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WO2019050830A1 - Method for recovery of methacrolein and methanol from methacrolein dimethylacetal - Google Patents

Method for recovery of methacrolein and methanol from methacrolein dimethylacetal Download PDF

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Publication number
WO2019050830A1
WO2019050830A1 PCT/US2018/049336 US2018049336W WO2019050830A1 WO 2019050830 A1 WO2019050830 A1 WO 2019050830A1 US 2018049336 W US2018049336 W US 2018049336W WO 2019050830 A1 WO2019050830 A1 WO 2019050830A1
Authority
WO
WIPO (PCT)
Prior art keywords
methacrolein
ion exchange
methanol
exchange resin
mda
Prior art date
Application number
PCT/US2018/049336
Other languages
French (fr)
Inventor
Alan E. SOPCHIK
William G. Worley
Rajesh Shah
Original Assignee
Dow Global Technologies Llc
Rohm And Haas Company
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 Dow Global Technologies Llc, Rohm And Haas Company filed Critical Dow Global Technologies Llc
Priority to JP2020512881A priority Critical patent/JP7245821B2/en
Priority to BR112020004257-9A priority patent/BR112020004257B1/en
Priority to US16/644,571 priority patent/US11098000B2/en
Priority to EP18778700.7A priority patent/EP3681855B1/en
Priority to SG11202002053RA priority patent/SG11202002053RA/en
Priority to KR1020207008867A priority patent/KR20200046074A/en
Priority to CN201880057054.8A priority patent/CN111051275A/en
Priority to MX2020002414A priority patent/MX2020002414A/en
Priority to CA3074717A priority patent/CA3074717A1/en
Publication of WO2019050830A1 publication Critical patent/WO2019050830A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to a process for recovery of methacrolein and methanol from methacrolein dimethylacetal, a reaction product from preparation of methyl methacrylate.
  • MMA methyl methacrylate
  • MDA methacrolein dimethyl acetal
  • MA key intermediate methacrolein
  • mis is done by hydrolyzing MDA in the presence of a mineral acid, which is undesirable due to possible corrosion and the increased process complexity due to neutralization, catalyst disposal, and wastewater treatment requirements.
  • Hydrolysis of acetals in the presence of ion exchange resins having sulfonic acid functionality is known, see, e.g., Coppola, G. M. Synthesis 1984,
  • the present invention is directed to a process for recovering methacrolein and methanol from methacrolein dimethyl acetal; said method comprising contacting a mixture comprising methyl methacrylate and methacrolein dimethyl acetal with a strong acid ion exchange resin in the presence of water; wherein said mixture comprises no more than 0.2 wt% sodium methacrylate.
  • the Figure is a schematic of an integrated process for producing methyl
  • a ''strong acid ion exchange resin is an ion exchange resin having sulfonic acid functionality.
  • the ion exchange resin is in the form of crosslinked polystyrene beads.
  • the MDA is generated in a process which comprises treating
  • oxidative esterification reactor OER
  • the reaction typically produces MMA and MDA, along with methacrylic acid and unreacted methanol.
  • the reaction products are fed to a methanol recovery distillation column which provides an overhead stream rich in methanol and methacrolein; preferably mis stream is recycled back to the OER.
  • the bottoms stream from the methanol recovery distillation column comprises MMA, MDA, methacrylic acid, salts and water.
  • MDA is hydrolyzed in a medium comprising MMA, MDA, methacrylic acid and water.
  • the strong acid ion exchange resin is a macroreticular resin.
  • the resin is in the form of beads having a harmonic mean size from 100 to 1200 microns; preferably at least 300 microns, preferably at least 400 microns, preferably at least 500 microns; preferably no more than 1100 microns, preferably no more than 1000 microns, preferably no more than 900 microns, preferably no more man 800 microns.
