CN110272408A - A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate - Google Patents
A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate Download PDFInfo
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- CN110272408A CN110272408A CN201810218388.0A CN201810218388A CN110272408A CN 110272408 A CN110272408 A CN 110272408A CN 201810218388 A CN201810218388 A CN 201810218388A CN 110272408 A CN110272408 A CN 110272408A
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- curing agent
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- solketal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
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Abstract
The present invention relates to photo-curing material fields, disclose a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate, comprising: 1) methacrylic acid and solketal are put into reaction unit；2) solvent is added, is warming up to 0-50 DEG C；3) mixture of dehydrating agent, catalysts and solvents is added dropwise, temperature is kept to stablize；4) it is stirred after being added dropwise, keeping the temperature at 0-50 DEG C, the reaction was continued, until solketal content is lower than 2%；5) cool down, filter, rinse, obtain filtrate；Or water is added into material, washs, obtain organic layer；Polymerization inhibitor is added into filtrate or organic layer；6) recycling design；7) rectification under vacuum obtains finished product.The method of the present invention uses methacrylic acid for raw material, participates in reaction using a series of dehydrating agent under room temperature, and reaction can be completed under room temperature even lower temperature, the polymerization of reaction product can be effectively reduced, yield, and simple process are improved, industrial production is suitble to.
Description
Technical field
The present invention relates to photo-curing material field more particularly to a kind of light curing agent dimethyl dioxin-pentane alcohol metering systems
The preparation method of acid esters.
Background technique
Dimethyl dioxin-pentane alcohol methacrylate is a kind of good ultraviolet curable agent, can be used for modified epoxy third
The synthesis of olefin(e) acid resin oligomers.In the prior art, there are mainly two types of the traditional synthetic methods of the substance:
One is using methacrylic chloride and solketal to react, target product is generated.For first method, need to make
Use methacrylic chloride and acid binding agent as raw material, product cost is higher, and the synthesis of methacrylic chloride is inevitable
It needs to be easy to cause a large amount of three wastes (especially exhaust gas) using each middle chlorination reagent.
Another kind is to generate target product using methyl methacrylate and solketal reaction, such as:
CN201610968412 discloses a kind of dimethyl dioxin-pentane alcohol methacrylate monomers and application, preparation method are specific
Are as follows: by molar ratio be solketal: methyl methacrylate=1:4 mixes, and hydroquinone of polymerization retarder, catalyst is then added
Dibutyl tin dilaurate, stirring heating heating, control reaction temperature is 110 DEG C, reacts 8 hours, there is methyl in reaction process
The azeotrope of methyl acrylate and methanol is distilled out of in 55-75 DEG C, after reaction, is evaporated under reduced pressure, at 80 DEG C of temperature, pressure
Under the conditions of power -0.1Mpa, unreacted methyl methacrylate and by-product carbinol are further removed, reacting coarse product is obtained.
For second method: although can reduce production cost using methyl methacrylate, due to needing that temperature is increased
To 110 DEG C or more, and polymerization reaction just easily occurs generally at more than 80 DEG C for target product, as the reaction time carries out, receives
Rate declines quickly.Such method is not suitable for industrial production.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of light curing agent dimethyl dioxin-pentane alcohol metering systems
The preparation method of acid esters, the method for the present invention use methacrylic acid for raw material, are participated in using a series of dehydrating agent under room temperature anti-
It answers, reaction can be completed under room temperature even lower temperature, the polymerization of reaction product can be effectively reduced, improve yield, and
And simple process, it is suitble to industrial production.
The specific technical proposal of the invention is: a kind of preparation of light curing agent dimethyl dioxin-pentane alcohol methacrylate
Method, comprising the following steps:
1) methacrylic acid and solketal are put into reaction unit.
2) solvent is added into reaction unit, is warming up to 0-50 DEG C.
3) mixture of dehydrating agent, catalysts and solvents is added dropwise into reaction unit, keeps reaction temperature during being added dropwise
Stablize.
4) it is stirred after being added dropwise, system temperature is maintained at 0-50 DEG C, and the reaction was continued, until solketal contains
Amount is lower than 2%.
5) it is cooled to 0-20 DEG C, by material filtering, filter cake solvent washing, rinse solvent merges with filtrate；Or it does not drop
Water is directly added in temperature into material after the reaction was completed, and washing obtains organic layer；Resistance is added into the filtrate or organic layer
Poly- agent.
6) normal pressure or vacuum distillation recovered solvent.
7) after solvent recovery, rectification under vacuum is carried out to material, obtains finished product.
