CN104448288B - A kind of method synthesizing Hydrin - Google Patents
A kind of method synthesizing Hydrin Download PDFInfo
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- CN104448288B CN104448288B CN201410589436.9A CN201410589436A CN104448288B CN 104448288 B CN104448288 B CN 104448288B CN 201410589436 A CN201410589436 A CN 201410589436A CN 104448288 B CN104448288 B CN 104448288B
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- epoxychloropropane
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Abstract
The invention discloses a kind of method synthesizing Hydrin, its processing method is: chloropropane passes through catalyst, and the catalysis of auxiliary agent to obtain epoxychloropropane standby.In equipped with the there-necked flask of stirrer, it is sequentially added into diethyl aluminum chloride, absolute ether, stirs 10 minutes, be cooled to 0 DEG C, then drip ring Ethylene Oxide.Reacting 30 50 minutes, extract volatile matter in time out, add the methanol solution containing sodium hydroxide, stirring at normal temperatures terminated reaction after 50 minutes.Reactant mixture is moved in separatory funnel, washing, layering.The crude product obtained with 5% hydrochloric acid, 5% sodium bicarbonate, distilled water is washed till neutrality.Reducing pressure with Rotary Evaporators, obtain Hydrin 8.23g, productivity is more than 84.9%.
Description
Technical field
The invention belongs to polyreaction field, relate to the synthetic method of a kind of Hydrin.
Background technology
Hydrin is faint yellow to amber thick liquid or solid.It is formed through epoxy chloropropionate alkene ring-opening polymerisation two.Poly-
Epoxychloropropane has the advantages such as oil resistivity, acid resistance, and resistance to gas penetration highlights.Its damping row and high temperature resistant row are also fine,
And there is good cohesive.Hydrin is carried out cinnamic acid paper flower, can be made into the photoresist of excellent performance.Polycyclic oxygen
Chloropropane can be used for manufacturing seal gasket and oil resistant PUR, sea water resistance, the adhesive of oil resistant etc. and fire-retardant, water-fast, oil resistant
Adhesive for polyurethane, coating.The ring opening polymerization product of epoxide is the heaviest as system in the middle of novel polymer material
Want.
The initiator of conventional synthesis polycyclic oxygen chloropropene mostly is Isosorbide-5-Nitrae-butanol bis trifluoromethyl sulfonic acid fat, trifluoroacetic acid etc.；This writes synthesis
Method is respectively arranged with advantage, but produces substantial amounts of oligomer in polymerization process.Therefore, it is necessary to polymerizate to be carried out necessity
Post processing, this means that technique is more loaded down with trivial details, and the product quality of system does not reaches desired performance.
Summary of the invention
In order to solve prior art synthesizes the substantial amounts of impurity of Hydrin output, reduce technique loaded down with trivial details, improve the matter of polycyclic thing
Amount.
The synthetic route of the present invention is:
The present invention relates to polyacrylic building-up process comprise the following steps:
1. the synthesis of epoxychloropropane:
(1) in 100mL four-hole boiling flask, put into the chloropropene of 30g and the catalyst phospho heteropoly tungstate/Ti0 of 6.5g2, in stirring
10mL hydrogen peroxide and 5g diammonium hydrogen phosphate is added, reaction lower with chloropropene backflow 6 hours under state；
(2) reaction terminates, system shared oil, suspension liquid of aqueous phase after standing 1-2 hour；
(3) oil reservoir is standby by the epoxychloropropane of rectification isolated 23.36mL.
2. initiator A lEt2The synthesis of Cl:
(1) first in equipped with the there-necked flask of stirrer, 5g diethyl aluminum chloride it is sequentially added into, anhydrous through the 50mL of molecular sieve drying
Ether, at normal temperatures stirring 10 minutes；
(2) the solution brine ice being stirred is cooled to 0 DEG C, at dropping 10mL expoxy propane, by controlling drop rate 1-2
Drop/sec and be maintained at the temperature of 0-20 DEG C, react 30 minutes, extraction volatile matter obtains thick initiator A lEt in time2Cl。
3. the synthesis of Hydrin:
(1) epoxychloropropane that addition 20mL prepares in advance in initiator solution keeps 0 DEG C of thermotonus 8 little at ice-water bath
Time；
(2) add the methanol solution that 10mL contains sodium hydroxide, under the protection of nitrogen after 25 DEG C of polymerizations 5 hours, terminate
Reaction；
(3) move to reactant mixture, in the separatory funnel of 1000mL, be washed with deionized, stratification, organic layer is shifted
In 1000mL alembic；
(4) then crude product being sequentially added into 40-50mL, the hydrochloric acid of 5%, 55-65mL5% sodium bicarbonate, during 100mL distilled water is washed till
Property, then reduce pressure with Rotary Evaporators, remove the small-molecule substances such as solvent at being heated up to 70-80 DEG C, obtain Hydrin
8.23g, productivity is 84.9%.