  • the resin has an average pore diameter from 20 to 600 A; preferably at least 50 A, preferably at least 100 A, preferably at least 200 A; preferably no more than 500 A.
  • the strong acid ion exchange resin is selected from the group consisting of AMBERLYST-15 resin, AMBERLYST 36, DOWEX DR-2030, DOWEX HCR-S, DOWEX HCR-W2, DOWEX HGR and DOWEX HGR-W2, DOWEX M-3, DOWEX G-26 and DOWEX 50WX series of resins.
  • the strong acid ion exchange resin is contained in a fluid or fixed bed in a continuous reactor.
  • Water is present when the strong acid ion exchange resin is contacted with MDA and MMA.
  • the source of the water is the process stream comprising MMA and MDA, water which is added to the MDA and MMA, the strong acid ion exchange resin, or a combination thereof.
  • At least a portion of salts generated as byproducts is removed prior to contacting the OER reaction mixture with the strong acid ion exchange resin, preferably at least 50 wt% of the salts, preferably at least 75 wt%, preferably at least 90 wt%, preferably at least 95 wt%, preferably substantially all of the salts.
  • the concentration of sodium methacrylate in mixture comprising methyl methacrylate and methacrolein dimethyl acetal is no greater than 0.15 wt%, preferably no greater than 0.1 wt%, preferably no greater than 0.05 wt%, preferably no greater than 0.02 wt%.
  • the present invention is further directed to an integrated process for production of methyl methacrylate.
  • MDA may be hydrolyzed by separating the bottoms stream from a methanol recovery distillation column; said stream comprising MMA, MDA, methacrylic acid, salts and water; and performing the hydrolysis in the organic phase. It may be necessary to add water to the organic phase to ensure that there is sufficient water for the MDA hydrolysis; these amounts may be determined easily from the composition of the organic phase.
  • the product of the MDA hydrolysis reactor is phase separated and the organic phase passes through one or more distillation columns to produce MMA product and light and/or heavy byproducts.
  • the Figure depicts an integrated process in which MDA hydrolysis occurs after phase separation of the bottoms stream from a methanol recovery column.
  • Feed stream 1 enters OER 2 which produces product stream 3 which then passes into distillation column 4.
  • the overhead stream 5 from column 4 which comprises methanol and methacrolein, is recycled to the OER, while bottoms stream 6 is sent to phase separator 7.
  • Organic phase 9 is sent to acetal hydrolysis reactor 11 along with stream 10 comprising water, while aqueous phase 8 comprising water and salts is removed.
  • Product 12 from reactor 11 goes into phase separator 13, with crude MMA product stream 15 passing into further purification while aqueous layer 14 is removed. Further purification of stream 15 by conventional distillation techniques provides methacrolein for recycle along with purified MMA.
  • Phosphoric acid hydrolysis kinetics was much slower compared to all other acids even at high 5% phosphoric acid levels.
  • pTSA was used as the monohydrate.
  • a 2 wt% pTSA solution was used. The reaction rates for MSA and pTSA were similar, each reaching equilibrium within ⁇ 30 minutes.
  • MAA Methacrylic Acid
  • MMA process impurity methacrylic acid was screened for hydrolysis catalyst activity.
  • MAA is present in the Methanol Recovery Column, but typically only at very low levels.
  • an MDA hydrolysis reaction was carried out using 4% MAA.
  • MAA catalyzed MDA hydrolysis albeit at an almost two-fold slower rate compared to the other acids studied here.
  • AMBERL YST- 15 (dry) IER resin was used for this example. Based on Amberlyst-15 > 4.7 eq/kg, the IER sulfonic acid content used here was about four times that in 2% pTSA experiments. The rate of Amberlyst-15 catalyzed acetal hydrolysis at both the 5 and 30- minute intervals were similar to those using 1 % sulfuric acid. Equilibrium was reached within 30 min. EFFECT OF SALTS

