CN104448288A - Method for synthesizing polyepichlorohydrin - Google Patents
Method for synthesizing polyepichlorohydrin Download PDFInfo
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- CN104448288A CN104448288A CN201410589436.9A CN201410589436A CN104448288A CN 104448288 A CN104448288 A CN 104448288A CN 201410589436 A CN201410589436 A CN 201410589436A CN 104448288 A CN104448288 A CN 104448288A
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- chloropropane
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Abstract
The invention discloses a method for synthesizing polyepichlorohydrin. The method comprises the following steps: catalyzing chloropropane by using a catalyst and additives, thereby obtaining epoxy chloropropane for later use; sequentially adding diethyl aluminum chloride and absolute ether into a three-opening flask with a stirrer, stirring for 10 minutes, cooling to be 0 DEG C, dropwise adding epoxypropane to react for 30-50 minutes, sucking out the volatile matters in time, further adding a methanol solution containing sodium hydroxide, stirring at normal temperature for 50 minutes, and stopping the reaction; moving the reaction mixture into a liquid separation funnel, washing, layering, and washing the obtained coarse product by using 5% hydrochloric acid, 5% sodium bicarbonate and distilled water till being neutral; and reducing the pressure by using a rotational evaporator, thereby obtaining 8.23g of polyepichlorohydrin. The polyepichlorohydrin yield is greater than 84.9%.
Description
Technical field
The invention belongs to polyreaction field, relate to a kind of synthetic method of Hydrin.
Background technology
Hydrin is faint yellow to amber thick liquid or solid.It is formed through the ring-opening polymerization two of epoxy chloropropionate alkene.The advantages such as Hydrin has oil-proofness, acid resistance, against gas transmission penetrance is given prominence to.Its damping row and high temperature resistant row are also fine, and have good binding property.Hydrin is carried out styracin paper flower, can be made into the photoresist material of excellent performance.Hydrin can be used for manufacturing seal gasket and oil resistant hot melt adhesive, sea water resistance, the sizing agent of oil resistant etc. and fire-retardant, water-fast, the adhesive for polyurethane of oil resistant, coating.The ring opening polymerization product of epoxy compounds becomes more and more important as system in the middle of novel polymer material.
The initiator of conventional synthesis polycyclic oxygen propenyl chloride mostly is Isosorbide-5-Nitrae-butanols bis trifluoromethyl sulfonic acid fat, trifluoroacetic acid etc.; This writes synthetic method respectively has advantage, but in polymerization process, produce a large amount of oligopolymers.Therefore, must carry out necessary aftertreatment to polymerisate, this just means that technique is more loaded down with trivial details, and the quality product of system does not reach the performance of hope.
Summary of the invention
In order to solve in prior art a large amount of impurity synthesizing Hydrin output, reducing technique loaded down with trivial details, improving the quality of polycyclic thing.
Synthetic route of the present invention is:
The present invention relates to polyacrylic building-up process to comprise the following steps:
1. the synthesis of epoxy chloropropane:
(1) in 100mL four-hole boiling flask, drop into the chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti0 of 6.5g
2), then add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate under whipped state, in the lower reaction of chloropropane backflow 6 hours;
(2) reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1-2 hour;
(3) oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.
2. initiator A lEt
2the synthesis of Cl:
(1) first in the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures;
(2) the solution icy salt solution be stirred is cooled to 0 DEG C, at dropping 10mL propylene oxide.By control drop rate 1-2 drop/sec and the temperature remaining on 0-20 DEG C.React 30 minutes, extract volatile matter in time out and obtain thick initiator A lEt
2cl.
3. the synthesis of Hydrin:
(1) in initiator solution, add the epoxy chloropropane that 20mL prepares in advance keep 0 DEG C of thermotonus 8 hours at ice-water bath;
(2) methanol solution that 10ml contains sodium hydroxide is added again, be polymerized 5 hours in 25 DEG C under the protection of nitrogen after, termination reaction;
(3) reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification.Organic layer is transferred in 1000ml matrass;
(4) then crude product is added 40-50mL successively, the hydrochloric acid of 5%, 55-65mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again with Rotary Evaporators decompression, heat except small-molecule substances such as desolventizings at 70-80 DEG C, obtain Hydrin 8.23g, productive rate is 84.9%.
