohol-containing light phase from this heavy phase, which in turn can be recycled. What is also special about this process is that the methacrolein was obtained on the basis of propanal and formaldehyde, with the former being obtained on the basis of C2 building blocks, e.g. from ethylene and synthesis gas.

Overall, all of these processes, regardless of the raw material basis for the methacrolein used, lead to MMA or, in general, to alkyl methacrylates, which as monomers themselves have a measurable yellow coloration.

As shown in the prior art, in the various MMA processes, regardless of the raw material basis, a large number of separation steps are carried out in order on the one hand to isolate the monomer according to specification and on the other hand to achieve a sufficiently low color number of the monomeric end product. Ultimately, transparent polymeric products can be produced with this.

The slight yellowing of the monomers also increases slightly during longer storage, for example in a storage tank, or due to the transport time for further processing. The slight yellowing of the monomers also leads to a yellowing of the downstream products, such as molding compounds or other polymers, for example Plexiglas-based granules and semi-finished products that are produced from MMA.

There is therefore a need for improvement such as identifying the source of this yellowing and removing it as efficiently as possible from the corresponding alkyl methacrylate, in particular MMA, before the polymerization. 5

To reduce the yellow value, EP 36 76241 explicitly proposes adjusting the pH and the water content specifically during the oxidative esterification and treating the crude product of this stage further in another reactor, with the water content being higher and the pH being lower in the aftertreatment is than in the original reaction. Although this procedure has proven to be effective, it has also proven to be technically complex.

As a third raw material alternative, there are also C2-based processes for the production of alkyl methacrylates, especially MMA. These processes also have methacrolein produced from formaldehyde and propanal, the latter being obtained from ethylene, as an intermediate. In this production of methacrolein according to the C2 process, the target product is obtained from formalin and propionaldehyde in the presence of a secondary amine and an acid, usually an organic acid. The reaction takes place via a Mannich reaction. The methacrolein (MAL) synthesized in this way can then be converted in a subsequent step by oxidation in the gas phase to form methacrylic acid or by oxidative esterification to form methyl methacrylate. Such a process for preparing methacrolein is described, inter alia, in the publications US Pat. No. 7,141,702, US Pat.

The processes based on a Mannich reaction that are suitable for preparing methacrolein are generally known to the person skilled in the art and are the subject of corresponding review articles, for example in Ullmann's Encyclopedia of Industrial Chemistry 2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Acrolein and Methacrolein , DOI:

10.1002/14356007. a01_149.pub2.

For this process to be used economically, a high yield and a low specific energy requirement must be achieved. The yellowing of this C2-based MMA is also less than that of MMA based on alternative raw material sources. Nevertheless, yellowing here, especially in the polymerized end product, is currently difficult to avoid completely and, without the addition of bluing agents, leads to relevant yellowing in colorless, transparent plastics made from the monomer, such as Plexiglas sheets.

In summary, it can be said that there are a large number of processes based on the raw materials ethylene, acetone or isobutene. Depending on the technologies and processing methods, also specific to the various manufacturing processes, a monomer quality - e.g. MMA - is produced that can actually differ based on the trace components.

For the C2-based LIMA process, it should be noted that the product does not contain any (meth)acrylonitrile, but a relatively high proportion in the ppm range of methyl isobutyrate, which is also referred to as methyl isobutyrate. The salary 6 typically fluctuates between 100 and 700 ppm. Other characteristic traces are dimethoxyisobutene and dimethoxyisobutane.

For the likewise C2-based ALPHA process, which, like the LIMA process, is also based on ethylene as a raw material, it should be noted that it does not contain any (meth)acrylonitrile. On the other hand, a relatively high value in the ppm range of propionic acid methyl ether, which is also referred to as methyl propionate, can be present here. The content varies between 10 to 100 ppm. Compared to the LIMA process, the isobutyric acid methyl ester is present in reduced form (several 10 ppm). Other characteristic traces of the MMA from the ALPHA process are pentanones such as diethyl ketone or isopropyl methyl ketone and ethanol.