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for recovering methacrolein and methanol from methacrolein dimethyl acetal. The method comprises a step of contacting a mixture comprising methyl methacrylate and methacrolein dimethyl acetal with a strong acid ion exchange resin in the presence of water. The mixture comprises no more than 0.2 wt% sodium methacrylate.

Description

METHOD FOR RECOVERY OF METHACROLEIN AND METHANOL FROM METHACROLEIN DIMETHYLACETAL
BACKGROUND OF THE INVENTION
The invention relates to a process for recovery of methacrolein and methanol from methacrolein dimethylacetal, a reaction product from preparation of methyl methacrylate.
A significant process yield loss in preparation of methyl methacrylate (MMA) is formation of methacrolein dimethyl acetal (MDA) as a result of a side reaction of the key intermediate methacrolein (MA) with methanol. Conventionally, mis is done by hydrolyzing MDA in the presence of a mineral acid, which is undesirable due to possible corrosion and the increased process complexity due to neutralization, catalyst disposal, and wastewater treatment requirements. Hydrolysis of acetals in the presence of ion exchange resins having sulfonic acid functionality is known, see, e.g., Coppola, G. M. Synthesis 1984,
1021. However, there has been no disclosure of MDA hydrolysis in the presence of acids other than mineral acids. There is a need for a more efficient process for recovering methacrolein and methanol from MDA resulting from preparation of methyl methacrylate.
SUMMARY OF THE INVENTION
The present invention is directed to a process for recovering methacrolein and methanol from methacrolein dimethyl acetal; said method comprising contacting a mixture comprising methyl methacrylate and methacrolein dimethyl acetal with a strong acid ion exchange resin in the presence of water; wherein said mixture comprises no more than 0.2 wt% sodium methacrylate.
BRIEF DESCRIPTION OF THE DRAWING
The Figure is a schematic of an integrated process for producing methyl
methacrylate.
DETAILED DESCRIPTION OF THE INVENTION
All percentage compositions are weight percentages (wt%), and all temperatures are in °C, unless otherwise indicated. A ''strong acid ion exchange resin" is an ion exchange resin having sulfonic acid functionality. Preferably, the ion exchange resin is in the form of crosslinked polystyrene beads.
Preferably, the MDA is generated in a process which comprises treating
methacrolein with methanol in an oxidative esterification reactor (OER). The reaction typically produces MMA and MDA, along with methacrylic acid and unreacted methanol. Preferably, the reaction products are fed to a methanol recovery distillation column which provides an overhead stream rich in methanol and methacrolein; preferably mis stream is recycled back to the OER. The bottoms stream from the methanol recovery distillation column comprises MMA, MDA, methacrylic acid, salts and water. In one embodiment of the invention, MDA is hydrolyzed in a medium comprising MMA, MDA, methacrylic acid and water.
Preferably, the strong acid ion exchange resin is a macroreticular resin. Preferably, the resin is in the form of beads having a harmonic mean size from 100 to 1200 microns; preferably at least 300 microns, preferably at least 400 microns, preferably at least 500 microns; preferably no more than 1100 microns, preferably no more than 1000 microns, preferably no more than 900 microns, preferably no more man 800 microns. Preferably, the resin has an average pore diameter from 20 to 600 A; preferably at least 50 A, preferably at least 100 A, preferably at least 200 A; preferably no more than 500 A. Preferably, the strong acid ion exchange resin is selected from the group consisting of AMBERLYST-15 resin, AMBERLYST 36, DOWEX DR-2030, DOWEX HCR-S, DOWEX HCR-W2, DOWEX HGR and DOWEX HGR-W2, DOWEX M-3, DOWEX G-26 and DOWEX 50WX series of resins. Preferably, the strong acid ion exchange resin is contained in a fluid or fixed bed in a continuous reactor.
Water is present when the strong acid ion exchange resin is contacted with MDA and MMA. The source of the water is the process stream comprising MMA and MDA, water which is added to the MDA and MMA, the strong acid ion exchange resin, or a combination thereof.
At least a portion of salts generated as byproducts (e.g., sodium methacrylate) is removed prior to contacting the OER reaction mixture with the strong acid ion exchange resin, preferably at least 50 wt% of the salts, preferably at least 75 wt%, preferably at least 90 wt%, preferably at least 95 wt%, preferably substantially all of the salts. Preferably, the concentration of sodium methacrylate in mixture comprising methyl methacrylate and methacrolein dimethyl acetal is no greater than 0.15 wt%, preferably no greater than 0.1 wt%, preferably no greater than 0.05 wt%, preferably no greater than 0.02 wt%.
