CA1061355A - Process for producing glycidyl methacrylate - Google Patents
Process for producing glycidyl methacrylateInfo
- Publication number
- CA1061355A CA1061355A CA226,929A CA226929A CA1061355A CA 1061355 A CA1061355 A CA 1061355A CA 226929 A CA226929 A CA 226929A CA 1061355 A CA1061355 A CA 1061355A
- Authority
- CA
- Canada
- Prior art keywords
- alkali metal
- process according
- transesterification
- glycide
- glycidyl methacrylate
- 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.)
- Expired
Links
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkali metal salt Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001339 alkali metal compounds Chemical class 0.000 abstract description 3
- 229940102838 methylmethacrylate Drugs 0.000 description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 101100367084 Caenorhabditis elegans such-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a process for producing glycidyl methacrylate which comprises the transesterification of methyl methacrylate with glycide in the presence of a catalyst selected from an alkali metal or an alkali metal compound. The methanol being formed during the reaction being immediately distilled off.
The present invention provides a process for producing glycidyl methacrylate which comprises the transesterification of methyl methacrylate with glycide in the presence of a catalyst selected from an alkali metal or an alkali metal compound. The methanol being formed during the reaction being immediately distilled off.
Description
~6~L35 Si The present invention relates to a process for producing glycidyl methacrylate.
Glycidyl methacrylate is a useful compound in polymer chemistry, where it is used in the field of lacquers and varnishes, particularly in powdered lacquers.
The following methods are known for the production of glycidyl methacrylate:
1. Reaction of potassium or sodium methacrylate with epichloro- ;
hydrin to glycidyl methacrylate while splitting off potassium or sodium chloride, partly in the presence of quaternary ammonium salts. (See US Patents Nos. 2 524 432, 2 537 981 and 2 567 842, French Patent No. 1 532 542, and British Patent No. 1 208 165).
Glycidyl methacrylate is a useful compound in polymer chemistry, where it is used in the field of lacquers and varnishes, particularly in powdered lacquers.
The following methods are known for the production of glycidyl methacrylate:
1. Reaction of potassium or sodium methacrylate with epichloro- ;
hydrin to glycidyl methacrylate while splitting off potassium or sodium chloride, partly in the presence of quaternary ammonium salts. (See US Patents Nos. 2 524 432, 2 537 981 and 2 567 842, French Patent No. 1 532 542, and British Patent No. 1 208 165).
2. Reaction of methacrylic chloride with glycide in the presence of a halogen acceptor. (See US Patent No. 2 680 109).
However the above methods only produce chlorine-contain-ing glycidyl methacrylate, whereby the quality of secondary pro-ducts of such glycidyl methacrylate is greatly reduced. Moreover, the yield of potassium or sodium chloride causes environmental problems.
Transesterification of methyl methacrylate with glycide is a more desirable method. Thus attention is directed to published Japanese Application (1972) - 38~1 (72.38.421), in which this transesterification in the presence of phosphines as catalysts is described. The amounts of glycidyl methacrylate detected therein were however determined only by gas chromatography and ~-were not obtained as a substance. It is known that the amounts `
of substance are substantially lower than the amounts detected by gas chromatography. These yield data usually are of no lnterest `
to industry since they cannot be achieved. However, if acid catalysts are used, as for example, p-toluene sulphonic acid, then there barely is a reaction (loc. cit.). In the opinion of the experts, other catalysts used for the transesterification, such - 1 - ~11 ~,,; , , .... , . , .. .,.. - , .,.. : .: :.- ' ,r~ :
.:
1~6~35S
such as sodium, magnesium, calcium alcoholates are unsuitable ~`
for this reaction since their use causes polymerization to an increased extent after a short period (loc. cit.). Moreover, .
according to the above Japanese application, the alcoholates are ~.
present at the end of the reaction not in a dissolved form but .
as a suspension. This means that the reaction took place in a heterogeneous system, which is technically more difficult to handle.
