CN1003516B - Synthesis of polyglycol-bis-(epoxy propyl ether) - Google Patents
Synthesis of polyglycol-bis-(epoxy propyl ether) Download PDFInfo
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- CN1003516B CN1003516B CN86104089.9A CN86104089A CN1003516B CN 1003516 B CN1003516 B CN 1003516B CN 86104089 A CN86104089 A CN 86104089A CN 1003516 B CN1003516 B CN 1003516B
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Abstract
The present invention relates to a synthetic method of polyglycol-bis-epoxy propyl ether(including ethylene glycol), which belongs to a synthetic method of bis-epoxy propyl ether. The present invention is characterized in that the polyglycol-bis-epoxy propyl ether is prepared form polyglycol and epichlorohydrin as raw materials and alkali or mixed alkali as condensing agents by stirring the mixture for reaction for 5 to 20 hours at the existence of phase transfer catalysts and organic solvents at the temperature of 30 to 70 DEG C, filtering the mixture, steaming the filtrate to remove solvents, reducing pressure and fractionating the mixture to obtain the polyglycol-bis-epoxy propyl ether. The yield of the polyglycol-bis-epoxy propyl ether is from 30 to 56%.
Description
The invention belongs to the synthetic method of diepoxypropyl ether.
Multicondensed ethylene glycol (comprising ethylene glycol) diepoxypropyl ether is widely used as the finishing composition of reactive thinner, paper and the fabric of Resins, epoxy; Wherein, the Triethylene glycol diepoxypropyl ether still has been used for clinical antitumor drug both at home and abroad.
In the prior art, the synthetic two kinds of approach (seeing the reaction formula I) that mainly contain of multicondensed ethylene glycol diepoxypropyl ether.
n=1，2，3…
The reaction formula I
Press approach 1, Saul etc. (J.Am.Chem, Soc.75,1733(1953)) and English Patent 794,632 have been synthesized the ethylene glycol bis glycidyl ethers; English Patent 901876 has been synthesized the Triethylene glycol diepoxypropyl ether.By the synthetic multicondensed ethylene glycol diepoxypropyl ether of this approach, reactions steps is more, troublesome poeration, and overall yield is on the low side.
В Л А ю л а н Ж у р н а л (о р г а н н ч e с к о й Х н м н н, 3(8), 1423(1967)) employing approach 2 has synthesized three kinds of multicondensed ethylene glycol diepoxypropyl ethers (n=1,2,3 in the reaction formula 1), but productive rate all is lower than 25%, and produces 60～70% polymerization by product in the system.Recently, (Synthesis such as Meada, (3), 185(1983)) employing approach 2 synthetic Triethylene glycol diepoxypropyl ethers, by changing reaction conditions (raw material feed ratio, temperature etc.), though can make productive rate reach 51%, but need in the reaction with excessive epoxy chloropropane (with the mol ratio of glycol be 6: 1), excessive alkali reagent-sodium hydroxide and yellow soda ash (the two mol ratio is 1: 1), the mol ratio of total alkali content and glycol is 12: 1, and the product separation purification step is many, consumes a large amount of solvents and reagent.
The objective of the invention is to improve the method for existing synthetic multicondensed ethylene glycol diepoxypropyl ether, simplify reaction and product separation purification step, improve reaction yield.
Main points of the present invention are: with multicondensed ethylene glycol, epoxy chloropropane is raw material, is condensing agent with alkali or mixed base, and in the presence of phase-transfer catalyst and organic solvent, single step reaction synthesizes multicondensed ethylene glycol diepoxypropyl ether (seeing the reaction formula II).
n＝1，2，3，4
The reaction formula II
Temperature of reaction is 30-70 ℃, and the reaction times is 5-20 hour, and after reaction finished, reaction mixture filtered, filtrate steaming removal solvent, vacuum fractionation gets product, productive rate 30-56%, epoxy chloropropane is industrial pure material or chemical pure in the reaction, analytical reagent, its consumption be stoichiometry or excessive 1-5 doubly.The phase-transfer catalyst that adopts is various molecular weight polyethylene glycol and derivative thereof, and its consumption is the 1-10mol% of alcohol.Alkali is the mixed base that sodium hydroxide, potassium hydroxide, salt of wormwood and they are formed by different ratios, and the consumption of alkali by stoichiometry or excessive 1-5 doubly.Used organic solvent is epoxy chloropropane, methylene dichloride, 1, and 2-ethylene dichloride, its consumption are every mole of glycol 200-1000 milliliter solvent.The working method of reaction is that raw material, solvent and reagent are dropped in the reaction flask (device) successively, and heating is stirred certain hour under assigned temperature.
Compared with the prior art, synthesis of polyglycol-bis-(epoxy propyl ether) of the present invention has the following advantages:
1. reactions steps is brief, mild condition.The synthetic multicondensed ethylene glycol diepoxypropyl ether of many patents all adopts two step or polystep reactions, press the synthetic route of approach 1 as described above, the first step reaction is carried out under 80-90 ℃ usually, under ice bath or lesser temps, carry out the reaction of second step then, thereby the operation trouble, and take a lot of work, take material, expense energy.Only with the synthetic multicondensed ethylene glycol diepoxypropyl ether of single step reaction, reaction is generally carried out getting final product in 10 hours about 40 ℃ in the present invention.