In the prior art, there are mainly two types of the traditional synthetic methods of the substance:
One is using methacrylic chloride and solketal to react, target product is generated.For first method, need to make
Use methacrylic chloride and acid binding agent as raw material, product cost is higher, and the synthesis of methacrylic chloride is inevitable
It needs to be easy to cause a large amount of three wastes (especially exhaust gas) using each middle chlorination reagent.
Another kind is to generate target product using methyl methacrylate and solketal reaction, such as:
CN201610968412 discloses a kind of dimethyl dioxin-pentane alcohol methacrylate monomers and application, preparation method are specific
Are as follows: by molar ratio be solketal: methyl methacrylate=1:4 mixes, and hydroquinone of polymerization retarder, catalyst is then added
Dibutyl tin dilaurate, stirring heating heating, control reaction temperature is 110 DEG C, reacts 8 hours, there is methyl in reaction process
The azeotrope of methyl acrylate and methanol is distilled out of in 55-75 DEG C, after reaction, is evaporated under reduced pressure, at 80 DEG C of temperature, pressure
Under the conditions of power -0.1Mpa, unreacted methyl methacrylate and by-product carbinol are further removed, reacting coarse product is obtained.
For second method: although can reduce production cost using methyl methacrylate, due to needing that temperature is increased
To 110 DEG C or more, and polymerization reaction just easily occurs generally at more than 80 DEG C for target product, as the reaction time carries out, receives
Rate declines quickly.Such method is not suitable for industrial production.
The method of the present invention uses methacrylic acid for raw material, reaction is participated in using a series of dehydrating agent under room temperature, in room
Reaction can be completed in (0-50 DEG C) under temperature even lower temperature, can be effectively reduced the polymerization (lower than 80 DEG C) of reaction product,
Yield, and simple process are improved, industrial production is suitble to.
Catalyst used in the present invention is the active amino with lone pair electrons, has very high nucleophilicity, can
Hydrogen under low temperature or room temperature on methacrylic acid carboxyl groups generates negative oxygen ion, makes it easier to react in generation with dehydrating agent
Mesosome, to be conducive to generate ester with the hydroxyl reaction on solketal.
Preferably, the molar ratio of the methacrylic acid and solketal is 0.9-1.5:1 in step 1).
Preferably, the solvent includes methylene chloride, dichloroethanes, tetrahydrofuran, methyl in step 2 and step 3)
One of tertbutyl ether, acetonitrile and N,N-dimethylformamide are a variety of.
Preferably, the dehydrating agent is N, N- dicyclohexylcarbodiimide, N, N'- diisopropyl carbon two in step 3)
Imines, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 2- (7- aoxidizes benzotriazole)-N, N, N', N'-
One of tetramethylurea hexafluorophosphoric acid ester is a variety of.
Preferably, the molar ratio of the dehydrating agent and solketal is 0.95-1.5:1 in step 3).
Preferably, the catalyst includes one of 4-dimethylaminopyridine, I-hydroxybenzotriazole in step 3)
Or two kinds.
Preferably, the molar ratio of the catalyst and dehydrating agent is 0.01-1:1 in step 3).
Preferably, the solvent is one of solvent described in step 2 or a variety of in step 5).
Preferably, the polymerization inhibitor is TEMPO, in hydroquinone, p-hydroxyanisole, phenthazine in step 5)
One or more, the additive amount of polymerization inhibitor is the 0.005%-1%mol of solketal.
Preferably, in step 1), with air in nitrogen displacement reaction unit after feeding intake.
It is compared with the prior art, the beneficial effects of the present invention are: the method for the present invention uses methacrylic acid for raw material, uses
A series of dehydrating agent under room temperature participates in reaction, and reaction can be completed under room temperature even lower temperature, can be effectively reduced
The polymerization of reaction product improves yield, and simple process, is suitble to industrial production.
Specific embodiment
The present invention will be further described with reference to the examples below.
Total embodiment
A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate, comprising the following steps:
1) methacrylic acid and solketal are put into reaction unit, with air in nitrogen displacement reaction unit.The methyl
The molar ratio of acrylic acid and solketal is 0.9-1.5:1.
2) solvent is added into reaction unit, is warming up to 0-50 DEG C.The solvent includes methylene chloride, dichloroethanes, four
One of hydrogen furans, methyl tertiary butyl ether(MTBE), acetonitrile and N,N-dimethylformamide are a variety of.
3) mixture of dehydrating agent, catalysts and solvents is added dropwise into reaction unit, keeps reaction temperature during being added dropwise
Stablize.Wherein, the dehydrating agent is N, N- dicyclohexylcarbodiimide, N, N'- diisopropylcarbodiimide, 1- (3- diformazan ammonia
Base propyl) -3- ethyl-carbodiimide hydrochloride, 2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid
One of ester is a variety of.The molar ratio of dehydrating agent and solketal is 0.95-1.5:1.The catalyst includes 4- diformazan
One or both of aminopyridine, I-hydroxybenzotriazole.The molar ratio of catalyst and dehydrating agent is 0.01-1:1.