It has now been discovered that the transesterification of methyl methacrylate with glycide to glycidyl methacrylate :.. -.: :
takes place in a homogeneous medium with very good yields and :
without polymerization when an alkali metal or an alkali metal compound such as alkali metal alcoholate or alkali metal hydride ;. :
is used as the transesterification catalyst and when the methanol ;~.
formed is immediately distilled off during the reaction.
Primarily sodium or lithium is a suitable alkali metal. ~ .
The alcoholates usually used in the transesterification are ~
applied as alcoholates. Alkali metal salts of methyl, ethyl and ~.
propyl alcohol are preferred. Sodium or lithium methylate or ethylate is particularly preferred. .
The catalysts are used in amounts of 0.05 to 1 % by weight, based on the sum of the reaction components methyl methacrylate and glycide, and preferably in amounts of 0.1 to O.5% by weight. ~mounts of 0.3 to 0.5% by weight were found to ~.
be particularly suitable.
It is very surprising to find that alkali metal and the alkali metal compounds such as mentioned hereinbefore are capable of causing a substantial increase in the yield, that is to say, as a substance, with the polymerization of methyl metha-crylate almost completely suppressed, in the transesterification. -.
The view that the ion polymerization of methyl methacrylate is caused by alkalis was expressed not only in the Japanese : -;:
- :2 -::
13~
publication mentioned hereinbefore but qulte generally by thetechnical world. In this respect the compounds of sodium, lithium and magnesium were considered equivalent (see "Kirk-Othmer-Encyclopedia of Chemical Technology, 2nd Edition, Vol 13, page 351").
Therefore, it could not be predicted that just the alkalis to be used according to the invention would promote the transes-terification but not the polymerization.
The transesterification and the distillation of methanol are carried out at temperatures from 50 to 100C, preferably from 70 to 80 C and at a pressure of from 100 to 760 torr. A pressure of 200 to 400 torr, at which the distillation sump is not significantly affected, is particularly favourable.
Since the transesterification is an equilibrium reaction, it is favourable to use one of the reactants in excess and,as metnioned hereinbefore, to immediately remove the methanol as it is formed. Methyl methacrylate and glycide are preferably used in a molar ratio of 5 to 10:1 since the rate of reaction and the yield are increased by the excess of methyl methacrylate.
Methyl methacrylate also serves as an entraining agent for re-moving the methanol formed, whose azeotrope with methyl methacry-late at 64.2 C lies at 760 torr. This azeotrope contains 82%
by volume of methanol.
Compounds suchashydroquinone, hydroquinone monomethyl !' ether, aromatic amines such as diphenyl amine and phenyl-~-naphtyl ;-~
amine can be used as polymerization inhibitors in a conventional manner. Oxygen or air or oxygen-containing gases may additionally ;~
be passed through the solution.
The mixture of glycide and methyl methacrylate is charged into the reactor first, whereupon the catalyst and the polymeri-zation inhibitor are added and oxygen or air is passed through simultaneously. This favourably affects the inhibition of the
However the above methods only produce chlorine-contain-ing glycidyl methacrylate, whereby the quality of secondary pro-ducts of such glycidyl methacrylate is greatly reduced. Moreover, the yield of potassium or sodium chloride causes environmental problems.
Transesterification of methyl methacrylate with glycide is a more desirable method. Thus attention is directed to published Japanese Application (1972) - 38~1 (72.38.421), in which this transesterification in the presence of phosphines as catalysts is described. The amounts of glycidyl methacrylate detected therein were however determined only by gas chromatography and ~-were not obtained as a substance. It is known that the amounts `
of substance are substantially lower than the amounts detected by gas chromatography. These yield data usually are of no lnterest `
to industry since they cannot be achieved. However, if acid catalysts are used, as for example, p-toluene sulphonic acid, then there barely is a reaction (loc. cit.). In the opinion of the experts, other catalysts used for the transesterification, such - 1 - ~11 ~,,; , , .... , . , .. .,.. - , .,.. : .: :.- ' ,r~ :
.:
1~6~35S
such as sodium, magnesium, calcium alcoholates are unsuitable ~`
for this reaction since their use causes polymerization to an increased extent after a short period (loc. cit.). Moreover, .
according to the above Japanese application, the alcoholates are ~.
present at the end of the reaction not in a dissolved form but .
as a suspension. This means that the reaction took place in a heterogeneous system, which is technically more difficult to handle.
