CN109020809A - A kind of preparation method of 1,4-butanediol dimethylacrylate - Google Patents
A kind of preparation method of 1,4-butanediol dimethylacrylate Download PDFInfo
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- CN109020809A CN109020809A CN201710879129.8A CN201710879129A CN109020809A CN 109020809 A CN109020809 A CN 109020809A CN 201710879129 A CN201710879129 A CN 201710879129A CN 109020809 A CN109020809 A CN 109020809A
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- butanediol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
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- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides one kind 1, the preparation method of 4- butanediol dimethylacrylate, under the effect of solid catalyst acid sodium bisulfate, and in the presence of polymerization inhibitor, azeotropic aqua, 1,4- butanediol reacts synthesis in 4-7 hours at 80-90 DEG C with methacrylic acid and obtains 1,4-butanediol dimethylacrylate；Methacrylic acid and 1,4-butanediol mol ratio are 2.10: 1, and azeotropic aqua n-hexane dosage is the 50% of reactant gross mass, and solid acid catalyst is the 3% of reactant gross mass, and polymerization inhibitor phenthazine dosage is the 0.05% of reactant gross mass.Catalyst used in the 1,4-butanediol dimethylacrylate synthetic method is cheap, and stability is good, easily separates with product, does not corrode equipment, has achieved the purpose that clean manufacturing, and yield is high, has broad application prospects.
Description
Technical field
The invention belongs to technical field of chemical paint, are related to a kind of preparation side of 1,4-butanediol dimethylacrylate
Method.
Background technique
Acrylate is a kind of important Organic chemical products, in each neck such as coating, plastics, adhesive, medicine, weaving
Domain has a wide range of applications.Dimethacrylate 1,4-butanediol ester is a kind of important trifunctional acrylate monomer, because double bond contains
Amount is high, has many advantages, such as that quick solidifying and cured film have excellent solvent resistance and wearability, is widely used to moulding, rubber
Glue, optical plastic, adhesive, dental material, wire and cable coating etc..Dimethacrylate fourth two is industrially prepared at present
Alcohol ester is prepared by 1,4-butanediol and methacrylic acid by acid-catalyzed esterification reaction, the acidic catalyst of catalytic esterification
The agent overwhelming majority is the concentrated sulfuric acid, but makees catalyst with the concentrated sulfuric acid, due to its strong oxidizing property and corrosivity, causes by-product more, is gathered
It is serious to close phenomenon, and equipment seriously corroded, catalyst sulfuric acid and the separation of reaction product difficulty, aftertreatment technology are multiple after reaction
Miscellaneous, environmental pollution is serious, and catalyst such as is difficult to recycle at the problems.
Chinese patent application, which discloses, illustrates monologue story-telling with gestures CN101337887, and publication date is on January 7th, 2009, prospectus
The middle preparation method for disclosing dimethacrylate 1,4-butanediol ester is to carry out ester using 1,4-butanediol and methacrylate
Exchange reaction uses lithium compound or calcium compound oxide or hydroxide as catalyst, and there are reaction temperatures for the reaction
High, reaction time is longer and equipment requirement is higher etc..
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the object of the present invention is to provide a kind of 1,4-butanediol two
The preparation method of methacrylate, the catalyst used do not corrode equipment, easily separate with product, can clean manufacturing.
Technical solution: in order to achieve the above-mentioned object of the invention, a kind of the technical solution adopted by the present invention are as follows: dimethacrylate
The preparation method of 1,4-butanediol ester, preparation step are specific as follows:
(1) methacrylic acid, 1,4-butanediol, solid acid catalyst hydrogen sulfate are added in the reaction flask equipped with water segregator
Sodium, polymerization inhibitor phenthazine and water entrainer normal hexane are mixed, and heating, methacrylic acid and 1,4-butanediol are at 80~90 DEG C
1,4-butanediol dimethylacrylate is prepared in 4~6 hours in lower reaction；The methacrylic acid rubs with 1,4-butanediol
That ratio are as follows: 2.05~2.15, catalyst sulfuric acid hydrogen sodium dosage is reactant gross mass 3%, and polymerization inhibitor phenthazine dosage is reaction
Object gross mass 0.05%, water entrainer hexamethylene dosage are reactant gross mass 50%, and reaction temperature is 86 DEG C or so, the reaction time
For 5h.