4) it is stirred after being added dropwise, system temperature is maintained at 0-50 DEG C, and the reaction was continued, until solketal contains
Amount is lower than 2%.
5) it is cooled to 0-20 DEG C, by material filtering, filter cake solvent washing, rinse solvent merges with filtrate；Or it does not drop
Water is directly added in temperature into material after the reaction was completed, and washing obtains organic layer；Resistance is added into the filtrate or organic layer
Poly- agent.The solvent is one of solvent described in step 2 or a variety of.The polymerization inhibitor is TEMPO, hydroquinone, to hydroxyl
One of base methyl phenyl ethers anisole, phenthazine are a variety of, and the additive amount of polymerization inhibitor is the 0.005%-1mol% of solketal.
6) normal pressure or vacuum distillation recovered solvent.
7) after solvent recovery, rectification under vacuum is carried out to material, obtains finished product.
Embodiment 1
Ensure that reaction flask is clean, it is dry.Flask is equipped with mechanical stirring, thermometer, dropping funel.Ensure reaction raw materials methyl-prop
Olefin(e) acid, solketal and methylene chloride moisture are lower than 0.1%.Methacrylic acid 172g, methylene chloride 660g and acetone are contracted sweet
Oily 250g puts into reaction flask, and with air in nitrogen displacement reaction unit, stirring, temperature control is to 20 DEG C.It is added dropwise into reaction unit
The mixed liquor of 412g N, N- dicyclohexylcarbodiimide, 2.4g 4-dimethylaminopyridine and 400g methylene chloride maintains reaction
Temperature is at 20 DEG C hereinafter, time for adding about 3 hours.Continue stirring 8 hours after completion of dropwise addition, sampling monitoring solketal makes
G/C content is lower than 1.5%, stops reaction.Material is cooled between 0-5 DEG C, is filtered, filtrate is rinsed with the methylene chloride of 50g, is closed
And filtrate, hydroquinone 1g is added into filtrate, 45 DEG C of normal pressures, which are steamed to solvent-free, to be distilled out of.Raffinate is drawn high into vacuum to 3-
5mmHg distills out product.Yield: 73%.
Embodiment 2
Ensure that reaction flask is clean, it is dry.Flask is equipped with mechanical stirring, thermometer, dropping funel.Ensure reaction raw materials methyl-prop
Olefin(e) acid, solketal and methylene chloride moisture are lower than 0.1%.Methacrylic acid 195g, methylene chloride 660g and acetone are contracted sweet
Oily 250g puts into reaction flask, and with air in nitrogen displacement reaction unit, stirring, temperature control is to 20 DEG C.It is added dropwise into reaction unit
The mixed liquor of 252g N, N'- diisopropylcarbodiimide and 7g 4-dimethylaminopyridine, maintaining reaction temperature are added dropwise at 25 DEG C
After continue stirring 10 hours, sampling monitoring solketal makes G/C content lower than 1%, stops reaction.Filtrate is with the two of 50g
Chloromethanes rinses, merging filtrate, phenthazine 0.1g is added into filtrate, normal pressure, which is steamed to solvent-free, to be distilled out of.Raffinate is drawn high very
Sky distills out product to 3-5mmHg.Yield: 77%.
Embodiment 3
Ensure that reaction unit is clean, it is dry.Ensure that reaction raw materials methacrylic acid, solketal and dichloroethanes moisture are lower than
0.1%.Methacrylic acid 207kg, dichloroethanes 500kg and solketal 264kg are put into reaction flask, replaced with nitrogen
Air in reaction unit, stirring, temperature control is to 30 DEG C.382kg1- (3- dimethylamino-propyl) -3- is added portionwise into reaction unit
Ethyl-carbodiimide hydrochloride and 270kg I-hydroxybenzotriazole, maintaining reaction temperature continue to stir after charging at 25 DEG C
It mixes 10 hours, sampling monitoring solketal makes G/C content lower than 1%, stops reaction.Into material plus water washing is layered, and is collected
Organic layer.Normal pressure, which is steamed to solvent-free, to be distilled out of.Raffinate is drawn high into vacuum to 3-5mmHg, distills out product.Yield: 70%.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (10)
1. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate, it is characterised in that including following step
It is rapid:
1) methacrylic acid and solketal are put into reaction unit；
2) solvent is added into reaction unit, is warming up to 0-50 DEG C；
3) mixture of dehydrating agent, catalysts and solvents is added dropwise into reaction unit, keeps reaction temperature to stablize during being added dropwise；
4) it is stirred after being added dropwise, system temperature is maintained at 0-50 DEG C, and the reaction was continued, until solketal content is low
In 2%；
5) it is cooled to 0-20 DEG C, by material filtering, filter cake solvent washing, rinse solvent merges with filtrate；Or do not cool down, directly
It connects and water is added into material after the reaction was completed, wash, obtain organic layer；Polymerization inhibitor is added into the filtrate or organic layer；
6) normal pressure or vacuum distillation recovered solvent；
7) after solvent recovery, rectification under vacuum is carried out to material, obtains finished product.
2. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 1), the molar ratio of the methacrylic acid and solketal is 0.9-1.5:1.
3. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 2 and step 3), the solvent includes methylene chloride, dichloroethanes, tetrahydrofuran, methyl tertbutyl
One of ether, acetonitrile and N,N-dimethylformamide are a variety of.
4. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 3), the dehydrating agent is N, N- dicyclohexylcarbodiimide, N, N'- diisopropylcarbodiimide, 1-
(3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, 2- (7- aoxidizes benzotriazole)-N, N, N', N'- tetramethylurea
One of hexafluorophosphoric acid ester is a variety of.
5. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1 or 4,
It is characterized in that, the molar ratio of the dehydrating agent and solketal is 0.95-1.5:1 in step 3).
6. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 3), the catalyst includes one or both of 4-dimethylaminopyridine, I-hydroxybenzotriazole.
7. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1 or 6,
It is characterized in that, the molar ratio of the catalyst and dehydrating agent is 0.01-1:1 in step 3).
8. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 5), the solvent is one of solvent described in step 2 or a variety of.
9. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as claimed in claim 1 or 8,
It is characterized in that, in step 5), the polymerization inhibitor be one of TEMPO, hydroquinone, p-hydroxyanisole, phenthazine or
A variety of, the additive amount of polymerization inhibitor is the 0.005%-1mol% of solketal.
10. a kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate as described in claim 1,
It is characterized in that, in step 1), with air in nitrogen displacement reaction unit after feeding intake.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810218388.0A CN110272408A (en) | 2018-03-16 | 2018-03-16 | A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810218388.0A CN110272408A (en) | 2018-03-16 | 2018-03-16 | A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate |
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| CN201810218388.0A Pending CN110272408A (en) | 2018-03-16 | 2018-03-16 | A kind of preparation method of light curing agent dimethyl dioxin-pentane alcohol methacrylate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0465835A1 (en) * | 1990-06-08 | 1992-01-15 | Dainippon Ink And Chemicals, Inc. | Anionic living polymers, their derivatives and composition comprising them |
| CN106588860A (en) * | 2016-11-06 | 2017-04-26 | 桂林理工大学 | Dimethyl dioxane pentyl alkanol methacrylate monomer and application thereof |
| WO2018031373A1 (en) * | 2016-08-12 | 2018-02-15 | Iowa State University Research Foundation, Inc. | Acrylated and acylated or acetalized polyol as a biobased substitute for hard, rigid thermoplastic and thermoplastic and thermoset materials |
-
2018
- 2018-03-16 CN CN201810218388.0A patent/CN110272408A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0465835A1 (en) * | 1990-06-08 | 1992-01-15 | Dainippon Ink And Chemicals, Inc. | Anionic living polymers, their derivatives and composition comprising them |
| WO2018031373A1 (en) * | 2016-08-12 | 2018-02-15 | Iowa State University Research Foundation, Inc. | Acrylated and acylated or acetalized polyol as a biobased substitute for hard, rigid thermoplastic and thermoplastic and thermoset materials |
| CN106588860A (en) * | 2016-11-06 | 2017-04-26 | 桂林理工大学 | Dimethyl dioxane pentyl alkanol methacrylate monomer and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| JUI-HSIANG LIU等: "Preparation and Characterization of Novel Polymers Having Pendant Ketal Moieties for Positive Photoresists", 《MACROMOLECULAR CHEMISTRY PHYSICS》 * |
| PHUOC DIEN PHAM等: "Glycerol-based co-oligomers by free-radical chain transfer polymerization: Towards reactive polymers bearing acetal and/or carbonate groups with enhanced properties", 《EUROPEAN POLYMER JOURNAL》 * |
| SAMUEL O. KYEREMATENG等: "Synthesis and characterization of random copolymers of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate and 2,3-dihydroxypropyl methacrylate", 《EUROPEAN POLYMER JOURNAL》 * |
| SATYASANKAR JANA等: "Transparent, flexible and highly conductive ion gels from ionic liquid compatible cyclic carbonate network", 《CHEMICAL COMMUNICATIONS》 * |
| 吴世敏等: "《简明精细化工大辞典》", 31 December 1999 * |
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