It has now been discovered that the transesterification of methyl methacrylate with glycide to glycidyl methacrylate :.. -.: :
takes place in a homogeneous medium with very good yields and :
without polymerization when an alkali metal or an alkali metal compound such as alkali metal alcoholate or alkali metal hydride ;. :
is used as the transesterification catalyst and when the methanol ;~.
formed is immediately distilled off during the reaction.
Primarily sodium or lithium is a suitable alkali metal. ~ .
The alcoholates usually used in the transesterification are ~
applied as alcoholates. Alkali metal salts of methyl, ethyl and ~.
propyl alcohol are preferred. Sodium or lithium methylate or ethylate is particularly preferred. .
The catalysts are used in amounts of 0.05 to 1 % by weight, based on the sum of the reaction components methyl methacrylate and glycide, and preferably in amounts of 0.1 to O.5% by weight. ~mounts of 0.3 to 0.5% by weight were found to ~.
be particularly suitable.
It is very surprising to find that alkali metal and the alkali metal compounds such as mentioned hereinbefore are capable of causing a substantial increase in the yield, that is to say, as a substance, with the polymerization of methyl metha-crylate almost completely suppressed, in the transesterification. -.
The view that the ion polymerization of methyl methacrylate is caused by alkalis was expressed not only in the Japanese : -;:
- :2 -::
13~
publication mentioned hereinbefore but qulte generally by thetechnical world. In this respect the compounds of sodium, lithium and magnesium were considered equivalent (see "Kirk-Othmer-Encyclopedia of Chemical Technology, 2nd Edition, Vol 13, page 351").
Therefore, it could not be predicted that just the alkalis to be used according to the invention would promote the transes-terification but not the polymerization.
The transesterification and the distillation of methanol are carried out at temperatures from 50 to 100C, preferably from 70 to 80 C and at a pressure of from 100 to 760 torr. A pressure of 200 to 400 torr, at which the distillation sump is not significantly affected, is particularly favourable.
Since the transesterification is an equilibrium reaction, it is favourable to use one of the reactants in excess and,as metnioned hereinbefore, to immediately remove the methanol as it is formed. Methyl methacrylate and glycide are preferably used in a molar ratio of 5 to 10:1 since the rate of reaction and the yield are increased by the excess of methyl methacrylate.
Methyl methacrylate also serves as an entraining agent for re-moving the methanol formed, whose azeotrope with methyl methacry-late at 64.2 C lies at 760 torr. This azeotrope contains 82%
by volume of methanol.
Compounds suchashydroquinone, hydroquinone monomethyl !' ether, aromatic amines such as diphenyl amine and phenyl-~-naphtyl ;-~
amine can be used as polymerization inhibitors in a conventional manner. Oxygen or air or oxygen-containing gases may additionally ;~
be passed through the solution.
The mixture of glycide and methyl methacrylate is charged into the reactor first, whereupon the catalyst and the polymeri-zation inhibitor are added and oxygen or air is passed through simultaneously. This favourably affects the inhibition of the
- 3 -,:
~L~D6~355 ~, ~
.
polymerization. As mentioned hereinbefore, immediately upon heating, the methanol formed is distilled ofE along with excess methyl methacrylate. Upon termination of the reaction the residual methyl methacrylate and in reacted glycide are separated in vacuo and the crude glycidyl methacrylate is conven~
tionally fractionated in vacuo.
