CN113896883A - Preparation method of acetyl terminated allyl alcohol polyether - Google Patents
Preparation method of acetyl terminated allyl alcohol polyether Download PDFInfo
- Publication number
- CN113896883A CN113896883A CN202111356902.5A CN202111356902A CN113896883A CN 113896883 A CN113896883 A CN 113896883A CN 202111356902 A CN202111356902 A CN 202111356902A CN 113896883 A CN113896883 A CN 113896883A
- Authority
- CN
- China
- Prior art keywords
- deacidification
- organic solvent
- allyl alcohol
- azeotropic
- membrane separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229920000570 polyether Polymers 0.000 title claims abstract description 50
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000007670 refining Methods 0.000 claims abstract description 16
- 230000005587 bubbling Effects 0.000 claims abstract description 15
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 238000010533 azeotropic distillation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000012527 feed solution Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000011552 falling film Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- -1 polysiloxane chain Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyethers (AREA)
Abstract
Disclosed is a process for the preparation of acetyl terminated allyl alcohol polyethers having the following structural formula: CH (CH)2＝CHCH2O(CH2CH2O)x[CH2CH(CH3)O]yCOCH3Wherein x + y is 3-100; the method comprises an acetylation reaction and a refining deacidification step, wherein the refining deacidification step comprises the following steps: nitrogen bubbling deacidification, organic solvent azeotropic deacidification and membrane separation deacidification.
Description
Technical Field
The invention relates to a preparation method of acetyl terminated allyl alcohol polyether, in particular to a refining method of acetyl terminated allyl alcohol polyether. The method has the advantage of high separation and purification efficiency, and can obtain high-purity products in a relatively short time.
Background
Allyl alcohol polyether is the main synthetic raw material of polyether modified organic silicon foam stabilizer, and is widely used for polyurethane foaming, oil field demulsifier, paint leveling agent, emulsifier, defoamer and the like.
The acetyl terminated allyl alcohol polyether is special polyether with the hydrogen on the terminal hydroxyl of the allyl alcohol polyether replaced by acetyl, has the characteristics of low foam, strong lipophilicity, low flow point, small viscosity, strong stability in acid and alkali, good oxidation stability, heat resistance and coking resistance, biodegradability and the like, is usually used as a raw material for modifying silicone oil and is used for producing Si-C type polyether modified silicone oil series products. The silicone oil modified by the product can effectively solve the cross-linking problem caused by hydroxyl-containing polyether, so that the product has better quality and better storage stability.
The polyether modified organic silicon surfactant is formed by connecting a polyether chain segment and a polysiloxane chain segment with great performance difference through chemical bonds. The connection mode between the chain segments includes Si-O-C type and Si-O type. However, the Si-O-C type foam stabilizer is not resistant to hydrolysis, has poor stability and is easy to gel failure; and the Si-O type foam stabilizer is not easy to hydrolyze, has good stability and easy structure setting and adjustment, and is suitable for preparing various polyether combined materials. Allyl alcohol polyether is hydrosilylated, and Si-O-C bonds are hardly avoided, so that crosslinking is easily caused in the copolymer, and the product quality is reduced. Therefore, the lower the hydroxyl value of the acetyl terminated polyether product, the higher the termination rate and the better the use effect.
Chinese patent CN101117379A discloses a method for synthesizing acetyl terminated allyl alcohol polyether, which comprises the steps of carrying out condensation reflux reaction on allyl alcohol polyether and acetic anhydride as raw materials, then removing most of acid by nitrogen bubbling under the vacuum condition, and removing the rest of acetic acid and acetic anhydride by a falling film evaporator under the high vacuum condition. The method has high requirements on equipment, high equipment investment cost and long product separation and purification time, is not beneficial to reducing the product cost, and more importantly, the high temperature generated by the falling film evaporator can generate adverse effect on unsaturated double bonds.
Chinese patent CN101497689A discloses a method for preparing acetyl terminated polyether, which comprises using allyl alcohol polyether and acetic anhydride as raw materials, firstly removing most of acid by nitrogen bubbling under vacuum condition, then adding water to hydrolyze the rest acetic anhydride into acetic acid, then removing acetic acid and trace acetic anhydride under high vacuum condition by vacuum and falling film evaporator, and finally obtaining acetyl terminated allyl alcohol polyether by polyether refined adsorbent adsorption. The method is simple to operate, but in order to remove acetic anhydride, water is introduced into a system, so that the produced acetyl terminated polyether is hydrolyzed in the presence of acid to produce acetic acid, the hydroxyl value is increased, and the termination rate is reduced.