For the C3-based ACH-Sulfo process, which is mainly based on acetone as the starting material, it should be noted that (meth)acrylonitrile is usually contained in concentrations of 30 to 250 ppm. Methyl propionate and methyl isobutyrate are also found, but in lower concentrations than in the C2-based methods. Pentanones such as diethyl ketone or isopropyl methyl ketone and ethanol are not found or can only be found in the single-digit ppm range.

The C4-based processes, in particular those that are carried out as gas-phase processes, have other specific traces. Traces of methyl isobutyrate and methyl propionate are also detected here, but dimethylfuran and pyruvic acid are particularly characteristic as trace components, which also have an influence on the yellowness index in the isolated monomer.

As a special C4-based process, the Asahi process must be highlighted at this point, which has a direct liquid-phase oxidative oxidation as the second reaction step. In this MMA grade, methyl isobutyrate is again found as a significant trace component.

In most processes, especially in the two C3- and C4-based processes, diactyl is a coloring component that has to be removed during the isolation process, but partially penetrates into the isolated MMA. In the case of commercially available MMA, levels between just over 0 and 10 ppm can be detected.

Taking into account this specific composition of the MMA monomer qualities produced according to the different processes, it was a particularly complex task to reduce the yellowing of the products and to counteract post-yellowing during transport and storage. 7

Overall, there is a great need to counteract the yellowing of MMA effectively and easily. In particular, this need exists regardless of the process used to produce MMA.

tasks

The object of the present invention was therefore to reduce the yellowness index of alkyl (meth)acrylates, in particular of MMA, in the simplest possible way.

In this context, the particular object was that this reduction should be able to be used independently of the production method for the alkyl (meth)acrylate.

A further object was that the reduction in yellowness should be sustained, i.e. even after long storage of the composition containing the alkyl (meth)acrylate.

A further object was to provide a monomeric product quality of the alkyl (meth)acrylate which has an improved yellowness index. In this context, the problem arose that this improved optical product quality of the monomers should lead to improved optical properties with a reduced yellowness index in the poly(meth)acrylates thus produced, even after polymerization.

Furthermore, the method for sustainable yellow value reduction should be toxicologically harmless and simple and inexpensive to use.

Furthermore, there was the task that the process should be realizable without major changes to the production facilities and without major investment.

Other tasks that are not explicitly stated can result from the description, the claims, the examples or the overall context of the present description of the invention.

solution

The task was solved using a new method for reducing the yellow value of alkyl (meth)acrylates. This process is characterized in that 0.5 to 500 ppm by weight of an aldehyde with the general formula R—HC=0 is added to the alkyl (meth)acrylate. Surprisingly, the aldehydes can be chosen relatively freely. According to the invention, aldehydes can be used which have an R radical of between 1 and 20 8th

Carbon atoms and optionally up to three oxygen atoms as ether and/or hydroxy groups. R can be a linear, branched or cyclic alkyl group, an aromatic group, an ether group or a combination of several of these groups.

Examples of common linear alkyl groups are ethyl, propyl, n-butyl, n-hexyl or n-dodecyl groups. Branched alkyl groups include those alkyl groups having one or more, for example, tertiary or quaternary carbon atoms. Examples of these are isopropyl, isobutyl or tertbutyl or ethylhexyl groups. Cyclic alkyl groups can be, for example, cyclohexyl, cyclopentyl or methylcyclohexyl groups.

In addition to the saturated alkyl groups, aromatic groups or combinations of aromatic and saturated alkyl groups can also be used. Examples of aromatic groups are phenyl or benzyl groups.

According to the invention, it is also possible to use radicals which contain a total of up to 20 carbon atoms and additional oxygen atoms in the form of one or more ether or hydroxyl groups.

