CN106008205A - Method for synthesizing (methyl) acrylate glyceride through catalysis of calcium glyceroxide - Google Patents
Method for synthesizing (methyl) acrylate glyceride through catalysis of calcium glyceroxide Download PDFInfo
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- CN106008205A CN106008205A CN201610323845.3A CN201610323845A CN106008205A CN 106008205 A CN106008205 A CN 106008205A CN 201610323845 A CN201610323845 A CN 201610323845A CN 106008205 A CN106008205 A CN 106008205A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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Abstract
The invention discloses a method for synthesizing (methyl) acrylate glyceride through catalysis of calcium glyceroxide and belongs to the field of fine chemical engineering. The method comprises the steps that a reaction-rectification technology is adopted, a refit rectification column filled with copper wire gauze is used, and alkyl (meth) acrylate, glycerol, a polymerization inhibitor and a catalyst are added; under the string condition, air is introduced, and heating is carried out until a reaction solution flows back, wherein the temperature ranges from 60 DEG C to 140 DEG C; after the reaction is finished, a reaction solution is cooled to 50 DEG C, active carbon is added, stirring is continuously carried out for 0.5-1 h with the temperature maintained, the reaction solution is subjected to pressure reduction suction filtration after the reaction is finished, filter liquor is subjected to pressure reduction rotary steaming to remove the excessive raw material ester, and the (methyl) acrylate glyceride reactive diluent product is obtained. The method overcomes the defects of an existing ester exchange catalyst, and is high in yield, simple in aftertreatment and easy to implement.
Description
Technical field
The invention belongs to field of fine chemical, relate to solid base catalyst catalyzing glycerol and (methyl) acrylate passes through ester
Exchange synthetic method prepares (methyl) glycerol acrylate.
Background technology
(methyl) glycerol acrylate double bond content is high, volatility is low, toxicity is little, crosslink density is high, curing rate is fast
Feature, its cured film formed is wear-resisting, solvent resistant, is that radiation curing field most widely used polyfunctional acrylic ester activity is dilute
Release agent, have a wide range of applications future in the various fields such as the modification of photocureable coating, ink and polymer and cross-linking agent
Formula 1 (methyl) glycerol acrylate class reactive diluent chemical constitution
Report according to existing document, the synthesis of (methyl) esters of acrylic acid reactive diluent can pass through direct esterification,
Chloride method and ester-interchange method.Direct esterification is to do catalyst alkyd direct esterification with strong acid such as concentrated sulphuric acids, and strong acid catalyst is not
But cause that side reaction is many, product separation and purification difficulty, high to equipment requirements, and cause the discharge of a large amount of waste water, cause environment
Pollute；Chloride method is to be first that then acyl chlorides is esterified with alcohol by acid chlorination, but chlorination process can increase reactions steps；(methyl) propylene
The synthesis of acid esters can be under the effect of catalyst, and (methyl) alkyl acrylate and alcohol are that raw material carries out ester exchange and prepares, essence
Sterling is obtained after evaporating.
The catalyst of ester exchange synthesis (methyl) acrylate can be p-methyl benzenesulfonic acid, calcium oxide and titanate esters etc., but
Being acidic catalyst meeting etching apparatus, base catalyst active selectable is low, neutral organo-metallic catalyst consumption to be considered
Problem and poisoning and deactivation problem.
In recent years, solid base catalyst because of have higher catalysis activity, environmental protection, the advantage such as cheap and easy to get and be subject to
Increasing concern.We use catalyzed by solid base ester exchange reaction to prepare the dilution of (methyl) glycerol acrylate class activity
Agent.
Summary of the invention
Object of the present invention is to provide solid base glycerol calcium and synthesize (methyl) glycerol acrylate as ester-interchange method
Catalyst, this catalyst has the advantages such as catalysis activity is high, aftertreatment technology is simple, catalyst is simple and easy to get, is suitable for industry
Metaplasia is produced.
For completing the object of the invention, adopt the following technical scheme that
A kind of method of glycerol calcium treating synthesis (methyl) glycerol acrylate, is carried out as steps described below:
(1) add (methyl) alkyl acrylate of certain mass, glycerol and catalyst glycerol calcium, be heated to reflux stirring,
The alcohol making reaction produce constantly steams from rectifying column upper end azeotropic, and reaction is to steaming stopping without alcohol.By reacting liquid filtering, recovery is urged
Agent, obtains product (methyl) glycerol acrylate.
