CN101701063B - Preparation method of polyepichlorohydrin - Google Patents
Preparation method of polyepichlorohydrin Download PDFInfo
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- CN101701063B CN101701063B CN2009102728101A CN200910272810A CN101701063B CN 101701063 B CN101701063 B CN 101701063B CN 2009102728101 A CN2009102728101 A CN 2009102728101A CN 200910272810 A CN200910272810 A CN 200910272810A CN 101701063 B CN101701063 B CN 101701063B
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Abstract
The invention relates to a preparation method of polyepichlorohydrin. Alkoxyl triphenyl phosphine compound is taken as initiating agent, anhydrous organic solvent is added in and mixing and stirring are carried out, stirring is carried out at normal temperature for 10-15 minutes, then Lewis acid is added in to be taken as catalyst, epoxy chloropropane is dropwise added, temperature is controlled to be minus 20 DEG C to 25 DEG C, and polymerization reaction and stopping polymerization reaction are carried out, thus obtaining the polyepichlorohydrin. Compared with the existing preparation method of polyepichlorohydrin, the polyepichlorohydrin prepared by the method of the invention is in light colour of colourless or white, is beneficial to processing of subsequent product, number-average molar mass is 500-10000, dispersion index of molecular weight is low and generally less than 1.5, preparation of the used initiating agent is simple, polymerization condition is mild, polymerization time is short, and yield of polymerization product is high.
Description
Technical field
The present invention relates to a kind of preparation method of Hydrin.
Background technology
Hydrin forms through the epoxy chloropropane ring-opening polymerization, and Hydrin is owing to its oil resistant, anti-solvent, acidproof, and marquis's property was good in anti-day; Ozone resistance is excellent, and the infiltration of gasproof body is outstanding, its damping performance; Resistance to elevated temperatures, and have good binding property and processing characteristics.Can be applicable to make seal gasket and oil resistant hot melt adhesive, sea water resistance, grease-proof sizing agent and Embedding Material, photoresist material, polyurethane elastomer, sizing agent etc. and fire-retardant, water-fast, grease-proof adhesive for polyurethane, coating and Embedding Material.
Hydrin is normally to be prepared through cationic ring-opening polymerization by epoxy chloropropane.At U.S.Pat.No.5, provided with 1 in 041,531,4-butyleneglycol bis trifluoromethyl sulphonate (BDT) prepares Hydrin for initiator.Number of patent application is 200810187705.3; Denomination of invention has provided small molecular weight initiator, bimetallic cyanide complex catalyst for the one Chinese patent application of " a kind of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation method thereof ", preparation terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.U.S.Pat.No.4,879,419 to have provided with the tin tetrachloride be catalyzer, 1, the 4-butyleneglycol is an initiator, trifluoroacetic acid is that promotor prepares Hydrin.U.S.Pat.No.3,850,857, having provided with HMF6 trialkyl oxonium salt is catalyzer, the cationic ring-opening polymerization of epoxy chloropropane, wherein M representes the element of the 5th main group, comprises phosphorus, arsenic, antimony.JP:04198319 has provided with SbCl
5Be catalyzer, terepthaloyl moietie is initiator, preparation terminal hydroxy group Hydrin.Other methods that prepare Hydrin comprise: BF3 also is used for epoxy chloropropane polyreaction (Grinevich TV, Korovina G V, Entelis S G.Polymerization of epoxide in the pesence of Lewis acides [J] .Vysokomol Sodin; Ser A; 1979,21 (6): 1244-1250.) sulfuric acid is used for epoxy chloropropane polyreaction (Kazaryan GA, Kirakosyan Kh A; Karapetyan A N; Et al.Polymerization mechanism of ECH by sulfuric acid innitromethane [J] .Arm Khim Zh, 1976,29 (10): 833.)