Aldehydes which contain olefinic groups cannot be used according to the invention, since these are potentially active in polymerization. In addition, they do not seem to have any effect, as can be seen at different concentrations of residual methacrolein in C2 or C4 MMA.

Furthermore, other heteroatoms, such as nitrogen or sulfur heteroatoms in particular, are excluded in the aldehyde, since these can, for example, be subject to oxidation sensitivity and can in turn lead to discoloration. Halogen atoms are again unsuitable for reasons of reactivity and from a toxicological point of view.

The aldehyde is particularly preferably acetaldehyde, propanal, 3-methylpentanal, iso- or n-butanal and n-pentanal.

The present process is particularly preferably used for adding additives to commercially available alkyl (meth)acrylates, such as methyl methacrylate (MMA). However, other monomers such as, in particular, n- or tert-butyl methacrylate, ethylhexyl methacrylate, ethyl or propyl methacrylate can also be additized. Furthermore, the process can also be used for acrylates, such as methyl or butyl acrylate. The yellow values of important functional (meth)acrylates, such as methacrylic acid, hydroxyethyl or hydroxypropyl (meth)acrylate, can also be reduced. The alkyl (meth)acrylate is preferably methyl methacrylate. 9

According to the invention, between 0.5 and 500 ppm by weight of the aldehyde are added to the respective monomer composition. The optimum amount depends on the (meth)acrylate to be added and the aldehyde used. This amount can be determined by a person skilled in the art for the respective combination with a few simple manual tests. For many of these combinations, a preferred amount of aldehyde added of between 1 and 250 ppm by weight, particularly preferably between 10 and 150 ppm by weight, has proven to be advantageous.

Preference is given to additionally adding between 1 and 300 ppm by weight of one or more polymerization stabilizers to the alkyl (meth)acrylate. Only one polymerization stabilizer is preferably used. Polymerization stabilizers for (meth)acrylates are generally known to those skilled in the art. In combination with the process according to the invention, preference is given to using 2,4-dimethyl-6-tert-butylphenol (DMBP) or a hydroquinone, very particularly preferably hydroquinone methyl ether (HQME).

The process according to the invention is preferably used in such a way that the alkyl (meth)acrylate has a yellowness value [D65/10] that is reduced by at least 10%, particularly preferably at least 15%, one hour after addition of the aldehyde. One hour after addition of the aldehyde, such as isobutanal, for example, the alkyl (meth)acrylate particularly preferably has a yellowness index [D65/10] that is reduced by at least 40%.

Surprisingly, it was found that the yellow index of a (meth)acrylate alkyl ester can be reduced markedly within a short time not only by simply adding the aldehydes described. At least as surprisingly, it was found that this reduction in the yellow value is so lasting that it can still be detected to the same or at least a similar extent even after several days of storage. This is observed even after storage at elevated temperatures such as 40°C.

The process according to the invention is preferably used in such a way that the alkyl (meth)acrylate still has a yellowness index [D65/10] reduced by at least 10%, particularly preferably at least 15%, 8 days, preferably 1 month, after addition of the aldehyde. As a rule, no increase in the yellowness index of the composition, or only a very small increase, is found over this period of time compared to the yellowness index one hour after addition of the aldehyde.

Furthermore, it was very surprisingly found that the yellowness index of polymers produced from alkyl (meth)acrylates with additives according to the invention is also significantly reduced compared to polymers produced analogously without the additives according to the invention. This effect is stable even when the polymers are stored for a long time, for example for a month. Even after weathering tests on the polymers, the color stabilization is easily measurable and surprisingly strong. 10

In principle, the process according to the invention can be used not only for reducing the yellowness index of pure alkyl (meth)acrylates such as MMA, but also of monomer mixtures consisting predominantly of different alkyl (meth)acrylates. The aldehyde can be added to the monomer mixture or, alternatively, one or more aldehydes have already been added to an admixed monomer according to the invention in such a way that the entire mixture is obtained with an inventive concentration of the aldehyde.