(2) synthetic method of a kind of (methyl) glycerol acrylate class reactive diluent, it is characterised in that with (methyl) third
Olefin(e) acid Arrcostab, glycerol are raw material, use reaction rectification coupling technique, use the repacking rectifying column of copper mesh filler, and addition is urged
Agent glycerol calcium, through simple last handling process, it is possible to obtain enough product purity and yield.
1) use reaction rectification technique, use the repacking rectifying column of copper mesh filler, add (methyl) acrylic acid alkyl
Ester, glycerol, polymerization inhibitor and catalyst, under stirring condition, be passed through air and be warming up to reactant liquor backflow, and temperature is at 60-140 DEG C.
After reaction terminates, reactant liquor is cooled to 50 DEG C, adds activated carbon, continues insulated and stirred 0.5h-1h, reactant liquor decompression is taken out after terminating
Filter, filtrate decompression rotation is steamed, and removes the starting ester of excess, obtains (methyl) glycerol acrylate class reactive diluent product.
Described (methyl) alkyl acrylateThe concrete structure of middle ester is:
Deng；
Described R is H or methyl；
Described R' is methyl.
Described alcohol (R "-OH) includes such as but is not limited only to: aliphatic straight chain monohydric alcohol, branched monobasic alcohol, alicyclic ring alcohol, virtue
Race's alcohol, comprises the alcohol of other functional group, the alcohol of the ethylene oxide adduct of ethylidene-urea, and concrete structure is: Deng；
Described raw materials glycerine is 1.0:6.0～1.0:9.0 with the mol ratio of (methyl) alkyl acrylate.
Described catalyst is solid alkaline compound glycerol calcium etc., compound self-control glycerol calcium, and its preparation method is as follows:
Calcium oxide after back flow reaction 2h, is cooled to room temperature, uses first in glycerol-methanol (volume ratio 1: 1) mixed solution
Alcohol washs, and 120 DEG C of dry 24h, in Muffle furnace, under uniform temperature, roasting 4h obtains glycerol calcium catalyst etc..Catalyst amount is anti-
Answer the 0.5%～5.0% of gross mass.
Described catalyst can be added, such as but not limited to by catalyst and first by the most known conventional mode of movement
Base acrylic acid methyl ester. is mixed into slurry mixture together.
Described polymerization inhibitor includes: diethyl hydroxylamine, MEHQ, hydroquinone, phenothiazine, 2,6-di-t-butyl pair
Cresol, 3,5-di-t-butyl-4-hydroxyanisol, 2,5-di-t-butyl hydroxyanisol, 4-hydroxyl-2,6,6-tetramethyl piperidine
Free radical and 4-hydroxyl-2,6,6-tetramethyl-N-hydroxy piperidines, preferably MEHQ.
When using above-mentioned polymerization inhibitor, typically the mol ratio of polymerization inhibitor Yu raw alcohol is controlled in (0.001～0.004): 1
In the range of；
The reaction temperature (i.e. the temperature of reactant mixture in ester-exchange reaction) of the inventive method is 60-140 DEG C,
Preferably 80-100 DEG C.Reaction pressure is 760 millimetress of mercury (atmospheric pressure).
Instant invention overcomes many deficiencies of existing ester exchange catalyst, yield is high, post processing is simple, simple and easy to get.With
Traditional catalyst is compared, including advantages below:
1) comparing with tradition ester-interchange method, the inventive method can improve total recovery and disposal ability, utilizes reaction heat for dividing
From required energy, reduce energy consumption, reduce investment.
2) the inventive method technological process is brief, and raw material is easy to get, and equipment is simple, it is easy to accomplish automatically control.
3) this method reaction condition is gentle, and purification refine technique is simple, and product is stablized easily separated, is not susceptible to polymerization existing
As.
4) double (methyl) acrylate of glycerol has difunctional, is used in mixed way with glycerol three (methyl) acrylate
Both can accelerate crosslinking curing speed, good dilution capacity can have been kept again, so can be containing a certain amount of in this product of major part
Corresponding dibasic acid esters.
Detailed description of the invention
Describe the present invention with specific embodiment.Protection scope of the present invention with detailed description of the invention is not
Limit, but be defined in the claims.
The preparation of embodiment 1 glycerol acrylate
In the there-necked flask having electromagnetic agitation, thermometer, rectifying column, adapting pipe, receiving bottle, add 77.5g
(0.9mol) acrylic acid methyl ester., glycerol 9.2g (0.1mol) and 0.5g glycerol calcium, is heated to reflux stirring, makes the methanol that reaction produces
Constantly steaming from rectifying column upper end azeotropic, reaction is to steaming stopping without methanol, by reacting liquid filtering, reclaims catalyst, steams former
Material acrylic acid methyl ester., obtains product 28.3g, and wherein glycerol diacrylate and three glycerol acrylate content are respectively 22.5% He
42.3%.