Therefore, the development of a method for preparing acetyl terminated allyl alcohol polyether, especially a method for separating and purifying the product thereof, which has the advantages of low equipment investment, high efficiency and high retention rate of double bonds of the obtained product, is needed in the field.
Disclosure of Invention
The invention aims to provide a preparation method of acetyl terminated allyl alcohol polyether, which aims to solve the problems of overlong refining time, product hydrolysis and low termination rate in the prior art.
Thus. The invention provides a preparation method of acetyl terminated allyl alcohol polyether, wherein the acetyl terminated allyl alcohol polyether has the following structural formula:
CH2＝CHCH2O(CH2CH2O)x[CH2CH(CH3)O]yCOCH3，
wherein x + y is 3-100;
it comprises the steps of acetylation reaction and refining deacidification,
the refining deacidification step comprises the following steps: nitrogen bubbling deacidification, organic solvent azeotropic deacidification and membrane separation deacidification.
Detailed Description
The acetyl terminated allyl alcohol polyether of the invention has the following structural formula:
CH2＝CHCH2O(CH2CH2O)x[CH2CH(CH3)O]yCOCH3，
wherein x + y is 3 to 100, preferably 10 to 95, more preferably 20 to 90. Preferably 30-80.
The preparation method of the acetyl terminated allyl alcohol polyether comprises an acetylation reaction step.
The acetylation reaction method to be used is not particularly limited, and may be a conventional acetylation reaction method known in the art. In one embodiment of the invention, the acetylation reaction comprises heating allyl alcohol polyether and acetic anhydride to reflux in a reaction kettle.
In one embodiment of the invention the acetylation reaction comprises heating the allyl alcohol random polyether at 130-140 ℃ under reflux for 2-4 hours.
In one embodiment of the present invention, the acetylation reaction comprises allyl alcohol polyether as a raw material, acetic anhydride as a capping agent, and a molar ratio of polyether to acetic anhydride of 1.0: 1.1 to 1.5; placing the mixture into a reaction kettle, replacing the mixture with nitrogen, heating the mixture to 60-100 ℃, and reacting for 2.0-5.0 hours.
The preparation method of the acetyl terminated allyl alcohol polyether further comprises a refining deacidification step, wherein the refining deacidification step comprises the following steps: nitrogen bubbling deacidification, organic solvent azeotropic deacidification and membrane separation deacidification
a) Nitrogen bubbling deacidification
The nitrogen bubbling deacidification method suitable for the method of the present invention is not particularly limited, and may be a conventional nitrogen bubbling deacidification method known in the art.
In an embodiment of the invention, the nitrogen bubbling deacidification method comprises the step of introducing nitrogen into a reaction kettle for bubbling deacidification after the acetylation reaction is finished, and the nitrogen bubbling deacidification is carried out at the temperature of 50-70 ℃ and preferably 55-65 ℃ for 1.0-2.5 hours and preferably for 1.3-2.2 hours under the condition that the vacuum degree is-0.070-0.095 Mpa and preferably-0.080-0.070 Mpa.
b) Azeotropic deacidification of organic solvent
Azeotropic deacidification of organic solvents is known per se from the prior art. Non-limiting examples of organic solvents suitable for azeotropic deacidification in accordance with the present invention are, for example, C6-C12Aromatic hydrocarbon solvents, e.g. mono-or poly-C1-4Alkylbenzenes such as benzene, toluene, xylene, mixtures thereof, and the like.
In one embodiment of the present invention, the step of azeotropic deacidification of the organic solvent comprises adding the organic solvent to the product obtained after the bubbling deacidification, and performing azeotropic distillation at a temperature of 60-100 ℃, preferably 65-95 ℃, and more preferably 70-90 ℃ under a vacuum degree of less than or equal to-0.096 Mpa for 0.5-1.0 hour.
In one embodiment of the present invention, the organic solvent is benzene or toluene, and the added amount of the organic solvent is 0.1% to 1.0% by weight of the total weight of the feed liquid.
c) Deacidifying by membrane separation
Membrane separation techniques are known per se from the prior art, for example CN1150918A discloses a perm-selective membrane and a method for its manufacture. The invention is based on the combined utilization of an azeotropic deacidification-membrane separation deacidification method in a refining deacidification step, and the combined deacidification method can be found to be capable of favorably replacing the traditional 'falling film evaporation deacidification + solvent acid carrying', so that the equipment cost is reduced, the treatment time is shortened, the high double bond retention rate and the high end capping rate are obtained, and the good effect is achieved.