Furthermore, the effect according to the invention also exists in the case of the polymers produced from these monomer mixtures.

Surprisingly, it was also found that many, more precisely all, of the aldehydes examined which correspond to the description above show the effect according to the invention. According to tests that have been carried out, for example methanal, acetaldehyde, propanal, iso- or n-butanal, pentanal, 2-methylpentanal, decanal, dodecanal are particularly suitable.

Aromatic aldehydes, such as benzaldehyde and 3-hydroxybenzaldehyde, also have an effect, albeit one that is initially reduced compared to aldehydes with pure alkyl groups. These can therefore be used according to the invention, but are less preferred.

In addition to the method according to the invention, compositions containing at least 97.5% by weight of an alkyl (meth)acrylate are also part of the present invention. According to the invention, these compositions are characterized in that they contain between 0.5 and 500 ppm by weight of an aldehyde having the general formula R—HC=0. The same applies to the aldehyde as stated above in the context of the method. According to the invention, particularly preferred aldehydes are isobutanal, n-pentanal or 3-methylpentanal.

The alkyl (meth)acrylate is particularly preferably, but not restrictively, methyl methacrylate (MMA). The composition preferably contains at least 99.5% by weight, ideally at least 99.9% by weight, of MMA. Further monomers which can be contained in the composition according to the invention have already been shown in the description of the method.

According to the invention, the composition preferably has at least 97.5% by weight of the alkyl (meth)acrylate and at least between 0.5 and 500 ppm by weight of the aldehyde. The composition preferably contains 99.5% by weight, particularly preferably 99.8% by weight, of alkyl (meth)acrylate and between 1 and 300 ppm by weight, in particular between 20 and 250 ppm by weight and very particularly preferably between 10 and 130 ppm by weight , in particular between 30 and 90 ppm by weight of the aldehyde. The aldehyde or aldehydes in the composition are particularly preferably methanal, acetaldehyde, propanal, iso- or n-butanal, pentanal, 2-methylpentanal, decanal, dodecanal or a mixture of at least two of these aldehydes. 11

The composition according to the invention preferably additionally contains between 1 and 300 ppm by weight of a polymerization stabilizer. These are preferably 2,4-dimethyl-6-tert-butylphenol or a hydroquinone, very particularly preferably hydroquinone methyl ether (HQME).

Surprisingly, it was also found that by using the method according to the invention or with the compositions according to the invention, color stabilization of functional or non-functional alkyl (meth)acrylates, in particular of the commercially most important MMA, can be achieved, independently of the respective underlying production process. However, it was particularly surprising that the effect according to the invention with MMA occurs in principle independently of the production process, but is dependent on the underlying production process with regard to the expression of the effect, in particular with regard to the degree of color reduction. Empirically, this can only be attributed to interactions with other components in the respective compositions. Nevertheless, it was in no way to be expected that the effect could be determined despite very different secondary components in the alkyl (meth)acrylate.

The effect according to the invention is particularly pronounced in the case of MMA or other alkyl (meth)acrylates, which were produced using the C3-based ACH process, among other things. According to analyses, this surprising effect is due in particular to the fact that the composition contains acrylonitrile and/or methacrylonitrile. It is particularly preferred if the total of less than 300 ppm by weight, in particular less than 200 ppm by weight, of acrylonitrile and methacrylonitrile is present in the composition.

The effect according to the invention is also particularly pronounced in the case of MMA or other alkyl (meth)acrylates, which were produced, inter alia, by means of a C2-based process. According to analyses, this surprising effect is due in particular to the fact that the composition contains at least two components selected from n-butanol, tert-butanol, methyl acrylate, methyl isobutyrate, methyl propionate, 1,1-dimethoxyisobutene and ethyl methacrylate, especially if the composition contains n-butanol, tert-butanol, methyl acrylate, methyl propionate and ethyl methacrylate. It is particularly preferred if all of these components are present, but in total less than 5 ppm by weight of n-butanol, tert-butanol, methyl acrylate, methyl propionate and ethyl methacrylate are present in the composition. It is just as preferred if the total amount of n-butanol, tert-butanol, methyl isobutyrate, methyl acrylate, methyl propionate and ethyl methacrylate is less than 700 ppm by weight.