Yet,, in polymerization process, all can produce a large amount of oligopolymer (comprising 2 or 4 epoxy chloropropane unit) although the polyreaction of the epoxy chloropropane that above-mentioned initiator causes respectively has its advantage.A little less than the nucleophilicity of nucleophilicity owing to Sauerstoffatom in the epoxy chloropropane than the Sauerstoffatom on the epoxy chloropropane polyether chain; Sauerstoffatom on the polymer chain to the ability of end of the chain active site attack greater than the ability of monomer to the attack of end of the chain active site; Make the end of the chain active site of polyreaction be easy to the epoxy chloropropane polyether chain on Sauerstoffatom intramolecular " reverse interlock " takes place, generate cyclic oligomers such as forming a large amount of stable cyclic dimers, cyclic tetramer.The functionality of these oligopolymers is zero, molecular weight is lower, and their existence will have a strong impact on indexs such as the molecular weight, average functionality of polyethers, thereby influences the quality of Hydrin.They as impurity or byproduct of reaction in reaction process along with the increase of the molecular weight of Hydrin and increase.Therefore, must carry out necessary aftertreatment to polymerisate and remove these impurity or byproduct of reaction.In addition, the Hydrin that generates of the polymerization of the epoxy chloropropane that causes of above-mentioned initiator has bigger molecular weight dispersed (ratio of polymer number-average molecular weight Mn being called the molecular weight dispersiveness with high molecular weight-average molecular weight Mw).The quality that this means the product of such Hydrin preparation will not reach desirable performance.
Summary of the invention
Problem to be solved by this invention is to above-mentioned prior art a kind of initiation of epoxy chloropropane polyreaction and the method that catalystsystem prepares Hydrin to be provided; The activity that has changed the end of the chain active site of polymkeric substance makes it that intramolecular " reverse interlock " can not take place with the Sauerstoffatom on the epoxy chloropropane polyether chain; Thereby reduce the generation of low-molecular-weight oligomer, improve the quality of Hydrin.
The present invention by the problem of the above-mentioned proposition of solution the employing solution be: a kind of preparation method of Hydrin; It is characterized in that with alkoxyl group triphenylphosphine compound be initiator, to wherein adding anhydrous organic solvent mixing stirring, normal temperature stirred 10-50 minute down; Add Lewis acid then as catalyzer; Drip epoxy chloropropane, controlled temperature is-20 ℃-25 ℃, prepares Hydrin through polyreaction, termination polyreaction.
Press such scheme, described Hydrin has the general structure that general formula (I) is represented:
R in the formula
1Be hydrogen, methyl, ethyl, phenyl, ethanoyl or phenmethyl organic group, R
2Be hydrogen, methyl, ethyl, phenyl, ethanoyl or phenmethyl organic group, n are 10-100.
Press such scheme, described alkoxyl group triphenylphosphine compound, it has the general structure of general formula (II) expression:
In the formula, R
1Be defined as with general formula (I) in definition identical, X is tetrafluoride boron (BF
4), six silicon fluoride (SiF
4), phosphorus hexafluoride (PF
6) or antimony hexafluoride (SbF
6) negatively charged ion.
Press such scheme, described Lewis acid is boron trifluoride, silicon tetrafluoride, phosphorus pentafluoride, aluminum chloride or zinc chloride.
Press such scheme, described anhydrous organic solvent is methylene dichloride, trichloromethane or 1, the 2-ethylene dichloride.
When temperature was higher than 5 ℃, the color of Hydrin was darker, and therefore, the temperature of preferred polyreaction is-5 ℃-5 ℃.
Press such scheme, described polymerization reaction time is 5-30 hour.
Press such scheme, described polymerization reaction time is preferably 8-20 hour.
Press such scheme, described churning time preferred range is 20-30 minute.
The terminator that above-mentioned termination polyreaction is taked is an alkali, water, and alcohol, phenol, lipid acid etc. are like water; Methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, phenol; Formic acid, acetate, vinylformic acid, phenylformic acid etc., the solution of described terminator are the water or the alcoholic solution of corresponding terminator.
The temperature of above-mentioned termination polyreaction is a room temperature, stops polymerization reaction time at 0.5-1 hour, and comparatively speaking, the select time scope is better in 40-50 minute.
Beneficial effect of the present invention is:
Compare with the preparation method of existing Hydrin, through the Hydrin lighter color of method preparation of the present invention, for colourless or white; Help the processing of its subsequent product, number-average molecular weight is 500-10000, and the molecular weight dispersion index is less; Be generally less than 1.5, employed initiator preparation is simple, and polymerizing condition is gentle; Polymerization time is shorter, and the polymerisate productive rate is high.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following enforcement.