In one embodiment of the present invention, a CRP multifunctional membrane separation test apparatus available from shanghai seoi separation technology engineering ltd, model number: SA-TA-05-2, adopting a selective permeable membrane with the aperture of 200nm, and the pressure difference between the inside and the outside of a penetrating fluid of a membrane separation device is 0.1-2.5 MPa; the material flow velocity at the membrane tube side of the membrane separation equipment is 0.5-3.0 m/s.
In one embodiment of the invention, the material liquid after azeotropic deacidification is sent to a membrane separation device to obtain a concentrated solution, namely the refined acetyl terminated allyl alcohol polyether.
The acid value of the product obtained after refining deacidification is less than or equal to 0.08mgKOH/g, and the total time of the refining deacidification step is less than or equal to 4 h. The double bond retention rate of the acetyl terminated allyl alcohol polyether obtained by the refining deacidification method is more than or equal to 90 percent, and the termination rate is more than or equal to 95 percent.
In one embodiment of the invention, the preparation method comprises the steps of sequentially adding allyl alcohol polyether and acetic anhydride into a reaction kettle, vacuumizing and replacing with nitrogen, sealing the reaction kettle, heating to 70 ℃, and stirring for reacting for 3 hours. Blowing nitrogen and adjusting the flow rate of the nitrogen to keep the vacuum degree between-0.070 and-0.095 Mpa, and keeping the constant temperature at 60 ℃ for 2 hours. Adding aromatic hydrocarbon organic solvent, and performing azeotropic distillation at 80 ℃ and under the vacuum degree of-0.096 Mpa for 1 hour; then cooling and introducing into a membrane separation device (model: SA-TA-05-2, purchased from Shanghai Saiko separation technology engineering Co., Ltd.) for about 0.4-0.6h to obtain the acetyl terminated allyl alcohol polyether.
Compared with the prior art, the method combines the nitrogen bubbling, azeotropic deacidification and membrane separation deacidification, can shorten the deacidification period, and reduce the damage of high temperature to unsaturated double bonds; compared with the circulating spraying and falling film evaporation deacidification, the equipment investment is small, and the economical efficiency is higher. Meanwhile, water is prevented from being introduced into the system, so that the product is prevented from being hydrolyzed in the refining process to generate acetic acid, the hydroxyl value is increased, and the end capping rate is reduced; but also is beneficial to long-term storage of the product. In addition, the solvent with the boiling point close to that of acetic acid and acetic anhydride is selected and removed through vacuum, so that the purposes of recovering the solvent and recycling are achieved.
Examples
The present invention is further illustrated by the following examples. In the examples, the hydroxyl number of the polyethers is, according to GB/T12008.3-2009, part III of Plastic polyether polyol: measurement of hydroxyl value [. Standard measurement ].
The capping rate is defined as:
example 1
1600 parts of allyl alcohol polyether (Mn is 1500g/mol) and 230 parts of acetic anhydride are sequentially added into a reaction kettle, vacuum pumping is performed for nitrogen replacement, then the reaction kettle is sealed, the temperature is raised to 70 ℃, and stirring reaction is performed for 3 hours. Blowing nitrogen and adjusting the flow rate of the nitrogen to keep the vacuum degree between-0.070 and-0.095 Mpa, and keeping the constant temperature at 60 ℃ for 2 hours.
Adding 20 parts of benzene, and performing azeotropic distillation for 1 hour at the temperature of 80 ℃ and the vacuum degree of-0.096 Mpa; then cooling and introducing into a membrane separation device (model: SA-TA-05-2, purchased from Shanghai Saikao separation technology engineering Co., Ltd.) for about 0.5h, wherein the flow rate of the material at the membrane tube side of the membrane separation device is 0.75m/s, and the pressure difference between the inside and the outside of the penetrating fluid of the membrane separation device is 0.7MPa, so as to obtain the acetyl terminated allyl alcohol polyether, the acid value is 0.08mgKOH/g, the double bond retention rate is 94.8%, and the termination rate is 96.3%.
Example 2
1600 parts of allyl alcohol polyether (Mn 5500g/mol) and 98 parts of acetic anhydride are sequentially added into a reaction kettle, vacuum pumping is performed for nitrogen replacement, then the reaction kettle is sealed, the temperature is raised to 90 ℃, and stirring reaction is performed for 5 hours. Blowing nitrogen and adjusting the flow rate of the nitrogen to keep the vacuum degree between-0.070 and-0.095 Mpa, and keeping the constant temperature at 60 ℃ for 2.5 hours.