The present invention is further directed to an integrated process for production of methyl methacrylate. MDA may be hydrolyzed by separating the bottoms stream from a methanol recovery distillation column; said stream comprising MMA, MDA, methacrylic acid, salts and water; and performing the hydrolysis in the organic phase. It may be necessary to add water to the organic phase to ensure that there is sufficient water for the MDA hydrolysis; these amounts may be determined easily from the composition of the organic phase. The product of the MDA hydrolysis reactor is phase separated and the organic phase passes through one or more distillation columns to produce MMA product and light and/or heavy byproducts.
The Figure depicts an integrated process in which MDA hydrolysis occurs after phase separation of the bottoms stream from a methanol recovery column. Feed stream 1 enters OER 2 which produces product stream 3 which then passes into distillation column 4. The overhead stream 5 from column 4 , which comprises methanol and methacrolein, is recycled to the OER, while bottoms stream 6 is sent to phase separator 7. Organic phase 9 is sent to acetal hydrolysis reactor 11 along with stream 10 comprising water, while aqueous phase 8 comprising water and salts is removed. Product 12 from reactor 11 goes into phase separator 13, with crude MMA product stream 15 passing into further purification while aqueous layer 14 is removed. Further purification of stream 15 by conventional distillation techniques provides methacrolein for recycle along with purified MMA.
EXAMPLES
Comparative examples of various strong organic and inorganic acids and heterogeneous AMBERLYST-15 resin catalyzed MDA hydrolysis are given below, Table 1. Hydrolysis experiments using mineral and organic acids were performed by charging a reaction flask with MMA and MDA, heating to 60 °C, then adding an aqueous acid charge. Reactions using AMBERLYST -15 resin catalysis first combined MMA, MDA, and Amberlyst-15 resin, heated to 60 °C, then the water was added. The progress of the hydrolysis was monitored using gas chromatography (GC) of the upper organic layer.
Figure imgf000004_0001
Experimentally, the equilibrium limit appeared to be about 180-ppm acetal at 60°C if methanol and methacrolein are not removed during the reaction. Hie MDA concentration used in mis study is approximately 10-fold greater than that expected in the bottom of the MeOH Recovery Column. RESULTS
Phosphoric Acid
Phosphoric acid hydrolysis kinetics was much slower compared to all other acids even at high 5% phosphoric acid levels.
Sulfuric Add and Methanesulfonic Acid (MSA)
MSA and sulfuric acid kinetics were both faster than phosphoric acid. At 5 wt% sulfuric acid, the reaction reached near equilibrium within 5 minutes. At 1 wt%, hydrolysis using both sulfuric and methanesulfonic acids reached equilibrium in about 30 minutes.
/^-Toluenesulfonic Add (pTSA)
pTSA was used as the monohydrate. To compare the hydrolysis rates of pTSA with MSA on a similar molar basis, a 2 wt% pTSA solution was used. The reaction rates for MSA and pTSA were similar, each reaching equilibrium within ~ 30 minutes.
Methacrylic Acid (MAA)
MMA process impurity methacrylic acid, was screened for hydrolysis catalyst activity. MAA is present in the Methanol Recovery Column, but typically only at very low levels. For demonstration purposes, an MDA hydrolysis reaction was carried out using 4% MAA. MAA catalyzed MDA hydrolysis albeit at an almost two-fold slower rate compared to the other acids studied here.
AMBERLYST-15
AMBERL YST- 15 (dry) IER resin was used for this example. Based on Amberlyst-15 > 4.7 eq/kg, the IER sulfonic acid content used here was about four times that in 2% pTSA experiments. The rate of Amberlyst-15 catalyzed acetal hydrolysis at both the 5 and 30- minute intervals were similar to those using 1 % sulfuric acid. Equilibrium was reached within 30 min. EFFECT OF SALTS
Additional hydrolysis experiments were conducted as described above, but with 0.48% sodium methacrylate (NaMAA) in the mixture. With 0.2% MSA there was no detectible conversion in two hours. With AMBERLYST-15 (dry) IER resin (0.41 g in 20.07 g total mixture) the conversion was only 13% in two hours. A control experiment with 0.2% MSA without salt led to 99% conversion in five minutes.