(2) after reaction, it is cooled to room temperature, filters, decolorizing with activated carbon, sodium bicarbonate saturated solvent is added into mixed liquor
Washing, then be washed to 1-2 times with distillation, stratification takes upper organic phase.
(3) vacuum distillation removes organic solvent, cooling to obtain product 1,4-butanediol dimethylacrylate.
In the preparation method of above-mentioned 1,4-butanediol dimethylacrylate, methacrylic acid and 1,4-butanediol mole
Proportion preferably 2.05~2.2, particularly preferably 2.10, methacrylic acid is excessive or too small with 1,4-butanediol mol ratio,
Other than having an impact to reaction, burden is brought to the rectifying load of product, energy consumption increases；Catalyst is preferably sulfamic acid, sulphur
Acid, to toluene sulfuric acid, sodium bisulfate, resin D072, particularly preferably sodium bisulfate；Catalyst amount is preferably 2~4%, special
It You Xuanwei 3%；Polymerization inhibitor phenthazine dosage is preferably 0.02~0.10%, and particularly preferably 0.05%；Azeotropic aqua is just
Hexane dosage is preferably 40~60%, and particularly preferably 50%；Reaction time is preferably 4.5~5.5 hours, particularly preferably 5
Hour；Reaction temperature is preferably 80~90 DEG C, and particularly preferably 84~86 DEG C.
Beneficial effects of the present invention
Compared with the prior art, the invention has the advantages that: the invention proposes methacrylic acids and 1,4-butanediol
1,4-butanediol dimethylacrylate is prepared under the catalytic action of sodium bisulfate, catalyst and raw material are cheap and easy to get, yield
Height, operation is simple, and stability is good, easily separates with product, does not corrode equipment, can clean manufacturing.
Detailed description of the invention
Fig. 1 is reacted using solid acid catalyst sodium bisulfate catalysis 1,4-butanediol with methacrylic acid in embodiment 1
Products obtained therefrom hydrogen nuclear magnetic resonance spectrogram (1H NMR)。
Specific embodiment
Embodiment 1:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.90.39g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.10: 1.0), 4.06g sulphur
Sour hydrogen sodium catalyst (the 3% of reactant total weight), 0.067g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
67.73g hexamethylene (the 50% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 86.0%.
Embodiment 2:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.88.24g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.05: 1.0), 4.0g sulfuric acid
Hydrogen sodium catalyst (the 3% of reactant total weight), 0.066g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
66.65g hexamethylene (the 50% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 79.4%.
Embodiment 3:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.92.54g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.15: 1.0), 4.13g sulphur
Sour hydrogen sodium catalyst (the 3% of reactant total weight), 0.069g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
68.80g hexamethylene (the 50% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 86.1%.
Embodiment 4:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.94.70g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.20: 1.0), 4.19g sulphur
Sour hydrogen sodium catalyst (the 3% of reactant total weight), 0.070g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
69.88g hexamethylene (the 50% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 82.1%.
Embodiment 5:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.90.39g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.10: 1.0), 4.06g sulphur
Sour hydrogen sodium catalyst (the 3% of reactant total weight), 0.067g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
54.18g hexamethylene (the 40% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 76.8%.
Embodiment 6:
Present embodiments provide a kind of preparation method of 1,4-butanediol dimethylacrylate.90.39g first is weighed respectively
Base acrylic acid, 45.06g 1,4-butanediol (molar ratio of methacrylic acid and 1,4-butanediol is 2.10: 1.0), 4.06g sulphur
Sour hydrogen sodium catalyst (the 3% of reactant total weight), 0.067g phenothiazine polymerization inhibitor (the 0.05% of reactant total weight) and
81.27g hexamethylene (the 60% of reactant total weight) is added in 500mL there-necked flask, load onto thermometer, reflux condensing tube and
Oil water separator opens magnetic agitation and heating, controls reaction temperature at 86 DEG C, reacts 5 hours, 1,4-butanediol diformazan is made
Base acrylate.Be cooled to room temperature, filter, decolorizing with activated carbon, into mixed liquor be added sodium bicarbonate saturated solvent washing, then with steaming
Distilled water is washed till 1-2 times, stratification, takes upper organic phase, and vacuum distillation removes organic solvent, obtains product 1,4-butanediol
Dimethylacrylate yield is 83.1%.