Specific embodiments:
The chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti0 of 6.5g is dropped in 100mL four-hole boiling flask
2), then add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate under whipped state, in the lower reaction of chloropropane backflow 6 hours.Reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1-2 hour; Oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.In the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively again, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures, the solution icy salt solution be stirred is cooled to 0 DEG C, at dropping 10mL propylene oxide.By control drop rate 1-2 drop/sec and remain on 0-20 DEG C temperature under.Reaction 30-50 minute, extracts volatile matter out in time, then adds the epoxy chloropropane that 20mL prepares in advance in solution and keep 0 DEG C of thermotonus 8 hours at ice-water bath.Add the methanol solution that 10ml contains sodium hydroxide again, under the protection of nitrogen in 25 DEG C polymerization 5 hours after termination reaction.Reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification.Organic layer is transferred in 1000ml matrass.Then crude product is added 40-50mL successively, the hydrochloric acid of 5%, 55-65mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again with Rotary Evaporators decompression, heat except small-molecule substances such as desolventizings at 70-80 DEG C, obtain Hydrin 8.23g, productive rate is 84.9%.
Example 1
The chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti0 of 6.5g is dropped in 100mL four-hole boiling flask
2), then add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate under whipped state, in the lower reaction of chloropropane backflow 6 hours.Reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1 hour; Oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.In the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively again, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures, the solution icy salt solution be stirred is cooled to 0 DEG C, at dropping 10mL propylene oxide.By control drop rate 1 drop/sec and remain on 5 DEG C temperature under.React 30 minutes, extract volatile matter out in time, then add the epoxy chloropropane that 20mL prepares in advance in solution and keep 0 DEG C of thermotonus 8 hours at ice-water bath.Add the methanol solution that 10ml contains sodium hydroxide again, under the protection of nitrogen in 25 DEG C polymerization 5 hours after termination reaction.Reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification.Organic layer is transferred in 1000ml matrass.Then crude product is added 40mL successively, the hydrochloric acid of 5%, 55mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again with Rotary Evaporators decompression, heat except small-molecule substances such as desolventizings at 70-80 DEG C, obtain Hydrin 8.15g, productive rate is 82.9%.
Example 2
In 100mL four-hole boiling flask, drop into the chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti02) of 6.5g, then under whipped state, add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate, in the lower reaction of chloropropane backflow 6 hours.Reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1.5 hours; Oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.In the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively again, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures, the solution icy salt solution be stirred is cooled to 10 DEG C, at dropping 10mL propylene oxide.By control drop rate 1 drop/sec and remain on 0 DEG C temperature under.React 30 minutes, extract volatile matter out in time, then add the epoxy chloropropane that 20mL prepares in advance in solution and keep 0 DEG C of thermotonus 8 hours at ice-water bath.Add the methanol solution that 10ml contains sodium hydroxide again, under the protection of nitrogen in 25 DEG C polymerization 5 hours after termination reaction.Reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification.Organic layer is transferred in 1000ml matrass.Then crude product is added 45mL successively, the hydrochloric acid of 5%, 60mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again with Rotary Evaporators decompression, heat except small-molecule substances such as desolventizings at 70-80 DEG C, obtain Hydrin 8.00g, productive rate is 80.5%.