The present invention will be further illustrated by way of the following Examples.
Example 1 500 g (5 moles) of methyl methacrylate, 37 g ~0.5 mole) of glycide and 1 g of hydroquinone monomethyl ether as the polymerization inhibitor are charged into a 2-litre three-necked ~;~
flask, whereupon 0.43 g of lithium methylate (0.5% by weight of catalyst, based on the reactants) is added. The mixture is then heated to a temperature of 70 to 80C. The methanol formed and the methyl methacrylate are immediately distilled off via a 20 cm packed column (Raschig rings, diameter 6 mm) at a pressure of 200 torr and at a reflux ratio of 3:1. During the reaction air is passed through via a capillary tube. After a reaction time of 2 hours the reaction rate of glycide is 98.5% and the yield of glycidyl methacrylate 95%. These two values were determined by gas chromatography. Upon ~iltering the solution the residual methyl methacrylate and in reacted glycide are distilled off in vacuo by means of a falling-film evaporator. The crude glycidyl methacrylate is once more distilled at 10 torr (b.p.10 = 74 to 75C). The glycidyl methacrylate is obtained as a colorless liquid. The yield is 58 g (82~ of the theoretical yield).
Example 2 As described in Example 1, 37 g (0.5 mole) of glycide are transesterified with 250 g (2.5 moles) of methyl methacrylate while adding 1 g of hydroquinone methyl ether as the inhibitor and 0.086 g of lithium methylate as the catalyst (0.1% by weight of : ' . , . , ~ .: , . : , .
~61355 catalyst, relative to the reactants?. After 2 1/2 hours the reaction rate of glycide is 90.9% and the yield of glycidyl methacrylate 95.7%.
Example 3 As described in Example 1, 37 g tO.5 mole) of glycide are transesterified with 500 g (5 moles) of methyl methacrylate while adding 1 g of hydroquinone monomethyl ether as the inhibitor and 0.086 g of lithium hydride as the catalyst (0.1% by weight of catalyst, relative to the reactants). After 2 hours the reaction rate of glycide is 98.6% and the yield of glycidyl methacrylate 95.1%. ``~ i Example 4 Example 1 was repeated except that 0.43 g of sodium methylate was used instead of lithium methylate. After a reaction time of 2 hours analogous results were obtained.
Example 5 For comparison, magnesium methylate was used instead of sodium methylate. In all other respects the experimental condi-tions were identical to those of the Examples 1 and 4. After 2 ho~rs no reaction had taken place.
~ ' ,.:' ' ";:"',' .:~ . ' .
,,,~ , ,~:,' ' '~
~L~D6~355 ~, ~
.
polymerization. As mentioned hereinbefore, immediately upon heating, the methanol formed is distilled ofE along with excess methyl methacrylate. Upon termination of the reaction the residual methyl methacrylate and in reacted glycide are separated in vacuo and the crude glycidyl methacrylate is conven~
tionally fractionated in vacuo.
The present invention will be further illustrated by way of the following Examples.
Example 1 500 g (5 moles) of methyl methacrylate, 37 g ~0.5 mole) of glycide and 1 g of hydroquinone monomethyl ether as the polymerization inhibitor are charged into a 2-litre three-necked ~;~
flask, whereupon 0.43 g of lithium methylate (0.5% by weight of catalyst, based on the reactants) is added. The mixture is then heated to a temperature of 70 to 80C. The methanol formed and the methyl methacrylate are immediately distilled off via a 20 cm packed column (Raschig rings, diameter 6 mm) at a pressure of 200 torr and at a reflux ratio of 3:1. During the reaction air is passed through via a capillary tube. After a reaction time of 2 hours the reaction rate of glycide is 98.5% and the yield of glycidyl methacrylate 95%. These two values were determined by gas chromatography. Upon ~iltering the solution the residual methyl methacrylate and in reacted glycide are distilled off in vacuo by means of a falling-film evaporator. The crude glycidyl methacrylate is once more distilled at 10 torr (b.p.10 = 74 to 75C). The glycidyl methacrylate is obtained as a colorless liquid. The yield is 58 g (82~ of the theoretical yield).
