CN109134245A - A kind of method of ester-interchange method production hydroxyethyl methacrylate - Google Patents
A kind of method of ester-interchange method production hydroxyethyl methacrylate Download PDFInfo
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- CN109134245A CN109134245A CN201811244356.4A CN201811244356A CN109134245A CN 109134245 A CN109134245 A CN 109134245A CN 201811244356 A CN201811244356 A CN 201811244356A CN 109134245 A CN109134245 A CN 109134245A
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- Prior art keywords
- ester
- hydroxyethyl methacrylate
- polymerization inhibitor
- interchange
- ethylene glycol
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 title claims abstract description 23
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 241001347978 Major minor Species 0.000 description 16
- 239000006227 byproduct Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Landscapes
- 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
The invention discloses a kind of methods of ester-interchange method production hydroxyethyl methacrylate, belong to chemical synthesis process.This method is, using p-methyl benzenesulfonic acid as catalyst, using phenthazine as polymerization inhibitor, to be reacted under conditions of temperature is 100~120 DEG C using methyl methacrylate and ethylene glycol as raw material, target product is prepared.The method of the present invention is safe, simple, used catalyst p-methyl benzenesulfonic acid is cheap and easy to get compared to catalyst such as cetyltrimethylammonium hydroxide, potassium cyanide, heavy metal salts, is easy to save and use, pollute small, with polymerization inhibitor with the use of working well, method is easier to industrial applications.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of method of ester-interchange method production hydroxyethyl methacrylate.
Background technique
Hydroxyethyl methacrylate (HEMA) is very widely used in Modern Fine Chemical Industry.Its related side of catalyzing and synthesizing
Method is at home and abroad all described in data.Currently, the methacrylate hydroxyl ethyl ester process for catalytic synthesis of comparative maturity mainly has ester
Exchange process and addition process, wherein addition process be under the action of catalyst and polymerization inhibitor, with ethylene oxide and methacrylic acid into
Row reaction preparation HEMA.Advantage is that yield is higher, but ethylene oxide gas belongs to A-grade in the first class's class chemicals, and explosion limit range is very wide,
It is breakneck inflammable and explosive chemicals, relatively high to the transport, storage, requirement of raw material, production control condition compares
Harshness, technical level require relatively high, transport, and storage will lead to serious accident with careless slightly in production process.With
The continuous reinforcement of safety in production and environmental protection supervision, the enterprise much produced with the technique just gradually consider to abandon
With the method, but there is presently no the feasible other alternatives of comparative maturity.In the presence of catalyst and polymerization inhibitor, use
The existing relevant report of method that MMA and ethylene glycol produce HEMA by ester-interchange method, but there are costs for used catalyst
The defects of height, not easy to maintain, use condition is harsh, seriously polluted, there is also be not easy from reaction system for used polymerization inhibitor
Separation makes the deficiencies of product is with color, and is not suitable for large-scale industrial production.
Summary of the invention
The present invention be directed to above-mentioned technical problems to provide a kind of ester-interchange method production hydroxyethyl methacrylate
Method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of method of ester-interchange method production hydroxyethyl methacrylate, this method is with methyl methacrylate and second two
Alcohol is raw material, using p-methyl benzenesulfonic acid as catalyst, using phenthazine as polymerization inhibitor, temperature be 100~120 DEG C under conditions of into
Row reaction, vacuum distillation remove low boiling component, collect 86-88 DEG C/0.67kPa and 98-100 DEG C/0.67kPa fraction respectively,
Principal product hydroxyethyl methacrylate and by-product ethylene glycol dimethacrylate are obtained, major-minor product purity reaches 99%
More than.
In technical solution of the present invention: the volume ratio of the methyl methacrylate and ethylene glycol is 1~2:1.
In technical solution of the present invention: the temperature of reaction is 100~115 DEG C.
In technical solution of the present invention: the mass ratio of ethylene glycol and catalyst is 5~20:1.
In technical solution of the present invention: the dosage of polymerization inhibitor is account for total mass of raw material 0.25~0.9%.
In technical solution of the present invention: the reaction time is 1~3h.
In technical solution of the present invention: reaction time 2.5h.
Beneficial effects of the present invention:
The present invention under catalyst and polymerization inhibitor effect, is closed using methyl methacrylate and ethylene glycol by ester-interchange method
Method safety, simple at hydroxyethyl methacrylate, used catalyst p-methyl benzenesulfonic acid is compared to cetyl trimethyl hydrogen
Amine-oxides, potassium cyanide, heavy metal salt it is of equal value it is honest and clean be easy to get, be easy to save, pollute it is small, with polymerization inhibitor with the use of working well,
Method is easier to industrial applications.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Examples 1 to 5
By oil bath heating to 110 DEG C, three mouthfuls of burnings that MMA (methyl methacrylate) 30mL (28.2g) pours into 250mL are measured
It in bottle, and weighs polymerization inhibitor phenthazine 0.25g and pours into three-necked flask, stir lower polymerization inhibitor dissolution and ethylene glycol is added after the completion
23.6mL (18.6g), and weigh p-methyl benzenesulfonic acid 1.72g and pour into three-necked flask, reacted in oil bath pan respectively 1h,
1.5h、2h、2.5h、3h。
After reaction, 50 DEG C are cooled to, vacuum distillation removes low-boiling-point substance, collects 86-88 DEG C of fraction/0.67kPa respectively
Principal product hydroxyethyl methacrylate and 98-100 DEG C/0.67kPa by-product ethylene glycol dimethacrylate, calculate yield and
Major-minor ratio.