Also pronounced, although not as clear as in the other cases, is the effect according to the invention in the case of MMA or other alkyl (meth)acrylates, which were produced, inter alia, by means of a C4-based process starting from isobutene, isobutanol or MTBE . 12

According to analyses, this surprising effect is due in particular to the fact that the composition contains dimethylfuran, methyl pyruvate and/or diacetyl, preferably all three components. It is particularly preferred if the sum total of these three components is less than 30 ppm by weight, in particular less than 10 ppm by weight, in the composition.

Reference List

Figure 1 compares the results of Examples 1 to 12 in relation to Comparative Examples VB1, 2 and 3 with regard to stabilization of C2, C3 or C4 MMA with different concentrations of isobutanal (see also Results in Table 1).

In Figure 2, the results of examples 13 to 16 of a stabilization of C3-MMA over a period of 8 weeks of storage (at 50 ° C) with different concentrations of isobutanal and in relation to comparative example VB4 are compared (see also results in Table 2).

In Figure 3, the results of examples 17 to 20 of a stabilization of C4-MMA over a period of 8 weeks of storage (at 50 ° C) with different concentrations of isobutanal and in relation to comparative example VB5 are compared (see also results in Table 2).

examples

Lowering the yellow value

In order to determine the reduction in the yellow value of methyl methacrylate from the C2, C3 or the C4 process by adding the aldehyde isobutanal according to the present invention, methyl methacrylate was doped with an aldehyde such as isobutanal. This procedure initially relates to Examples 1 to 12. Subsequently or at the specified times, the yellowness value Y.1. D65/10° determined according to DIN 6167. The following raw materials were used to produce the doped methyl methacrylate samples:

Methyl methacrylate from a Rohm C2 process, produced using the LiMA process (hereinafter C2-MMA)

Methyl methacrylate from a Rohm C3 process, manufactured using the ACH process (hereinafter C3-MMA)

Methyl methacrylate from a Rohm C4 process, produced from isobutene which had already been stabilized with 50 ppm hydroquinone monomethyl ether (hereinafter C4-MMA) 13 isobutanal from Merck KGaA

To prepare the isobutanal-doped methyl methacrylate samples to be examined, methyl methacrylate was placed in a glass beaker, the hydroquinone monomethyl ether stabilizer was dissolved therein if required, and isobutanal was added. The mixture was homogenized with a magnetic stirrer for one hour. The yellow value was then determined to assess the optical quality.

Comparative example CE1 (reference example for yellow value):

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether, without adding an aldehyde Example 1:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 12 ppm isobutanal

Example 2:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 25 ppm isobutanal

Example 3:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 60 ppm isobutanal

Example 4:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 100 ppm isobutanal

Comparative example VB2 (reference example):

C4-MMA already containing 50 ppm hydroquinone monomethyl ether without the addition of an aldehyde

Example 5:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 12 ppm isobutanal

Example 6:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether, with 25 ppm iso-butanal 14

Example 7:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 60 ppm isobutanal

Example 8:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 100 ppm isobutanal

Comparative example VB3 (reference example):

C2-MMA, already containing 50 ppm hydroquinone monomethyl ether without the addition of an aldehyde

Example 9:

C2-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 12 ppm isobutanal

Example 10:

C2-MMA, already containing 50 ppm hydroquinone monomethyl ether, with 25 ppm isobutanal Example 11:

C2-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 60 ppm isobutanal

Example 12:

C2-MMA, already containing 50 ppm hydroquinone monomethyl ether, mixed with 100 ppm isobutanal

