EP4161892A1 - Inhibiteurs de polymérisation - Google Patents

Inhibiteurs de polymérisation

Info

Publication number
EP4161892A1
EP4161892A1 EP21728070.0A EP21728070A EP4161892A1 EP 4161892 A1 EP4161892 A1 EP 4161892A1 EP 21728070 A EP21728070 A EP 21728070A EP 4161892 A1 EP4161892 A1 EP 4161892A1
Authority
EP
European Patent Office
Prior art keywords
methyl
ethyl
dimethyl
diethyl
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21728070.0A
Other languages
German (de)
English (en)
Inventor
Jan Niclas GORGES
Rebecca SURE
Friederike Fleischhaker
Friedrich-Georg Martin
Christian Rein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4161892A1 publication Critical patent/EP4161892A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a mixture containing at least one substituted hydroquinone monoether and at least one polymerizable compound.
  • Chemical compounds which have one or more ethylenically unsaturated groups have a pronounced tendency towards free radical polymerization.
  • such compounds are therefore also referred to as polymerizable compounds.
  • these compounds are used as monomers for the manufacture of polymers.
  • the pronounced tendency towards radical polymerization of these compounds is disadvantageous in that it occurs both during storage and transport and during chemical and / or physical processing, such as distillation or rectification, in particular under the action of energy such as heat and / or light , undesired, spontaneous radical polymerization can occur.
  • uncontrolled polymerizations can lead to the gradual formation of polymer coatings, for example on heated surfaces, which necessitates removal of the polymer coatings and thus often leads to a reduction in operating times.
  • the uncontrolled polymerizations can even run explosively.
  • Polymerization inhibitors can be used as individual chemical compounds or as mixtures of compounds. Depending on the area of application of the polymerization inhibitor, certain requirements are placed on it. For the suitability of a polymerization inhibitor as a transport and / or storage stabilizer for ethylenically unsaturated compounds, it is important that the efficiency of the polymerization inhibitor, ie the degree of polymerization inhibition, can be regulated.
  • the polymerization inhibitor should adequately prevent or slow down the undesired, spontaneous free radical polymerization, whereas the desired free radical polymerization of the ethylenically unsaturated compounds should be possible under appropriate polymerization conditions without necessity agility, the polymerization inhibitors used during storage and / or transport bitor to have to disconnect beforehand. If the stabilizer used during storage and / or transport is not separated off during the desired polymerization, it is important that it does not adversely affect the desired polymerization, for example acts unintentionally as a regulator.
  • acrylic acid is certainly one of the most important ethylenically unsaturated compounds.
  • acrylic acid is stabilized during storage and / or transport with 0.018 to 0.022% by weight of hydroquinone monomethyl ether (MEHQ), based on the amount of acrylic acid, against undesired, spontaneous free-radical polymerization.
  • MEHQ hydroquinone monomethyl ether
  • the oxygen is dissolved in sufficient quantities in the acrylic acid.
  • Sufficient amounts of oxygen are usually dissolved in the acrylic acid when acrylic acid is stored and / or transported in an atmosphere with 5 to 21% by volume of oxygen.
  • the oxygen content dissolved in the acrylic acid is reduced, as a result of which the efficiency of MEHQ for polymerization inhibition is reduced to such an extent that acrylic acid can be polymerized in the presence of MEHQ.
  • MEHQ is also used as a polymerization inhibitor in the storage and / or transport of methacrylic acid, acrylic acid esters and / or methacrylic acid esters or mixtures containing one or more of the aforementioned compounds.
  • MEHQ is one of the most important storage and / or transport stabilizers for polymerizable compounds, in particular for acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters.
  • Polymerizable compounds are stored in suitable, permanently installed containers, such as storage tanks or storage containers (see, for example, Acrylic Acid, A Summary of Safety andparty, 4th Edition 2013, 7 Bulk Storage Facilities and Accessories). It is preferred that the polymerizable compounds are in the respective containers for at least one minute, particularly preferably at least 10 minutes, very particularly preferably at least 60 minutes, during storage. Although the storage period is theoretically unlimited under the appropriate conditions, the storage period is usually reduced to a minimum for economic reasons. It is preferred that the polymerizable compounds are stored for a maximum of 180 days, particularly preferably for a maximum of 90 days, very particularly preferably for a maximum of 30 days, in the respective in containers. Particularly preferred ranges result from any combination of the aforementioned lower and upper limits.