Claims

CLAIMS:
1. A process for recovering methacrolein and methanol from methacrolein dimethyl acetal; said method comprising contacting a mixture comprising methyl methacrylate and methacrolein dimethyl acetal with a strong acid ion exchange resin in the presence of water; wherein said mixture comprises no more than 0.2 wt% sodium methacrylate.
2. The process of claim 1 wherein the strong acid ion exchange resin is a
macroreticular resin.
3. The process of claim 2 wherein the strong acid ion exchange resin is in the form of beads having a harmonic mean size from 100 to 1200 microns.
4. The process of claim 3 wherein the strong acid ion exchange resin is contained in a fluid or fixed bed in a continuous reactor.
5. The process of claim 4 wherein the strong acid ion exchange resin has an average pore diameter from 20 to 600 A.
6. The process of claim 5 wherein said mixture comprises no more than 0.1 wt% sodium methacrylate.
PCT/US2018/049336 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal WO2019050830A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
JP2020512881A JP7245821B2 (en) 2017-09-11 2018-09-04 Method for recovering methacrolein and methanol from methacrolein dimethylacetal
BR112020004257-9A BR112020004257B1 (en) 2017-09-11 2018-09-04 PROCESS FOR RECOVERING METHACROLEIN AND METHANOL FROM METHACROLEIN DIMETHYL ACETAL
US16/644,571 US11098000B2 (en) 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal
EP18778700.7A EP3681855B1 (en) 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal
SG11202002053RA SG11202002053RA (en) 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal
KR1020207008867A KR20200046074A (en) 2017-09-11 2018-09-04 Method for recovering methacrolein and methanol from methacrolein dimethylacetal
CN201880057054.8A CN111051275A (en) 2017-09-11 2018-09-04 Method for recovering methacrolein and methanol from methacrolein dimethyl acetal
MX2020002414A MX2020002414A (en) 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal.
CA3074717A CA3074717A1 (en) 2017-09-11 2018-09-04 Method for recovery of methacrolein and methanol from methacrolein dimethylacetal

Applications Claiming Priority (2)

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US201762556527P 2017-09-11 2017-09-11
US62/556,527 2017-09-11

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JP (1) JP7245821B2 (en)
KR (1) KR20200046074A (en)
CN (1) CN111051275A (en)
BR (1) BR112020004257B1 (en)
CA (1) CA3074717A1 (en)
MX (1) MX2020002414A (en)
SG (1) SG11202002053RA (en)
WO (1) WO2019050830A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4428116A1 (en) 2023-03-07 2024-09-11 Röhm GmbH New process for the preparation of methyl methacrylate via acetalic intermediates

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US5079266A (en) * 1988-01-04 1992-01-07 Betz Laboratories, Inc. Method of generating acrolein
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EP0150280A2 (en) * 1984-02-01 1985-08-07 Degussa Aktiengesellschaft Process for the preparation of acetals
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4428116A1 (en) 2023-03-07 2024-09-11 Röhm GmbH New process for the preparation of methyl methacrylate via acetalic intermediates

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MX2020002414A (en) 2020-07-13
EP3681855B1 (en) 2021-08-11
KR20200046074A (en) 2020-05-06
JP2020533285A (en) 2020-11-19
CA3074717A1 (en) 2019-03-14
SG11202002053RA (en) 2020-04-29
BR112020004257A2 (en) 2020-09-29
US20210061746A1 (en) 2021-03-04
BR112020004257B1 (en) 2023-05-16
JP7245821B2 (en) 2023-03-24
US11098000B2 (en) 2021-08-24
CN111051275A (en) 2020-04-21

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