Example 3
The chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti0 of 6.5g is dropped in 100mL four-hole boiling flask
2), then add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate under whipped state, in the lower reaction of chloropropane backflow 6 hours; Reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1-2 hour; Oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.In the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively again, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures, the solution icy salt solution be stirred is cooled to 0 DEG C, at dropping 10mL propylene oxide.By control drop rate 1 drop/sec and remain on 20 DEG C temperature under.React 30 minutes, extract volatile matter out in time, then add the epoxy chloropropane that 20mL prepares in advance in solution and keep 0 DEG C of thermotonus 8 hours at ice-water bath.Add the methanol solution that 10ml contains sodium hydroxide again, stir termination reaction after 50 minutes at normal temperatures.Reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification.Organic layer is transferred in 1000ml matrass.Then crude product is added 50mL successively, the hydrochloric acid of 5%, 65mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality.Again with Rotary Evaporators decompression, heat except small-molecule substances such as desolventizings at 70-80 DEG C, obtain Hydrin 8.13g, productive rate is 81.6%.
Claims (3)
1. synthesize a method for Hydrin, it is characterized in that the synthesis of epoxy chloropropane:
(1) in 100mL four-hole boiling flask, drop into the chloropropane of 30g and the catalyzer (phospho heteropoly tungstate/Ti0 of 6.5g
2), then add 10mL hydrogen peroxide and 5g diammonium hydrogen phosphate under whipped state, in the lower reaction of chloropropane backflow 6 hours;
(2) reaction terminates, and leaves standstill system shared oil, suspension liquid of aqueous phase after 1-2 hour;
(3) oil reservoir is for subsequent use by the smart epoxy chloropropane staying separation to obtain 23.36mL.
2. a kind of method of synthesizing Hydrin according to claim 1, is characterized in that:
(1) first in the there-necked flask that stirrer is housed, add 5g diethyl aluminum chloride successively, through the 50ml anhydrous diethyl ether of molecular sieve drying, stir 10 minutes at normal temperatures;
(2) the solution icy salt solution be stirred is cooled to 0 DEG C, at dropping 10mL propylene oxide.By control drop rate 1-2 drop/sec and the temperature remaining on 0-20 DEG C.React 30 minutes, extract volatile matter in time out and obtain thick initiator A lEt
2cl.
3. a kind of method of synthesizing Hydrin according to claim 1, is characterized in that:
(1) in initiator solution, add the epoxy chloropropane that 20ml prepares in advance keep 0 DEG C of thermotonus 8 hours at ice-water bath;
(2) methanol solution that 10ml contains sodium hydroxide is added again, be polymerized 5 hours in 25 DEG C under the protection of nitrogen after, termination reaction;
(3) reaction mixture is moved in the separating funnel of 1000mL, with deionized water wash, stratification, organic layer is transferred in 1000ml matrass;
(4) then crude product is added 40mL successively, the hydrochloric acid of 5%, 55mL5% sodium bicarbonate, 100mL distilled water is washed till neutrality; Again with Rotary Evaporators decompression, to heat at 70-80 DEG C except the small-molecule substance such as desolventizing, obtain Hydrin 8.23mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892922A (en) * | 2015-04-14 | 2015-09-09 | 中国科学院长春应用化学研究所 | Hydroxyl terminated polyepichlorohydrin and preparation method thereof |
| CN114292395A (en) * | 2021-12-22 | 2022-04-08 | 天元(杭州)新材料科技有限公司 | Purification method for preparing PECH by cationic polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN102746257A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method for preparing epichlorohydrin by chloropropene epoxidation |
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- 2014-10-28 CN CN201410589436.9A patent/CN104448288B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN102746257A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method for preparing epichlorohydrin by chloropropene epoxidation |
Non-Patent Citations (1)
| Title |
|---|
| 王芳: "环氧氯丙烷合成新工艺", 《天津化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892922A (en) * | 2015-04-14 | 2015-09-09 | 中国科学院长春应用化学研究所 | Hydroxyl terminated polyepichlorohydrin and preparation method thereof |
| CN104892922B (en) * | 2015-04-14 | 2017-04-05 | 中国科学院长春应用化学研究所 | A kind of Based On Hydroxy-terminated Polyepichlorohydrin and preparation method thereof |
| CN114292395A (en) * | 2021-12-22 | 2022-04-08 | 天元(杭州)新材料科技有限公司 | Purification method for preparing PECH by cationic polymerization |
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Granted publication date: 20160831 Termination date: 20211028 |