The respective yellowing values of the isobutanal-doped methyl methacrylate samples of C3-MMA, respectively C4-MMA and C2-MMA were compared to the respective yellowing value of the pure methyl methacrylate from the C3, respectively C4 and C2 process (VB1, VB2 or VB3) set. This results in the percentage reduction in the yellow value compared to the initial value. The values are shown in Table 1 and visually compared with one another in FIG. 15

Table 1 Observation of the decrease in the yellow value over time

In order to show a stable reduction in the yellow value over a longer period of time, samples of C3 and C4 MMA were mixed with isobutanal as the aldehyde according to the present invention and stored at 50.degree. Corresponding tests can be found in Examples 9 to 16 and the associated comparative examples VB4 and VB5. The yellow value Y.l. D65/10° was measured according to DIN 6167 after the times given in Table 2. The same raw materials as in Examples 1 to 12 were used.

In order to produce the samples to be examined, which were doped with isobutanal, methyl methacrylate was placed in a beaker, the stabilizer hydroquinone monomethyl ether was dissolved in it if necessary, and isobutanal was added. The mixture was homogenized with a magnetic stirrer for one hour. Then 25±1 g of the solution were filled into brown 30 mL narrow-necked bottles and stored at 50° C. in a circulating air drying cabinet.

To assess the optical quality, the yellowness value was determined at the start of storage at 50°C and after a storage time of 4 weeks and 8 weeks at a corresponding storage temperature of 50°C. 16

Comparative example CE4 (reference example for yellow value after storage):

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether, without addition of an aldehyde with storage at 50 °C in a circulating air drying cabinet for 8 weeks

Example 13:

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 12 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks Example 14:

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 25 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks Example 15:

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 60 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks Example 16:

C3-MMA, stabilized with 50 ppm hydroquinone monomethyl ether and mixed with 100 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks

Comparative example VB5 (reference example):

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether without addition of an aldehyde with storage at 50°C in a circulating air drying cabinet for 8 weeks

Example 17:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether and mixed with 12 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks

Example 18:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether and mixed with 25 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks

Example 19:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether and mixed with 60 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks 17

Example 20:

C4-MMA, already containing 50 ppm hydroquinone monomethyl ether and mixed with 100 ppm isobutanal and storage at 50°C in a circulating air drying cabinet for 8 weeks

The respective yellowing values of the methyl methacrylate samples of C3-MMA and C4-MMA doped with isobutanal were compared without storage and after storage for 4 or 8 weeks to the respective yellowing value of the pure methyl methacrylate from the C3 or C4 process set. This results in the percentage reduction in the yellow value compared to the initial value. The values can be found in Table 2, or shown graphically with the percentage reduction in FIG. 2 for C3-MMA and FIG. 4 for C4-MMA. Table 2

Comparative example VB1 (reference example):

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether without the addition of an aldehyde

Examples 21 to 34:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether, mixed with an aldehyde as specified in Table 3 and stored at 50° C. in a circulating air drying cabinet for 8 weeks, with measurements of the yellow value after 4 weeks and 8 weeks, respectively. The results can be found in Table 3.

Comment on example 27: the measurement of the yellow value after the direct addition of 10 ppm by weight of dodecanal appears to be due to a measurement error. In this example, too, the reduction in the yellow value after 4 or 8 weeks is consistent with the other examples or the results to be expected according to the invention. 18

Example 35 to 40:

C3-MMA stabilized with 50 ppm hydroquinone monomethyl ether, mixed with n-pentanal, according to Table 4 and storage at 50° C. in a circulating air drying cabinet for 8 weeks with measurements of the yellow value after 4 weeks and 8 weeks. The results can be found in Table 4.