2. the product separation purification step is few, and prior art is various to product separation purification formality, needs to consume a large amount of reagent and solvent usually.As (see before and state) such as Meada in the process of separating purification Triethylene glycol diepoxypropyl ether, need to use the benzene diluted reaction mixture, filter, after filtrate steaming is removed benzene, add saturated aqueous sodium chloride in the debris, with this aqueous solution of dichloromethane extraction, methylene dichloride is behind anhydrous sodium sulfate drying, and steaming desolventizes, vacuum fractionation just gets product, and the present invention only needs to filter to the product separation purification, and steaming desolventizes, vacuum fractionation.
3. productive rate is higher.The productive rate of synthesizing glycol diepoxypropyl ethers such as Saul is 20%, and the productive rate of the synthetic glycol ether diepoxypropyl ether of Б л я ю а н is lower than 25%, and the productive rate of the synthetic Triethylene glycol diepoxypropyl ether of Meada is 51%.The productive rate of the synthetic four kinds of multicondensed ethylene glycol diepoxypropyl ethers of the present invention (n=1 in the reaction formula (), 2,3,4) is respectively 30,38,54,56%.
Following example is seen in concrete operations of the present invention.
Example 1
31 gram ethylene glycol, 278 gram epoxy chloropropane, 276 gram salt of wormwood, 10 milliliters of polyoxyethylene glycol-400 are added in the reaction flask, heating, 50 ℃ were stirred 15 hours down.Filter, filtrate steaming is removed excessive epoxy chloropropane, and vacuum fractionation is collected 90-2 ℃/0.3-0.4mmHg fraction, gets ethylene glycol bis glycidyl ethers 26.4 grams, productive rate 30%, α-oxirane value % is a 18.2(calculated value 18.4).
Example 2
With 53 gram-diglycol ethylenes, 185 gram epoxy chloropropane, 300 milliliters of methylene dichloride, 112 gram potassium hydroxide, 138 restrain salt of wormwood, 20 milliliters of polyoxyethylene glycol-400 add in the reaction flask, and heating is stirred, and reacts 10 hours down between 40 ℃.Filter, filtrate steaming removal solvent, vacuum fractionation is collected 121-3 ℃/0.2-0.3mmHg fraction, gets glycol ether diepoxypropyl ether 41.4 grams, productive rate 38%; α-oxirane value % is a 15.2(calculated value 14.7).
Example 3
75 gram Triethylene glycols, 139 gram epoxy chloropropane, 400 milliliters of methylene dichloride, 54 gram potassium hydroxide, 10 milliliters of polyoxyethylene glycol-400 are added in the reaction flask, heating, 45 ℃ were stirred 10 hours down.Product separation is purified with example 2, collects 146-8 ℃/0.4-0.5mmHg fraction, productive rate 54%, α-oxirane value % is a 11.9(calculated value 12.2).
Example 4
97 gram tetraethylene-glycols, 185 gram epoxy chloropropane, 400 milliliters of methylene dichloride, 56 gram potassium hydroxide, 5 milliliters of polyoxyethylene glycol-400 are added in the reaction flask, heating, 50 ℃ were stirred 10 hours down, product separation is purified with example 2, collect 180～3 ℃/0.4-0.5mmHg fraction, productive rate 56%, α-oxirane value % is a 9.12(calculated value 10.5).
Claims (5)
1, a kind of synthetic multicondensed ethylene glycol (n=1,2,3,4) method of diepoxypropyl ether, it is characterized in that with multicondensed ethylene glycol, epoxy chloropropane be raw material, make condensing agent, in the presence of phase-transfer catalyst and organic solvent, react with alkali or mixed base, reaction mixture after filtering, filtrate steaming removal solvent, vacuum fractionation gets product.
2, synthetic method according to claim 1, used alkali are the mixed base that sodium hydroxide, potassium hydroxide, salt of wormwood and they are formed by different ratios.
3, synthetic method according to claim 1, used phase-transfer catalyst are various molecular weight polyethylene glycol and derivative thereof.
4, synthetic method according to claim 1, used solvent are the mixed solvent that epoxy chloropropane, methylene dichloride, ethylene dichloride and they are formed by different ratios.
5, synthetic method according to claim 1, temperature of reaction are 40～50 ℃, and the reaction times is 5～20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104089.9A CN1003516B (en) | 1986-06-17 | 1986-06-17 | Synthesis of polyglycol-bis-(epoxy propyl ether) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104089.9A CN1003516B (en) | 1986-06-17 | 1986-06-17 | Synthesis of polyglycol-bis-(epoxy propyl ether) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86104089A CN86104089A (en) | 1987-01-24 |
| CN1003516B true CN1003516B (en) | 1989-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86104089.9A Expired CN1003516B (en) | 1986-06-17 | 1986-06-17 | Synthesis of polyglycol-bis-(epoxy propyl ether) |
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| CN (1) | CN1003516B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5761775B2 (en) * | 2010-01-07 | 2015-08-12 | 株式会社Adeka | Diβ-methylglycidyl ether of bisphenol A propylene oxide adduct and curable resin composition using the same |
| CN104356378B (en) * | 2014-09-22 | 2016-08-24 | 南京航空航天大学 | A kind of preparation method of 3 D-printing low viscosity photocuring prepolymer |
| CN106146325B (en) * | 2015-04-24 | 2019-01-29 | 北京键凯科技股份有限公司 | A kind of Y type multicondensed ethylene glycol derivative and preparation method thereof |
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1986
- 1986-06-17 CN CN86104089.9A patent/CN1003516B/en not_active Expired
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| CN86104089A (en) | 1987-01-24 |
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