According to the yield of differential responses time major and minor product and major-minor table 1 for example than calculated result.
The relationship in table 1 reaction time and reactants and products
| Reaction time/h | Principal product yield % | By-product yields % | Major-minor ratio |
| 1.0 (embodiments 1) | 92.27 | 7.69 | 12.00:1 |
| 1.5 (embodiments 2) | 92.50 | 7.52 | 12.29:1 |
| 2.0 (embodiments 3) | 88.20 | 11.80 | 7.47:1 |
| 2.5 (embodiments 4) | 89.30 | 10.70 | 8.35:1 |
| 3.0 (embodiments 5) | 90.29 | 9.76 | 9.25:1 |
Embodiment 6~10
It measures MMA30mL (28.2g) to pour into the three-necked flask of 250mL, and weighs polymerization inhibitor phenthazine 0.25g and pour into three
In mouth flask, addition ethylene glycol 23.6mL (18.6g) after the completion of lower polymerization inhibitor dissolution is stirred, and weigh p-methyl benzenesulfonic acid
1.72g is poured into three-necked flask, is reacted 2.5 hours in oil bath, and reaction temperature is 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120
DEG C, after reaction, 50 DEG C are cooled to, vacuum distillation removes low-boiling-point substance, collects 86-88 DEG C of fraction/0.67kPa main product respectively
Object hydroxyethyl methacrylate and 98-100 DEG C/0.67kPa by-product ethylene glycol dimethacrylate calculate yield and major-minor
Than.
Table 2 is summed up than calculated result according to the major and minor products collection efficiency of differential responses temperature and major-minor.
The relationship of table 2 reaction temperature and reactants and products
| Reaction temperature/DEG C | Principal product yield/% | By-product yields/% | Major-minor ratio |
| 100 (embodiments 6) | 97.18 | 2.82 | 34.50:1 |
| 105 (embodiments 7) | 90.04 | 9.96 | 9.04:1 |
| 110 (embodiments 8) | 92.16 | 7.84 | 11.75:1 |
| 115 (embodiments 9) | 83.18 | 16.82 | 4.95:1 |
| 120 (embodiments 10) | 96.85 | 3.09 | 31.33:1 |
Embodiment 11~15
By oil bath heating to 110 DEG C, measures MMA30mL (28.2g) and pour into the three-necked flask of 250mL, weigh polymerization inhibitor
Phenthazine 0.25g is poured into three-necked flask, and stirring lower polymerization inhibitor dissolution, weighing p-methyl benzenesulfonic acid 1.72g pours into three mouthfuls after the completion
In flask, and the ethylene glycol for measuring 5 parts of different volumes is respectively 17.31mL (13.67g), 18.89mL (14.92g), 20.46mL
(16.16g), 22.04mL (17.41g), 23.61mL (18.65g) are poured into three-necked flask, are put and are reacted 2.5h in oil bath, instead
After answering, 50 DEG C are cooled to, vacuum distillation removes low-boiling-point substance, collects 86-88 DEG C of fraction/0.67kPa principal product methyl respectively
Hydroxy-ethyl acrylate and 98-100 DEG C/0.67kPa by-product ethylene glycol dimethacrylate calculate yield and major-minor ratio.
Table 3 is summed up than calculated result according to the major and minor products collection efficiency of differential responses temperature and major-minor.
The dosage of 3 ethylene glycol of table and the relationship of reactants and products
| Ethylene glycol dosage/ml | Principal product yield/% | By-product yields/% | Major-minor ratio |
| 17.31 (embodiments 11) | 93.55 | 6.45 | 14.51:1 |
| 18.89 (embodiments 12) | 82.69 | 17.31 | 4.78:1 |
| 20.46 (embodiments 13) | 85.67 | 14.34 | 5.97:1 |
| 22.04 (embodiments 14) | 90.93 | 9.10 | 9.99:1 |
| 23.61 (embodiments 15) | 94.43 | 5.57 | 16.97:1 |
Embodiment 16~20
By oil bath heating to 110 DEG C, measures MMA30mL and pour into the three-necked flask of 250mL, and weigh polymerization inhibitor phenthazine
0.25g is poured into three-necked flask, stirs addition ethylene glycol 20.46mL (16.16g) after the completion of lower polymerization inhibitor dissolution, and weigh five
The p-methyl benzenesulfonic acid of part different quality is respectively that 2.54g, 2.13g, 1.72g, 1.31g, 0.90g pour into five three-necked flasks
In, it is placed in oil bath pan and reacts 2.5 hours, after reaction, be cooled to 50 DEG C, vacuum distillation removes low-boiling-point substance, collects respectively
86-88 DEG C of fraction/0.67kPa principal product hydroxyethyl methacrylate and 98-100 DEG C/0.67kPa by-product ethylene glycol dimethyl
Acrylate calculates yield and major-minor ratio.