Specific embodiments:
The chloropropene of 30g and the catalyst phospho heteropoly tungstate/Ti0 of 6.5g is put in 100mL four-hole boiling flask2, under stirring
Adding 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, reaction lower with chloropropene backflow 6 hours, reaction terminates, and stands 1-2 hour
Rear system shared oil, suspension liquid of aqueous phase；Oil reservoir is standby by the epoxychloropropane of rectification isolated 23.36mL.Again equipped with
The there-necked flask of stirrer is sequentially added into 5g diethyl aluminum chloride, through the 50mL absolute ether of molecular sieve drying, at normal temperatures
Stir 10 minutes, the solution brine ice being stirred is cooled to 0 DEG C, then drips 10mL expoxy propane.Dripped by control
Speed 1-2 drop/sec and being maintained at a temperature of 0-20 DEG C.React 30-50 minute, extract out in volatile matter, then solution in time and add
Enter the epoxychloropropane that 20mL prepares in advance and keep 0 DEG C of thermotonus 8 hours at ice-water bath.Add 10mL and contain hydrogen-oxygen
Change the methanol solution of sodium, after being polymerized 5 hours in 25 DEG C under the protection of nitrogen, terminate reaction.Reactant mixture is moved to
In the separatory funnel of 1000mL, it is washed with deionized, stratification.Organic layer is transferred in 1000mL alembic.So
After crude product is sequentially added into 40-50mL, the hydrochloric acid of 5%, 55-65mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again
Reduce pressure with Rotary Evaporators, remove the small-molecule substances such as solvent at being heated up to 70-80 DEG C, obtain Hydrin 8.23g,
Productivity is 84.9%.
Example 1
The chloropropene of 30g and the catalyst phospho heteropoly tungstate/Ti0 of 6.5g is put in 100mL four-hole boiling flask2, under stirring
Add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, reaction lower with chloropropene backflow 6 hours.Reaction terminates, after standing 1 hour
System shared oil, suspension liquid of aqueous phase；Oil reservoir is standby by the epoxychloropropane of rectification isolated 23.36mL.Again equipped with stirring
Mix in the there-necked flask of son and be sequentially added into 5g diethyl aluminum chloride, through the 50mL absolute ether of molecular sieve drying, stir at normal temperatures
Mix 10 minutes, the solution brine ice being stirred is cooled to 0 DEG C, at dropping 10mL expoxy propane.By controlling dropping speed
Rate 1 drop/sec and being maintained at a temperature of 5 DEG C.React 30 minutes, extract addition 20mL thing in volatile matter, then solution in time out
The epoxychloropropane first prepared keeps 0 DEG C of thermotonus 8 hours at ice-water bath.Add the first that 10ml contains sodium hydroxide
Alcoholic solution, terminates reaction after being polymerized 5 hours in 25 DEG C under the protection of nitrogen.Reactant mixture is moved to the separatory of 1000mL
In funnel, it is washed with deionized, stratification.Organic layer is transferred in 1000mL alembic.Then crude product is depended on
Secondary addition 40mL, the hydrochloric acid of 5%, 55mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Reduce pressure with Rotary Evaporators again,
Removing the small-molecule substances such as solvent at being heated up to 70-80 DEG C, obtain Hydrin 8.15g, productivity is 82.9%.