The preparation of embodiment 2 glycerol acrylate
Stir to being furnished with air and be passed through in the 250mL four-hole boiling flask of mouth, copper mesh filling extract rectification post and temperature measuring equipment addition magnetic force
Mix son, add 9.2g (0.1mol) glycerol, glycerol calcium 0.50g (0.5% qualities of glycerin) and 0.05g MEHQ, heat up
To reactant liquor 60 DEG C, acrylic acid methyl ester. 77.5g is put into 2-3h dropping in constant pressure funnel, be passed through air and be warming up to anti-
Answering liquid to reflux, in course of reaction, timing sampling carries out gas chromatographic analysis reaction end.Reaction adds in 0.1g after reaching home
Property activated carbon about 50 DEG C reflux 0.5h-1h, reduce pressure after terminating sucking filtration by reactant liquor, take filtrate rotation steaming obtain product 31.4g,
Glycerol diacrylate and three glycerol acrylate content are respectively 32.4% and 45.1%.
The preparation of embodiment 3 (methyl) glycerol acrylate
In the there-necked flask having electromagnetic agitation, thermometer, rectifying column, adapting pipe, receiving bottle, add 90.1g
(0.9mol) acrylic acid methyl ester., glycerol 9.2g (0.1mol) and 0.5g glycerol calcium, is heated to reflux stirring, makes the methanol that reaction produces
Constantly steaming from rectifying column upper end azeotropic, reaction is to steaming stopping without methanol, by reacting liquid filtering, reclaims catalyst, steams former
Material acrylic acid methyl ester., obtains product propylene acid glyceride 29.6g, two (methyl) glycerol acrylate and three (methyl) acrylic acid glycerol
Ester content is respectively 37.5% and 40.4%.
The preparation of embodiment 4 (methyl) glycerol acrylate
Stir to being furnished with air and be passed through in the 250mL four-hole boiling flask of mouth, copper mesh filling extract rectification post and temperature measuring equipment addition magnetic force
Mix son, add 9.2g (0.1mol) glycerol, glycerol calcium 0.50g (0.5% qualities of glycerin) and 0.05g MEHQ, heat up
To reactant liquor 60 DEG C, methyl methacrylate 90.1g (0.9mol) is put into 2-3h dropping in constant pressure funnel, is passed through sky
Gas is also warming up to reactant liquor backflow, and in course of reaction, timing sampling carries out gas chromatographic analysis reaction end.Reaction is reached home
Rear addition 0.1g neutral active charcoal is at about the 50 DEG C 0.5h-1h that reflux, and reduce pressure after terminating sucking filtration by reactant liquor, takes filtrate rotation and steams
It is respectively 52.2% He to product 32.5g, two (methyl) glycerol acrylate and three (methyl) glycerol acrylate content
37.3%.
The preparation of comparative example 1 trimethylolpropane tris (methyl) acrylate
Being added by the mixture of following components with temperature indicator/thermostat, magnetic stirring apparatus, dry air leads to
Entrance, equipped with the copper mesh filled column of the diameter 29cm of still head, distillation ratio-removal vapour pressure temperature controller and progressively distilling
In the 250ml four-neck flask of liquid receptor: 13.42g (0.5mol) trimethylolpropane (TMP), 77.5g (0.9mol) MA,
0.07g (0.0006mol) MEHQ, 0.50g (0.004mol) Anhydrous potassium carbonate, is passed through air and is warming up to reactant liquor backflow, surely
Fixed reaction is to reaction end.Reactant liquor is cooled to 50 DEG C by post processing, adds 0.10g neutral active charcoal, continues insulated and stirred 1h, knot
Reduce pressure after bundle sucking filtration by reactant liquor, and filtrate decompression rotation is steamed, and three esters that reaction produces are best result with dibasic acid esters total content and are not
77.1% and 90.1%.