  • Polymerizable compounds are usually transported in suitable, transportable containers such as tanks or containers by ship, railroad car and / or truck (see, for example, Acrylic Acid, A Summary of Safety and Handling, 4th Edition 2013, 9 Safe Transport of Acrylic Acid) .
  • the transportable containers can also be permanently installed on the corresponding means of transport, for example ship tanks or rail tank cars.
  • the containers it is also possible for the containers to be stored at a specific location for a certain period of time before they are transported to another location.
  • the transport of polymerizable compounds can also take place in pipes or hoses, for example after cleaning the polymerizable compounds to the storage tank, when loading from the storage tank into a transportable container and / or when loading from one transportable container to another.
  • the polymerizable compounds are in the respective containers for at least 10 seconds, preferably at least one minute, particularly preferably at least 10 minutes, very particularly preferably at least 60 minutes, during transport. Although the duration is theoretically unlimited under the appropriate conditions, the duration is usually reduced to a minimum for economic and safety reasons. It is preferred that the polymerizable compounds are in the respective containers for a maximum of 180 days, particularly preferably for a maximum of 90 days, very particularly preferably for a maximum of 30 days, during transport. Particularly preferred ranges result from any combination of the aforementioned lower and upper limits.
  • the polymerization inhibitors should ensure adequate stabilization of the compounds capable of polymerization against undesired free radical polymerization. In the case of the desired radical polymerization, however, there should be no need to separate the poly merization inhibitors from the mixture before the polymerization.
  • the polymerization inhibitors should therefore not act as polymerization regulators and / or polymerization inhibitors for the desired free-radical polymerization.
  • R is Cr to Cr-alkyl, preferably Cr to C ß- alkyl, particularly preferably Cr or C 2 -alkyl, very particularly preferably Cr-alkyl,
  • R 1 is Cr or C 2 -alkyl, very particularly preferably Cr-alkyl
  • R 2 to R 4 independently of one another, are H, Cr or C 2 -alkyl, very particularly preferably, independently of one another, H or Cr-alkyl, and at least one polymerizable compound.
  • R is Cr to Cr-alkyl, preferably Cr to C 3 -alkyl, particularly preferably Cr or C 2 -alkyl, very particularly preferably Cr-alkyl,
  • R 1 and R 2 independently of one another, are Cr or C 2 -alkyl, very particularly preferably Cr-alkyl, and
  • R 3 and R 4 independently of one another, are H, Cr or C 2 -alkyl, very particularly preferably independently of one another, H or Cr-alkyl, and at least one polymerizable compound.
  • R is Cr to Cr-alkyl, preferably Cr to C 3 -alkyl, particularly preferably Cr or C 2 -alkyl, very particularly preferably Cr-alkyl, R 1 , R 2 and R 3, independently of one another, are Cr or C2-alkyl, very particularly preferably Cr-alkyl, and
  • R 4 is H, Cr or C2-alkyl, very particularly preferably H or Cr-alkyl, and at least one polymerizable compound.
  • Suitable compounds of the general formula (I) are, for example, 2-methyl-4-methoxyphenol, 2,3-dimethyl-4-methoxyphenol, 2,5-dimethyl-4-methoxyphenol, 2,6-dimethyl 4- methoxyphenol, 2,3,5-trimethyl-4-methoxyphenol, 2,3,6-trimethyl-4-methoxyphenol, 2,3,5,6-tetramethyl-4-methoxyphenol, 2-ethyl-4-methoxyphenol, 2-ethyl-3-methyl-4-methoxyphenol, 2-methyl-3-ethyl-4-methoxyphenol, 2-ethyl-5-methyl-4-methoxy- phenol, 2-methyl-5-ethyl-4-methoxyphenol, 2-ethyl-6-methyl-4-methoxyphenol, 2-methyl-6-ethyl-4-methoxyphenol, 2-ethyl-3, 5-dimethyl-4-methoxyphenol, 2,3-dimethyl-5-ethyl-4-methoxyphenol, 2,5-dimethyl-3-e
  • the total amount of the compounds of the general formula (I) in the mixture is preferably from 0.0001 to 0.1000% by weight, preferably from 0.0002 to 0.0750% by weight, particularly preferably from 0.0005 up to 0.0500% by weight, very particularly preferably from 0.0010 to 0.0250% by weight, based in each case on the total amount of polymerizable compounds.
  • the total amount of polymerizable compounds is preferably at least 5% by weight, preferably at least 50% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 99% by weight, each based on the Total weight of the mixture.
  • Polymerizable compounds are preferably mono-, di- or triethylenically unsaturated C3- to Cs-carboxylic acids, mono-, di- or triethylenically unsaturated C3- to Cs-aldehydes, mono-, di- or triethylenically unsaturated C3- to Cs -Carboxylic acid esters with 1 to 20 carbon atoms in the ester groups, mono-, di- or triethylenically unsaturated C3- to Cs-carboxamides, mono-, di- or triethylenically unsaturated C3- to Cs-nitriles, mono-, di- or triethylenically unsaturated C3 to Cs carboxylic anhydrides, vinyl esters of saturated C2 to C2o carboxylic acids, vinyl ethers of saturated C to Cio alcohols, vinyl aromatics, vinyl heteroaromatics, vinyl lactams with 3 to 10 carbon atoms in the ring, open