Table 3: Yellowness scores and percent reduction from baseline of C3-MMA

Table 4: Yellowness values and percentage reduction compared to the initial value of C3-MMA (acetone-based MMA method) with the addition of n-pentanal

Claims

21 claims

1 . Process for reducing the yellow value of alkyl (meth)acrylates, characterized in that 0.5 to 500 ppm by weight of an aldehyde having the general formula R-HC=0 are added to the alkyl (meth)acrylate, where R is between 1 and 20 Carbon atoms and optionally up to three oxygen atoms as ether and/or hydroxy groups and R is a linear, branched or cyclic alkyl group, an aromatic group, an ether group or a combination of several of these groups.

2. The method according to claim 1, characterized in that the alkyl (meth)acrylate is methyl methacrylate.

3. Process according to Claim 1 or 2, characterized in that between 1 and 150 ppm by weight of the aldehyde are added to the alkyl (meth)acrylate.

4. The method according to at least one of claims 1 to 3, characterized in that the alkyl (meth) acrylate additionally between 1 and 300 ppm by weight of one or more polymerization stabilizers, preferably DMBP (2,4-dimethyl-6-tert-butylphenol) or HQME (hydroquinone monomethyl ether) can be added.

5. The process as claimed in at least one of claims 1 to 4, characterized in that the alkyl (meth)acrylate has a yellowness index [D65/10] which is reduced by at least 5% 1 h after addition of the aldehyde.

6. The method according to claim 5, characterized in that the alkyl (meth)acrylate has a reduced by at least 15% yellow value [D65/10] 1 h after addition of the aldehyde.

7. The method according to at least one of claims 1 to 6, characterized in that the aldehyde is methanal, acetaldehyde, propanal, iso- or n-butanal, pentanal, 2-methylpentanal, decanal, dodecanal, benzaldehyde, 3-hydroxybenzaldehyde acts.

8. Composition containing at least 97.5% by weight of an alkyl (meth)acrylate, characterized in that the composition contains between 0.5 and 500 ppm by weight of an aldehyde with the general formula R-HC=0, where R is between 1 and 20 carbon atoms and optionally up to three oxygen atoms as an ether and/or hydroxy group and R is a linear, branched or cyclic alkyl group, an ether group, an aromatic group or a combination of several of these groups. 22

9. Composition according to Claim 8, characterized in that the alkyl (meth)acrylate is methyl methacrylate (MMA) and that the composition contains at least 99.5% by weight of MMA.

10. The composition according to claim 8 or 9, characterized in that the composition comprises at least 99.8% by weight of an alkyl (meth)acrylate and between 1 and 250 ppm by weight of the aldehyde.

11 . Composition according to Claim 10, characterized in that the composition has between 10 and 130 ppm by weight of the aldehyde.

12. Composition according to at least one of claims 8 to 11, characterized in that the aldehyde is methanal, acetaldehyde, propanal, iso- or n-butanal, pentanal, 2-methylpentanal, decanal, dodecanal or a mixture of at least two of these aldehydes.

13. The composition as claimed in at least one of claims 8 to 12, characterized in that the composition contains acrylonitrile and/or methacrylonitrile, with the sum total of less than 200 ppm by weight of acrylonitrile and methacrylonitrile being present in the composition.

14. Composition according to at least one of claims 8 to 12, characterized in that the composition contains dimethylfuran,

Contains methyl pyruvate and diacetyl, with a total of less than 30 ppm by weight of dimethylfuran, diacetyl and methyl pyruvate in the composition.

15. The composition according to at least one of claims 8 to 12, characterized in that the composition contains at least two components selected from n-butanol, tert-butanol, methyl isobutyrate, methyl acrylate, 1,1-dimethoxyisobutene, methyl propionate and ethyl methacrylate, with less in total as 700 ppm by weight of n-butanol, tert-butanol, methyl isobutyrate,

Methyl acrylate, 1,1-dimethoxyisobutene, methyl propionate and ethyl methacrylate are present.

16. The composition as claimed in at least one of claims 8 to 15, characterized in that the composition additionally contains between 1 and 300 ppm by weight of a polymerization stabilizer, preferably HQME (hydroquinone monomethyl ether).