Example 2 As described in Example 1, 37 g (0.5 mole) of glycide are transesterified with 250 g (2.5 moles) of methyl methacrylate while adding 1 g of hydroquinone methyl ether as the inhibitor and 0.086 g of lithium methylate as the catalyst (0.1% by weight of : ' . , . , ~ .: , . : , .
~61355 catalyst, relative to the reactants?. After 2 1/2 hours the reaction rate of glycide is 90.9% and the yield of glycidyl methacrylate 95.7%.
Example 3 As described in Example 1, 37 g tO.5 mole) of glycide are transesterified with 500 g (5 moles) of methyl methacrylate while adding 1 g of hydroquinone monomethyl ether as the inhibitor and 0.086 g of lithium hydride as the catalyst (0.1% by weight of catalyst, relative to the reactants). After 2 hours the reaction rate of glycide is 98.6% and the yield of glycidyl methacrylate 95.1%. ``~ i Example 4 Example 1 was repeated except that 0.43 g of sodium methylate was used instead of lithium methylate. After a reaction time of 2 hours analogous results were obtained.
Example 5 For comparison, magnesium methylate was used instead of sodium methylate. In all other respects the experimental condi-tions were identical to those of the Examples 1 and 4. After 2 ho~rs no reaction had taken place.
~ ' ,.:' ' ";:"',' .:~ . ' .
,,,~ , ,~:,' ' '~
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing glycidyl methacrylate which comprises the transesterification of methyl methacrylate with glycide in the molar ratio of 5 to 10:1, in the presence of a catalyst selected from an alkali metal, an alkali metal hydride and an alkali metal alcoholate in an amount of 0.05 to 1% by weight based on the total reaction components methyl methacrylate and glycide and in the presence of a polymerization inhibitor selected from hydroquinone, hydroquinone monomethyl ether and an aromatic amine the methanol formed during the reaction being immediately distilled off, the transesterification and the distillation of methanol being carried out at tempera-tures from 50°C to 100°C and pressures of 100 to 760 torr.
2. A process according to claim 1 in which the cata-lyst is an alkali metal salt of methyl, ethyl or propyl alcohol.
3. A process according to claim 1 in which the cata-lyst is lithium or sodium methylate or ethylate.
4. A process according to claim 1, 2 or 3 in which the catalyst is present in an amount of 0.1 to 0.5% based on the total reaction components.
5. A process according to claim 1, 2 or 3 in which the catalyst is present in an amount of 0.3 to 0.5% based on the total reaction components.