  • Mono-, di- or triethylenically unsaturated C3- to Cs-carboxylic acids for example acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid, itaconic acid and maleic acid, mono-, di- or triethylenically unsaturated C3 - To Cs-carboxylic acid esters with 1 to 20 carbon atoms in the ester groups, for example acrylic acid esters with Cr to C2o-alkyl, methacrylic acid esters with Cr to C2o-alkyl, dimethacrylic acid esters with Cr to C2o-alkyl, ethacrylic acid esters with Cr to C20-alkyl , Citraconic acid esters with Cr to C20 alkyl, methylenemalonic acid esters with Cr to C2o-alkyl, crotonic acid esters with Cr
  • polymerizable compounds are dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, glycerol triacrylate, ethoxylated glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 2-methylolpropane triacrylate, 2-methylolpropane triacrylate, 2-methylolpropane triacrylate, 2-methylolpropane triacrylate, 2-hydroxy-ethyl acrylate, dimethylolpropane triacrylate, 2-hydroxy-ethylacrylate, 2-hydroxy-ethylacrylate, 2-hydroxy-ethylacrylate, 2-hydroxy-ethylacrylate, hydroxy-ethylacrylate, hydroxy-ethylacrylate, glycerol triacrylate, polyethylene glycol, glycerol triacrylate, glycerol triacrylate, 2
  • the total amount of the compounds of the general formula (I) in the mixture is preferably from 0.0050 to 0.1000% by weight, preferably from 0.0100 to 0.0750% by weight, particularly preferred from 0.0120 to 0.0500% by weight, very particularly preferably from 0.0150 to 0.0250% by weight, based in each case on acrylic acid.
  • the total amount of the compounds of the general formula (I) in the mixture is preferably from 0.0001 to 0.0100% by weight, preferably from 0.0002 to 0.0075% by weight, particularly preferably from 0.0005 to 0.0050% by weight, very particularly preferably from 0.0010 to 0.0020% by weight, based in each case on the total amount of Methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • the present invention also provides the use of at least one compound of the general formula (I), as defined above, for inhibiting polymerization of at least one polymerizable compound.
  • the present invention further provides a process for storing and / or transporting a mixture containing at least one compound of the general formula (I), as defined above, and at least one polymerizable compound.
  • the mixture is usually stored and / or transported under an atmosphere containing oxygen.
  • the mixture is preferably stored in a container under an oxygen-containing atmosphere with an oxygen content of 5 to 10% by volume and the mixture in the container is regularly circulated, for example by pumping the entire contents of the tank around at least once a week.
  • the relatively low oxygen content prevents ignitable gas mixtures in the container.
  • the circulation replaces used dissolved oxygen in the liquid polymerizable compound.
  • the monomer used was double distilled to remove the polymerization inhibitor MEHQ.
  • the monomer obtained was each admixed with the specified amount of the specified polymerization inhibitor.
  • the relative effectiveness is calculated from the quotient of the time up to the polymerisation of the sample with the examined polymerisation inhibitor and the time up to the polymerisation of the sample with MEHQ. For MEHQ itself, the effectiveness is therefore 100%.
  • MEHQ hydroquinone monomethyl ether
  • TM MP 2,3,6-trimethyl-4-methoxyphenol
  • TMEP 2,3,6-trimethyl-4-ethoxyphenol
  • TMPP 2,3,6-trimethyl-4-propoxyphenol
  • DMMP 2,6-dimethyl-4 -methoxyphenol
  • Table 3 Mixtures with methyl acrylate
  • Table 4 Mixtures with ethyl acrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un mélange qui contient au moins un monoéther d'hydroquinone substitué et au moins un composé polymérisable.
EP21728070.0A 2020-06-05 2021-05-25 Inhibiteurs de polymérisation Pending EP4161892A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20178453 2020-06-05
PCT/EP2021/063807 WO2021244894A1 (fr) 2020-06-05 2021-05-25 Inhibiteurs de polymérisation

Publications (1)

Publication Number Publication Date
EP4161892A1 true EP4161892A1 (fr) 2023-04-12

Family

ID=71016385

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21728070.0A Pending EP4161892A1 (fr) 2020-06-05 2021-05-25 Inhibiteurs de polymérisation

Country Status (5)

Country Link
US (1) US20230242472A1 (fr)
EP (1) EP4161892A1 (fr)
CN (1) CN115697954A (fr)
TW (1) TW202204302A (fr)
WO (1) WO2021244894A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1011315A (en) * 1963-11-12 1965-11-24 Ici Ltd Stabilisers for acrylic or methacrylic esters
JP7298446B2 (ja) * 2019-11-07 2023-06-27 信越化学工業株式会社 アクリロイルオキシ基またはメタクリロイルオキシ基を有する有機ケイ素化合物の製造方法

Also Published As

Publication number Publication date
TW202204302A (zh) 2022-02-01
WO2021244894A1 (fr) 2021-12-09
US20230242472A1 (en) 2023-08-03
CN115697954A (zh) 2023-02-03

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