Example 2
The chloropropene of 30g and the catalyst phospho heteropoly tungstate/Ti0 of 6.5g is put in 100mL four-hole boiling flask2, under stirring
Add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, reaction lower with chloropropane backflow 6 hours.Reaction terminates, and stands 1.5 hours
Rear system shared oil, suspension liquid of aqueous phase；Oil reservoir is standby by the epoxychloropropane of rectification isolated 23.36mL.Again equipped with
The there-necked flask of stirrer is sequentially added into 5g diethyl aluminum chloride, through the 50mL absolute ether of molecular sieve drying, at normal temperatures
Stir 10 minutes, the solution brine ice being stirred is cooled to 10 DEG C, then drips 10mL expoxy propane.Dripped by control
Rate of acceleration 1 drop/sec and being maintained at a temperature of 0 DEG C.React 30 minutes, extract addition 20mL in volatile matter, then solution in time out
The epoxychloropropane prepared in advance keeps 0 DEG C of thermotonus 8 hours at ice-water bath.Add 10mL and contain sodium hydroxide
Methanol solution, terminates reaction after being polymerized 5 hours in 25 DEG C under the protection of nitrogen.Reactant mixture is moved to dividing of 1000mL
In liquid funnel, it is washed with deionized, stratification.Organic layer is transferred in 1000mL alembic.Then by crude product
Being sequentially added into 45mL, the hydrochloric acid of 5%, 60mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Subtract with Rotary Evaporators again
Pressure, removes the small-molecule substances such as solvent, obtains Hydrin 8.00g at being heated up to 70-80 DEG C, productivity is 80.5%.
Example 3
The chloropropene of 30g and the catalyst phospho heteropoly tungstate/Ti0 of 6.5g is put in 100mL four-hole boiling flask2, under stirring
Add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, reaction lower with chloropropane backflow 6 hours；Reaction terminates, and stands 1-2 hour
Rear system shared oil, suspension liquid of aqueous phase；Oil reservoir stays the epoxychloropropane of isolated 23.36mL standby by essence.Again equipped with
The there-necked flask of stirrer is sequentially added into 5g diethyl aluminum chloride, through the 50mL absolute ether of molecular sieve drying, at normal temperatures
Stir 10 minutes, the solution brine ice being stirred is cooled to 0 DEG C, then drips 10mL expoxy propane.Dripped by control
Speed 1 drop/sec and being maintained at a temperature of 20 DEG C.React 30 minutes, extract addition 20mL in volatile matter, then solution in time out
The epoxychloropropane prepared in advance keeps 0 DEG C of thermotonus 8 hours at ice-water bath.Add 10mL and contain sodium hydroxide
Methanol solution, stirring at normal temperatures terminated reaction after 50 minutes.Reactant mixture is moved in the separatory funnel of 1000mL, use
Deionized water wash, stratification.Organic layer is transferred in 1000mL alembic.Then crude product is sequentially added into
50mL, the hydrochloric acid of 5%, 65mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Reduce pressure with Rotary Evaporators again, be heated up to
Removing the small-molecule substances such as solvent at 70-80 DEG C, obtain Hydrin 8.13g, productivity is 81.6%.
Claims (1)
1. the method synthesizing Hydrin, it is characterised in that concretely comprising the following steps of synthesis:
(1) in 100mL four-hole boiling flask, put into the chloropropene of 30g and the catalyst phospho heteropoly tungstate of 6.5g
/TiO2, under stirring, add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, reaction 6 lower with chloropropene backflow
Hour；
(2) reaction terminates, system shared oil, suspension liquid of aqueous phase after standing 1-2 hour；
(3) oil reservoir is standby by the epoxychloropropane of rectification isolated 23.36mL；
(4) first in equipped with the there-necked flask of stirrer, 5g diethyl aluminum chloride it is sequentially added into, through molecular sieve drying
50mL absolute ether, at normal temperatures stirring 10 minutes；
(5) the solution brine ice being stirred is cooled to 0 DEG C, then drips 10mL expoxy propane, dripped by control
Rate of acceleration 1-2 drop/sec and be maintained at the temperature of 0-20 DEG C, react 30 minutes, and extraction volatile matter obtains in time
Thick initiator A lEt2Cl；
(6) epoxychloropropane that addition 20mL prepares in advance in initiator solution keeps 0 DEG C of temperature at ice-water bath
React 8 hours；
(7) methanol solution that 10mL contains sodium hydroxide is added, little in 25 DEG C of polymerizations 5 under the protection of nitrogen
Shi Hou, terminates reaction；
(8) move to reactant mixture, in the separatory funnel of 1000mL, be washed with deionized, stratification,
Organic layer is transferred in 1000mL alembic；
(9) then crude product being sequentially added into 40mL, the hydrochloric acid of 5%, 55mL5% sodium bicarbonate, 100mL distills washing
To neutral；Reduce pressure with Rotary Evaporators again, remove the small-molecule substances such as solvent at being heated up to 70-80 DEG C, obtain
Hydrin 8.23mL.
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