Table 4 is summed up than calculated result according to the major and minor products collection efficiency of different catalysts dosage and major-minor.
The dosage of 4 catalyst of table and the relationship of reactants and products
| Catalyst amount/g | Principal product yield/% | By-product yields/% | Major-minor ratio |
| (2.5400 embodiment 16) | 90.51 | 9.46 | 9.56:1 |
| (2.1300 embodiment 17) | 91.54 | 8.43 | 10.86:1 |
| (1.7200 embodiment 18) | 89.30 | 10.70 | 8.35:1 |
| (1.3100 embodiment 19) | 96.03 | 3.97 | 24.19:1 |
| 0.9020 (embodiment 20) | 96.16 | 3.93 | 24.46:1 |
Embodiment 21~25
By oil bath heating to 110 DEG C, measures MMA30mL (28.2g) and pour into the three-necked flask of 250mL, and weigh five parts
The phenthazine of different quality is respectively that 0.1375g, 0.1925g, 0.25g, 0.3025g, 0.3575g pour into five three-necked flasks
In, addition ethylene glycol 23.6mL (18.6g) after the completion of lower polymerization inhibitor dissolution is stirred, and weigh p-methyl benzenesulfonic acid 1.72g and pour into
In three-necked flask, it is placed in oil bath pan and reacts 2.5 hours.After reaction, 50 DEG C are cooled to, vacuum distillation removes low-boiling-point substance,
86-88 DEG C of fraction/0.67kPa principal product hydroxyethyl methacrylate and 98-100 DEG C/0.67kPa by-product second two are collected respectively
Alcohol dimethylacrylate calculates yield and major-minor ratio.
Table 5 is summed up than calculated result according to the yield of the major and minor product of different polymerization inhibitor dosages and major-minor.
The dosage of 5 polymerization inhibitor of table and the relationship of reactants and products
| Polymerization inhibitor dosage/g | Principal product yield/% | By-product yields/% | Major-minor ratio |
| 0.1375 (embodiment 21) | 93.57 | 6.24 | 15.00:1 |
| 0.1925 (embodiment 22) | / | / | / |
| 0.2500 (embodiment 23) | 89.78 | 10.24 | 8.76:1 |
| 0.3025 (embodiment 24) | / | / | / |
| 0.3575 (embodiment 25) | 87.88 | 12.12 | 7.25:1 |
Note: embodiment 22,24 polymerize.
Embodiment 26~34
By oil bath heating to 105~115 DEG C, measures MMA30mL and pour into the three-necked flask of 250mL, and weigh phenthazine
It pours into three-necked flask, stirs addition ethylene glycol after the completion of lower polymerization inhibitor dissolution, and weigh p-methyl benzenesulfonic acid and pour into three mouthfuls of burnings
In bottle, it is placed in oil bath pan and reacts.
Table 6
Claims (7)
1. a kind of method of ester-interchange method production hydroxyethyl methacrylate, it is characterised in that: this method is with methacrylic acid
Methyl esters and ethylene glycol are raw material, are 100~120 DEG C in temperature using phenthazine as polymerization inhibitor using p-methyl benzenesulfonic acid as catalyst
Under conditions of reacted, target product is prepared.
2. the method for producing hydroxyethyl methacrylate according to ester-interchange method described in right 1, it is characterised in that: the methyl
The volume ratio of methyl acrylate and ethylene glycol is 1~2:1.
3. the method for producing hydroxyethyl methacrylate according to ester-interchange method described in right 1, it is characterised in that: the temperature of reaction
It is 100~115 DEG C.
4. according to ester-interchange method described in right 1 produce hydroxyethyl methacrylate method, it is characterised in that: ethylene glycol with urge
The mass ratio of agent is 5~20:1.
5. the method for producing hydroxyethyl methacrylate according to ester-interchange method described in right 1, it is characterised in that: the use of polymerization inhibitor
Amount is to account for the 0.25~0.9% of total mass of raw material.
6. the method for producing hydroxyethyl methacrylate according to ester-interchange method described in right 1, it is characterised in that: the reaction time is
1~3h.
7. the method for producing hydroxyethyl methacrylate according to ester-interchange method described in right 1, it is characterised in that: the reaction time is
2.5h。
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| CN201811244356.4A CN109134245A (en) | 2018-10-22 | 2018-10-22 | A kind of method of ester-interchange method production hydroxyethyl methacrylate |
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| CN201811244356.4A CN109134245A (en) | 2018-10-22 | 2018-10-22 | A kind of method of ester-interchange method production hydroxyethyl methacrylate |
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| CN109134245A true CN109134245A (en) | 2019-01-04 |
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|---|---|---|---|---|
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Inventor after: Li Jian Inventor after: He Fengyun Inventor after: Sun Ting Inventor after: Zhang Qian Inventor after: Yu Zhiwen Inventor after: Yu Yajun Inventor after: Gao Chunshuang Inventor before: Li Jian Inventor before: He Fengyun |
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| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190104 |