Embodiment 1:
, the there-necked flask of stirrer adds the 35ml methylene dichloride in being housed successively; 0.001mol oxyethyl group triphenylphosphine tetrafluoride boron; Normal temperature stirs after 25 minutes down, adds the 0.5ml boron trifluoride again, and system temperature is reduced to 0 ℃; Begin to drip the 18ml epoxy chloropropane again, through control drop rate 1--2 drip/second and ice-water bath remain on 0 ℃ temperature.React after 8 hours, add massfraction that 10ml contains NaOH and be 10% methanol solution, stir termination reaction after 50 minutes at normal temperatures.Isolate thick product.Then that thick product is extremely neutral with the zero(ppm) water repetitive scrubbing.Again with Rotary Evaporators decompression, 70 ℃ are removed small-molecule substance such as desolvate down.The resulting polymers productive rate is 80%, and using PS to be standard specimen, THF (THF) is in gel permeation chromatography (GPC) test of moving phase, number-average molecular weight be 3244, the molecular weight dispersion index is 1.34.
Embodiment 2:
According to the step of the preparation Hydrin of embodiment 1, the Hydrin of using oxyethyl group triphenylphosphine tetrafluoride boron and Tetrafluoroboric acid triethyl oxygen (embodiment as a comparison) to prepare respectively respectively for initiator.Its result is as shown in table 1.In table 1; I/M is initiator/monomeric mol ratio; Productive rate is to calculate with the polymer yield behind the purifying, and molecular weight and molecular weight dispersion index are to use PS to be standard specimen through gel permeation chromatography (GPC), and THF (THF) obtains for the moving phase test.
The polyreaction of the epoxy chloropropane under the various conditions of table 1
| Initiators for polymerization | I/M | Solvent | Catalyzer | Temperature of reaction (℃) | Reaction times (hour) | Productive rate (%) | Number-average molecular weight (Mn) | The molecular weight dispersion index |
| Tetrafluoroboric acid triethyl oxygen | 1/200 | 1.2-ethylene dichloride | ?----- | 25 ℃ of room temperatures | 50 | 50 | 310 | 3.46 |
| Oxyethyl group triphenylphosphine tetrafluoride boron | 1/200 | Methylene dichloride | Boron trifluoride | 0℃ | 8 | 75 | 2251 | 1.37 |
Embodiment 3:
According to the step of the preparation Hydrin of embodiment 1, with 0.001mol methoxyl group triphenylphosphine tetrafluoride boron, 40ml1; The 2-ethylene dichloride; Normal temperature stirred down after 20 minutes, added the 0.001mol silicon tetrafluoride, and system temperature is reduced to 5 ℃; Begin Dropwise 35 ml epoxy chloropropane again, through control drop rate 1--2 drip/second and water-bath remain on 5 ℃ temperature.React after 12 hours, add 10ml acetate, stirred at normal temperatures 30 minutes, add 15ml methyl alcohol, stirred 10 minutes.Isolate thick product.Then that thick product is extremely neutral with the zero(ppm) water repetitive scrubbing.Again with Rotary Evaporators decompression, 70 ℃ are removed small-molecule substance such as desolvate down.The resulting polymers productive rate is 78%, and number-average molecular weight is 4321, and the molecular weight dispersion index is 1.31.
Embodiment 4:
Step according to the preparation Hydrin of embodiment 1; With 0.001mol hydroxyl triphenylphosphine tetrafluoride boron; 20ml methylene dichloride, normal temperature stirred down after 20 minutes, added the 0.001mol boron trifluoride; Drip the 30ml epoxy chloropropane, drip/25 ℃ of reactions down of second drop rate and maintenance through control 1--2.React after 18 hours, add 30ml water, stirred at normal temperatures 30 minutes, isolate thick product.Then that thick product is extremely neutral with the zero(ppm) water repetitive scrubbing.Again with Rotary Evaporators decompression, 70 ℃ are removed small-molecule substance such as desolvate down.The resulting polymers productive rate is 80%, and number-average molecular weight is 2327, and the molecular weight dispersion index is 1.49.
Embodiment 5:
Step according to the preparation Hydrin of embodiment 1; With 0.001mol hydroxyl triphenylphosphine six silicon fluorides, 20ml methylene dichloride, normal temperature stir after 20 minutes down; Add the 0.001mol zinc chloride; And system temperature reduced to 0 ℃, drip the 25ml epoxy chloropropane, through control 1--2 drip/second drop rate with keep 0 ℃ of reaction down.React after 30 hours, add 30ml water, stirred at normal temperatures 30 minutes, isolate thick product.Then that thick product is extremely neutral with the zero(ppm) water repetitive scrubbing.Again with Rotary Evaporators decompression, 70 ℃ are removed small-molecule substance such as desolvate down.The resulting polymers productive rate is 80%, and number-average molecular weight is 2980, and the molecular weight dispersion index is 1.47.
Claims (9)
1. the preparation method of a Hydrin, it is characterized in that: with alkoxyl group triphenylphosphine compound is initiator, to wherein adding anhydrous organic solvent mixing stirring; Normal temperature stirred 10-50 minute down, added Lewis acid then as catalyzer, dripped epoxy chloropropane; Controlled temperature is-20 ℃-25 ℃; Prepare Hydrin through polyreaction, termination polyreaction, described alkoxyl group triphenylphosphine compound, it has the general structure of general formula (II) expression:
In the formula, R
1Be methyl or ethyl, X is tetrafluoride boron, six silicon fluorides, phosphorus hexafluoride or antimony hexafluoride negatively charged ion.
2. by the preparation method of the described Hydrin of claim 1, it is characterized in that: described Hydrin has the general structure that general formula (I) is represented:
R in the formula
1Be methyl or ethyl, R
2Be methyl or ethyl, n is 10-100.
3. by the preparation method of the described Hydrin of claim 1, it is characterized in that: described Lewis acid is boron trifluoride, silicon tetrafluoride, phosphorus pentafluoride, aluminum chloride or zinc chloride.
4. by the preparation method of the described Hydrin of claim 1, it is characterized in that: described anhydrous organic solvent is methylene dichloride, trichloromethane or 1, the 2-ethylene dichloride.
5. by the preparation method of the described Hydrin of claim 1, it is characterized in that: the temperature of polyreaction is-5 ℃-5 ℃.
6. by the preparation method of the described Hydrin of claim 5, it is characterized in that: the time of polyreaction is 5-30 hour.
7. by the preparation method of the described Hydrin of claim 6, it is characterized in that: described polymerization reaction time is 8-20 hour.
8. by the preparation method of the described Hydrin of claim 1, it is characterized in that: described churning time is 20-30 minute.
9. by the preparation method of the described Hydrin of claim 1, it is characterized in that: the temperature that stops polyreaction is a room temperature, and the time that stops polyreaction is 0.5-1 hour.
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|---|---|---|---|
| CN2009102728101A CN101701063B (en) | 2009-11-18 | 2009-11-18 | Preparation method of polyepichlorohydrin |
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|---|---|---|---|
| CN2009102728101A CN101701063B (en) | 2009-11-18 | 2009-11-18 | Preparation method of polyepichlorohydrin |
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| CN101701063B true CN101701063B (en) | 2012-01-11 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174185B (en) * | 2011-01-31 | 2012-10-10 | 武汉工程大学 | Synthesis technology of hydroxyl terminated polyepichlorohydrin |
| CN102731570B (en) * | 2012-07-10 | 2015-05-20 | 武汉工程大学 | Synthesis process of triphenyl alkoxyl phosphine salt |
| CN103965384B (en) * | 2014-05-16 | 2016-01-06 | 武汉工程大学 | The preparation method of polymethylmethacrylate |
| CN104448288B (en) * | 2014-10-28 | 2016-08-31 | 常州大学 | A kind of method synthesizing Hydrin |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104956A (en) * | 1985-06-26 | 1986-07-02 | 浙江大学 | The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst |
| CN101497691A (en) * | 2008-12-31 | 2009-08-05 | 青岛科技大学 | High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof |
-
2009
- 2009-11-18 CN CN2009102728101A patent/CN101701063B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104956A (en) * | 1985-06-26 | 1986-07-02 | 浙江大学 | The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst |
| CN101497691A (en) * | 2008-12-31 | 2009-08-05 | 青岛科技大学 | High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| 孙亚斌.端羟基聚环氧氯丙烷的合成与表征.《化学推进剂与高分子材料》.2005,第3卷(第6期),第33-37页. * |
| 宋晓庆.端羟基聚环氧氯丙烷制备过程中齐聚物的生成与去除.《化学推进剂与高分子材料》.2007,第5卷(第6期),第44-47页. * |
| 张九轩.液体端羟基聚环氧氯丙烷的合成.《黎明化工》.1994,(第6期),第26-29页. * |
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