Comparative example 1:
Using sulfamic acid catalyst as a comparison, measures physical and chemical index and be included in table 1.
Comparative example 1:
Using to toluene sulfuric acid catalyst as a comparison, measures physical and chemical index and be included in table 1.
Comparative example 1:
Using sulfuric acid catalyst as a comparison, measures physical and chemical index and be included in table 1.
Comparative example 1:
Using resin D072 catalyst as a comparison, measures physical and chemical index and be included in table 1.
Influence of 1 catalyst type of table to experimental result
Claims (5)
1. a kind of preparation method of 1,4-butanediol dimethylacrylate, which is characterized in that preparation step is as follows:
(1) equipped with water segregator reaction flask in be added methacrylic acid, 1,4-butanediol, solid acid catalyst sodium bisulfate,
Polymerization inhibitor phenthazine and water entrainer n-hexane are mixed, heating, and methacrylic acid and 1,4-butanediol are anti-at 80~90 DEG C
It answers 4.5~5.5 hours and 1,4-butanediol dimethylacrylate is prepared；The methacrylic acid and 1,4-butanediol mole
Optimum proportioning is 2.10: 1, and catalyst sulfuric acid hydrogen sodium dosage is reactant gross mass 3%, and polymerization inhibitor phenthazine dosage is reactant
Gross mass 0.05%, water entrainer hexamethylene dosage are reactant gross mass 50%, and reaction temperature is 84~86 DEG C or so, best anti-
It is 5h between seasonable.
(2) after reaction, it is cooled to room temperature, filters, decolorizing with activated carbon, sodium bicarbonate saturated solvent is added into mixed liquor and washes
It washs, then is washed to 1-2 times with distillation, stratification takes upper organic phase.
2. preparation method according to claim 1, it is characterised in that in the step (1), catalyst is sodium bisulfate.
3. preparation method according to claim 1, it is characterised in that in the step (1), react in 84~86 DEG C of conditions
Lower progress.
4. preparation method according to claim 1, it is characterised in that in the step (1), methacrylic acid and Isosorbide-5-Nitrae-fourth
The molar ratio of glycol is 2.10: 1.
5. preparation method according to claim 1, it is characterised in that in the step (1), water entrainer is n-hexane, dosage
It is the 50% of reactant total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710879129.8A CN109020809A (en) | 2017-09-22 | 2017-09-22 | A kind of preparation method of 1,4-butanediol dimethylacrylate |
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| CN201710879129.8A CN109020809A (en) | 2017-09-22 | 2017-09-22 | A kind of preparation method of 1,4-butanediol dimethylacrylate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668939A (en) * | 2019-11-12 | 2020-01-10 | 江苏正丹化学工业股份有限公司 | Synthesis method of 1, 4-butanediol dimethyl benzene enoate |
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| JP2007254384A (en) * | 2006-03-23 | 2007-10-04 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| CN101337887A (en) * | 2007-07-05 | 2009-01-07 | 罗姆有限公司 | Method for preparing butanediol dimethylacrylate |
| CN101462955A (en) * | 2007-12-17 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing 1,4-butanediol diacrylate |
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2017
- 2017-09-22 CN CN201710879129.8A patent/CN109020809A/en active Pending
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| JP2007254384A (en) * | 2006-03-23 | 2007-10-04 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| CN101337887A (en) * | 2007-07-05 | 2009-01-07 | 罗姆有限公司 | Method for preparing butanediol dimethylacrylate |
| WO2009003743A1 (en) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Method for producing butanediol dimethacrylates |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668939A (en) * | 2019-11-12 | 2020-01-10 | 江苏正丹化学工业股份有限公司 | Synthesis method of 1, 4-butanediol dimethyl benzene enoate |
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Application publication date: 20181218 |