Adding 16 parts of toluene, performing azeotropic distillation for 1.0 hour at 90 ℃ and under the vacuum degree of-0.096 Mpa, cooling, introducing into a membrane separation device for about 0.5 hour, wherein the flow rate of a material at the membrane tube side of the membrane separation device is 0.95m/s, and the internal and external pressure difference of a penetrating fluid of the membrane separation device is 1.2MPa, so as to obtain the acetyl terminated allyl alcohol polyether, the acid value of which is 0.05mgKOH/g, the double bond retention rate of which is 94.4 percent and the termination rate of which is 97.5 percent.
Comparative example 1
1200 parts of allyl alcohol random polyether (Mn 2000g/mol) and 120 parts of acetic anhydride were sequentially added to a reaction vessel, vacuum-pumping was performed with nitrogen gas, the reaction vessel was sealed, the temperature was raised to 120 ℃, and the reaction was stirred for 4 hours. And (3) switching on a reduced pressure distillation device, keeping the temperature at 125 ℃, and keeping the vacuum degree at 0.095-0.1 Mpa for 1.5 hours. And then blowing nitrogen and adjusting the flow rate of the nitrogen to ensure that the vacuum degree is kept at 0.080-0.085 Mpa, and reducing the temperature at 120 ℃ for 1 hour. Stopping blowing nitrogen, starting a circulating spraying device, continuously and circularly spraying and deacidifying for 2 hours under the condition that the vacuum degree is kept at 0.095-0.1 Mpa and the temperature is 125 ℃, and measuring the acid value of a sample to be 0.07 mgKOH/g.
And (3) cooling to 65-70 ℃, adding deionized water with the mass fraction of 3%, stirring at constant temperature for 30 minutes, heating to 108 ℃, keeping the vacuum degree at 0.095MPa, dehydrating for 2 hours, cooling to 50 ℃, and discharging to obtain the acetyl terminated allyl random polyether, wherein the double bond retention rate is 93.4%, and the termination rate is 94.4%.
Comparative example 2
1600 parts of allyl alcohol random polyether (Mn 1000g/mol) and 310 parts of acetic anhydride are sequentially added into a reaction kettle, and then a condensation reflux device is connected, the temperature is raised to 140 ℃, and reflux reaction is carried out for 3 hours. And (3) switching on a reduced pressure distillation device, blowing nitrogen and adjusting the flow rate of the nitrogen to keep the vacuum degree of 0.080-0.090 Mpa, and carrying out bubbling deacidification for 3.0 hours. Cooling to 70 ℃, transferring into a falling film evaporator, deacidifying for 2.0 hours under the conditions that the temperature is 120 ℃ and the vacuum degree is less than or equal to 100Pa, cooling to 70 ℃, adding 25 parts of heptane, desolventizing for 1.5 hours under the conditions that the temperature is 120-130 ℃ and the vacuum degree is-0.098 MPa, cooling to 60 ℃, discharging, and obtaining the acetyl terminated allyl random polyether, wherein the acid value is 0.10mgKOH/g, the double bond retention rate is 94.3%, and the termination rate is 95.2%.
The results of the above tests are listed below:
| serial number | Duration of refining/h | Acid value mgKOH/g | Double bond retention/% | End-capping rate/%) |
| Example 1 | 3.5 | 0.08 | 94.8 | 96.3 |
| Example 2 | 4.0 | 0.05 | 94.4 | 97.5 |
| Comparative example 1 | 7.0 | 0.07 | 93.4 | 94.4 |
| Comparative example 2 | 6.5 | 0.10 | 94.3 | 95.2 |
As can be seen from the above test results, the combination of the azeotropic deacidification and the membrane separation deacidification method of the invention can not only omit the high-cost falling-film evaporator, but also can well maintain the end-capping rate of the final product and the double bond retention rate at a high level due to the relatively low temperature of the membrane separation.
Claims (5)
1. A process for preparing an acetyl terminated allyl alcohol polyether having the formula:
CH2＝CHCH2O(CH2CH2O)x[CH2CH(CH3)O]yCOCH3，
wherein x + y is 3-100;
it comprises the steps of acetylation reaction and refining deacidification,
the refining deacidification step comprises the following steps: nitrogen bubbling deacidification, organic solvent azeotropic deacidification and membrane separation deacidification.
2. The method of claim 1 wherein said step of azeotropic deacidification of organic solvent comprises using C6-C12The aromatic hydrocarbon solvent acts as an azeotropic organic solvent.