Comparative example 2 glycol diacrylate
Adding the mixture of following components with temperature indicator/thermostat, magnetic stirring apparatus, dry air is passed through
Mouthful, equipped with the copper mesh filled column of the diameter 29cm of still head, distillation ratio-removal vapour pressure temperature controller and progressively distillate
In the 100ml four-neck flask of receptor: 3.1g (0.05mol) ethylene glycol, 25.83g (0.3mol) acrylic acid methyl ester. (MA),
0.03g (0.0002mol) MEHQ and 0.11g (0.0002mol) dibutyl tin laurate.Then by mixture liter
Temperature is to backflow.In course of reaction, it is passed through a certain amount of air, at ambient pressure continuous heating backflow, removes reaction vapor of mixture simultaneously
Thing MA-methanol.After reaction is reached home, reactant liquor is cooled to 50 DEG C, adds 0.10g neutral active charcoal, continues insulated and stirred 0.5-1
Hour, reduce pressure after terminating sucking filtration by reactant liquor, and filtrate decompression rotation is steamed, and obtains glycol diacrylate 5.35g, and yield is
76.9%, purity 54.8%.
Claims (6)
1. the method for glycerol calcium treating synthesis (methyl) glycerol acrylate, it is characterised in that carry out as steps described below:
1) use reaction rectification technique, use the repacking rectifying column of copper mesh filler, add (methyl) alkyl acrylate, sweet
Oil, polymerization inhibitor and catalyst, under stirring condition, be passed through air and be warming up to reactant liquor backflow, and temperature is at 60-140 DEG C；Reaction knot
Shu Hou, reactant liquor is cooled to 50 DEG C, adds activated carbon, continues insulated and stirred 0.5h-1h, and reduce pressure after terminating sucking filtration by reactant liquor, filter
Liquid vacuum rotary steam, removes the starting ester of excess, obtains (methyl) glycerol acrylate class reactive diluent product.
The method of a kind of glycerol calcium treating synthesis (methyl) glycerol acrylate the most according to claim 1, its feature exists
In described (methyl) alkyl acrylateThe concrete structure of middle ester is: Deng；
Described R is H or methyl；
Described R' is methyl.
The method of a kind of glycerol calcium treating synthesis (methyl) glycerol acrylate the most according to claim 1, its feature exists
Include such as in described alcohol (R "-OH) but be not limited only to: aliphatic straight chain monohydric alcohol, branched monobasic alcohol, alicyclic ring alcohol, aromatic alcohol,
Comprise the alcohol of other functional group, the alcohol of the ethylene oxide adduct of ethylidene-urea, concrete structure is:
Deng；
Described raw materials glycerine is 1.0:6.0～1.0:9.0 with the mol ratio of (methyl) alkyl acrylate.
The method of a kind of glycerol calcium treating synthesis (methyl) glycerol acrylate the most according to claim 1, its feature exists
Being solid alkaline compound glycerol calcium in described catalyst, its preparation method is as follows:
Calcium oxide after back flow reaction 2h, is cooled to room temperature, washes with methanol in glycerol-methanol (volume ratio 1: 1) mixed solution
Washing, 120 DEG C of dry 24h, in Muffle furnace, under uniform temperature, roasting 4h obtains glycerol calcium catalyst etc.；Catalyst amount is total for reaction
The 0.5%～5.0% of quality；
Described catalyst can be added, such as but not limited to by catalyst and methyl-prop by the most known conventional mode of movement
E pioic acid methyl ester is mixed into slurry mixture together.
The method of a kind of glycerol calcium treating synthesis (methyl) glycerol acrylate the most according to claim 1, its feature exists
Include in described polymerization inhibitor: diethyl hydroxylamine, MEHQ, hydroquinone, phenothiazine, DBPC 2,6 ditertiary butyl p cresol,
3,5-di-t-butyl-4-hydroxyanisol, 2,5-di-t-butyl hydroxyanisol, 4-hydroxyl-2,6,6-tetramethyl piperidine are freely
Base and 4-hydroxyl-2,6,6-tetramethyl-N-hydroxy piperidines, preferably MEHQ；
When using above-mentioned polymerization inhibitor, typically the mol ratio of polymerization inhibitor Yu raw alcohol is controlled in (0.001～0.004): the model of 1
In enclosing.
The method of a kind of glycerol calcium treating synthesis (methyl) glycerol acrylate the most according to claim 1, its feature exists
In reaction temperature (i.e. the temperature of reactant mixture in ester-exchange reaction) be 60-140 DEG C, preferably 80-100 DEG C.Instead
Answering pressure is 760 millimetress of mercury (atmospheric pressure).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500373A (en) * | 2020-04-27 | 2020-08-07 | 浙江工业大学 | Preparation method of biodiesel |
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- 2016-05-16 CN CN201610323845.3A patent/CN106008205A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500373A (en) * | 2020-04-27 | 2020-08-07 | 浙江工业大学 | Preparation method of biodiesel |
| CN111500373B (en) * | 2020-04-27 | 2023-04-11 | 浙江工业大学 | Preparation method of biodiesel |
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Application publication date: 20161012 |