6. A process as claimed in claim 1 in which the temp-erature is from 70°C to 80°C.
7. A process as claimed in claim 6 in which the pressure is from 200 to 400 torr.
8. A process according to claim 1, 2 or 3 in which oxygen or air is passed through during transesterification.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742423405 DE2423405C3 (en) | 1974-05-14 | 1974-05-14 | Process for the production of glycidyl methacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061355A true CA1061355A (en) | 1979-08-28 |
Family
ID=5915531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA226,929A Expired CA1061355A (en) | 1974-05-14 | 1975-05-14 | Process for producing glycidyl methacrylate |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS6137268B2 (en) |
| AT (1) | AT341538B (en) |
| BE (1) | BE829033A (en) |
| CA (1) | CA1061355A (en) |
| CH (1) | CH599949A5 (en) |
| DD (1) | DD118413A5 (en) |
| DE (1) | DE2423405C3 (en) |
| FR (1) | FR2271222B1 (en) |
| GB (1) | GB1441085A (en) |
| IT (1) | IT1032669B (en) |
| NL (1) | NL7505019A (en) |
| SU (1) | SU942595A3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7605330A (en) * | 1975-06-05 | 1976-12-07 | Degussa | PROCESS FOR PREPARING GLYCIDYL METHA CRYLATE. |
| JPS543007A (en) | 1977-06-06 | 1979-01-11 | Nippon Oil & Fats Co Ltd | Preparation of glycidyl (meth)acrylate |
| JPS5793930A (en) * | 1980-12-03 | 1982-06-11 | Mitsui Toatsu Chem Inc | Preparation of methacrylic ester |
| DE3140764A1 (en) | 1981-10-14 | 1983-04-28 | Röhm GmbH, 6100 Darmstadt | METHOD FOR PRODUCING THE ESTER VOPN CARBONIC ACIDS WITH ALCOHOLS CONTAINING EPOXY GROUPS |
| DE3423441A1 (en) * | 1984-06-26 | 1986-01-02 | Röhm GmbH, 6100 Darmstadt | METHOD FOR THE PRODUCTION OF ESTERS OF ACRYLIC AND METHACRYLIC ACID BY TRANSESTERATION |
| US4780555A (en) * | 1988-01-04 | 1988-10-25 | Dow Corning Corporation | Method for preparing and stabilizing acryl-functional halosilanes |
| DE102009057699A1 (en) | 2009-12-07 | 2011-06-09 | Kruk, Sandra | Bottom part for flat solar collector, is provided with thermal insulation of insulating material adjacent to its inner side, where part is designed as one-piece multi-layer body having fiber-reinforced polyester layer |
| JP5606132B2 (en) * | 2010-04-12 | 2014-10-15 | 三菱レイヨン株式会社 | Method for producing (meth) acrylic acid ester |
| CN112625007B (en) * | 2019-10-09 | 2023-05-26 | 佳化化学(上海)有限公司 | Method for preparing glycidyl methacrylate |
| CN116535367A (en) * | 2023-04-17 | 2023-08-04 | 湖北荆洪生物科技股份有限公司 | A kind of method for preparing glycidyl methacrylate |
-
1974
- 1974-05-14 DE DE19742423405 patent/DE2423405C3/en not_active Expired
-
1975
- 1975-04-11 SU SU752121916A patent/SU942595A3/en active
- 1975-04-15 IT IT6795375A patent/IT1032669B/en active
- 1975-04-24 GB GB1700975A patent/GB1441085A/en not_active Expired
- 1975-04-28 NL NL7505019A patent/NL7505019A/en not_active Application Discontinuation
- 1975-05-05 CH CH577375A patent/CH599949A5/xx not_active IP Right Cessation
- 1975-05-12 DD DD18596475A patent/DD118413A5/xx unknown
- 1975-05-13 JP JP5553275A patent/JPS6137268B2/ja not_active Expired
- 1975-05-13 AT AT364975A patent/AT341538B/en not_active IP Right Cessation
- 1975-05-13 BE BE6045011A patent/BE829033A/en not_active IP Right Cessation
- 1975-05-14 CA CA226,929A patent/CA1061355A/en not_active Expired
- 1975-05-14 FR FR7515043A patent/FR2271222B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6137268B2 (en) | 1986-08-22 |
| BE829033A (en) | 1975-11-13 |
| DE2423405A1 (en) | 1975-11-27 |
| DE2423405C3 (en) | 1983-05-19 |
| DE2423405B2 (en) | 1978-03-23 |
| JPS50154205A (en) | 1975-12-12 |
| IT1032669B (en) | 1979-06-20 |
| FR2271222A1 (en) | 1975-12-12 |
| GB1441085A (en) | 1976-06-30 |
| SU942595A3 (en) | 1982-07-07 |
| NL7505019A (en) | 1975-11-18 |
| AT341538B (en) | 1978-02-10 |
| CH599949A5 (en) | 1978-06-15 |
| ATA364975A (en) | 1977-06-15 |
| DD118413A5 (en) | 1976-03-05 |
| FR2271222B1 (en) | 1977-07-08 |
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