3. The method according to claim 1 or 2, wherein the organic solvent is selected from benzene or toluene, and is added in an amount of 0.1 to 1.0% based on the total weight of the feed solution.
4. The method according to claim 1 or 2, wherein the step of azeotropic deacidification of the organic solvent comprises adding the organic solvent to the product obtained after the step of bubble deacidification, and performing azeotropic distillation for 0.5 to 1.0 hour at a temperature of between 60 and 100 ℃ and under a vacuum degree of less than or equal to-0.096 Mpa.
5. The preparation method according to claim 1, wherein the membrane separation deacidification adopts a selective permeable membrane with the pore diameter of 200nm, and the pressure difference between the inside and the outside of a penetrating fluid of a membrane separation device is 0.1-2.5 MPa; the material flow velocity at the membrane tube side of the membrane separation equipment is 0.5-3.0 m/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356902.5A CN113896883A (en) | 2021-11-16 | 2021-11-16 | Preparation method of acetyl terminated allyl alcohol polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356902.5A CN113896883A (en) | 2021-11-16 | 2021-11-16 | Preparation method of acetyl terminated allyl alcohol polyether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113896883A true CN113896883A (en) | 2022-01-07 |
Family
ID=79194504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111356902.5A Pending CN113896883A (en) | 2021-11-16 | 2021-11-16 | Preparation method of acetyl terminated allyl alcohol polyether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113896883A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279668A (en) * | 2016-08-19 | 2017-01-04 | 浙江皇马科技股份有限公司 | A kind of acetyl blocked polyethers and preparation method thereof |
| CN110268001A (en) * | 2017-02-09 | 2019-09-20 | 巴斯夫欧洲公司 | The method for purifying polyether block copolymer |
-
2021
- 2021-11-16 CN CN202111356902.5A patent/CN113896883A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279668A (en) * | 2016-08-19 | 2017-01-04 | 浙江皇马科技股份有限公司 | A kind of acetyl blocked polyethers and preparation method thereof |
| CN110268001A (en) * | 2017-02-09 | 2019-09-20 | 巴斯夫欧洲公司 | The method for purifying polyether block copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 周春隆: "精细化工实验法", vol. 1, 中国石化出版社, pages: 40 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110885435B (en) | Process for preparing high functionality polyether polyols | |
| WO2017185874A1 (en) | Hydroxyl silicone oil and continuous method for preparing same | |
| US20220056209A1 (en) | Method for preparing reactive sealant resin | |
| CN106279668B (en) | A kind of acetyl blocked polyethers and preparation method thereof | |
| CN109942803B (en) | Esterified capped allyl polyether and preparation method thereof | |
| WO2019051886A1 (en) | Amine polyether polyol, preparation method therefor, and application thereof | |
| CN110818901B (en) | Preparation method of hydroxyl silicone oil | |
| CN112831040A (en) | Method for synthesizing polyester ether polyol | |
| CN113896883A (en) | Preparation method of acetyl terminated allyl alcohol polyether | |
| CN112029086A (en) | Preparation method of autocatalytic soft foam polyether polyol for sponge | |
| CN109851771B (en) | High molecular weight esterification terminated allyl polyether and synthesis method thereof | |
| CN112940239A (en) | Preparation method of hybrid block polyether polyol | |
| CN114920921B (en) | Polyether demulsifier modified by Mannich reaction and preparation method thereof | |
| CN112759565B (en) | Grease-based polyamine curing agent and preparation method and application thereof | |
| CN112920397A (en) | Polyether polyol and preparation method thereof | |
| CN112480392A (en) | Double-end olefinic bond terminated polyether and synthetic method thereof | |
| CN113754536A (en) | Preparation method of triethylene glycol di-n-caprylate | |
| CN113667111A (en) | Preparation method of sorbitol-based high molecular weight polyether polyol | |
| CN111378107B (en) | Preparation method of reactive sealant resin | |
| CN114213695B (en) | Polyurethane foam stabilizer with excellent foam pore performance, preparation method and application | |
| CN115353626B (en) | Production process of high-transparency 107 silicon rubber | |
| CN112011042A (en) | Preparation method of high molecular weight low viscosity polyether polyol | |
| CN112625242A (en) | Preparation method of single-end hydroxyl silicone oil | |
| CN115305049B (en) | High-stability methanol-removing type silicone sealant and preparation method thereof | |
| CN116082622A (en) | Aging-resistant degradable modified double-bio-based polyether polyol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |