CN108947779A - A kind of preparation method of tripropylene glycol - Google Patents
A kind of preparation method of tripropylene glycol Download PDFInfo
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- CN108947779A CN108947779A CN201810926628.2A CN201810926628A CN108947779A CN 108947779 A CN108947779 A CN 108947779A CN 201810926628 A CN201810926628 A CN 201810926628A CN 108947779 A CN108947779 A CN 108947779A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of preparation methods of tripropylene glycol, and catalyst is added in 1,2-PD and is uniformly mixed, form premix, then premix is reacted in metering pump input micro passage reaction respectively with propylene oxide, after the degassed tower removing low-boiling-point substance of reactant, product is made；1,2- propylene glycol and the molar ratio of propylene oxide are 1:2.There is minimum reaction channel and great specific surface area (>=20000m using micro passage reaction2/m3), boundary layer thickness can be effectively reduced, molecule diffusion time is greatly shortened, mass transfer, heat transfer efficiency are improved, realizes instantaneous mixing, moment reaction, and thus substantially increase the reaction efficiency of material, side reaction is reduced, to the maximum extent to guarantee the purity of product.
Description
Technical field
Invention is related to a kind of preparation method of tripropylene glycol, belongs to technical field of organic synthesis.
Background technique
Tripropylene glycol is mainly for the production of UV photo-curing monomer tri (propylene glycol) diacrylate, it is also possible to gather
The raw material of ammoniacum elastomer, paint adhesive etc., the foundation stabilization for tunnel, dam, the waterproofing and leakage-stopping in pit and building.
Its common production method: 1,2- propylene glycol and propylene oxide carry out instead in a kettle under potassium hydroxide catalyst catalysis
Answer, 1,2-PD: propylene oxide: catalyst molar ratio is 1:2~2.5:0.0002, and tripropylene glycol contains in this method product
Amount only has 29wt% or so, and the later period need to separate by rectifying.
Patent CN1803743 proposes to make catalyst using dimethylaminoethanol, and the dosage of appropriate larger catalyst, 1,2-
Propylene glycol: propylene oxide: catalyst molar ratio 1:2.5:0.0003~0.02, though this method improves two contractings 3 third compared with the above method
Glycol content reaches 45~55wt%, but tripropylene glycol content is still lower, and color remains on relatively deep, color 20~30
Number (black Zeng Danwei).
Patent CN200810020084.X uses general technology and is made into tripropylene glycol crude product, then through rectification under vacuum point
Tripropylene glycol out, two contracting things content reach 99wt%, up to 99.96wt%, the black Zeng Danwei in color≤10.This method energy
Consumption is big, and rectifying separates under the conditions of 130~190 DEG C of temperature, vacuum degree≤40kpa absolute pressure, and product yield is low.
Patent CN201010264318.2 is using 1,2-PD as raw material, in triphenylphosphine or barium hydroxide catalyst action
Under, then with propylene oxide, the obtained tripropylene glycol of reaction, 1,2-PD: epoxy third under certain temperature and pressure condition
Alkane: catalyst molar ratio 1:1.4:0.02~2.2:0.0005:0.02.Tripropylene glycol content can achieve in products obtained therefrom
48~65wt%, but three four propylene glycol object contents of contracting are 15~25wt%, and four five content of propylene glycol of contracting are 0~1.5wt%, are also needed
It will be through the available tripropylene glycol of high temperature rectification step.
Summary of the invention
The present invention is directed to the deficiency of prior art, provides a kind of synthetic method of tripropylene glycol, has preparation simply,
Products obtained therefrom lighter color, the high feature of tripropylene glycol content.Specific technical solution is as follows:
Catalyst is added in 1,2-PD and is uniformly mixed by a kind of preparation method of tripropylene glycol, forms premix
Then material reacts premix with propylene oxide in metering pump input micro passage reaction respectively, reactant is degassed
After tower removes low-boiling-point substance, product is made；
1,2- propylene glycol and the molar ratio of propylene oxide are 1:2.
In micro passage reaction, reaction temperature is 50~90 DEG C, and reaction pressure is 0.01~5MPa, residence time of material
For 0.01s~0.5s.
There is minimum reaction channel and great specific surface area (>=20000m using micro passage reaction2/m3), it can
Boundary layer thickness is effectively reduced, molecule diffusion time is greatly shortened, improves mass transfer, heat transfer efficiency, realizes instantaneous mixing, moment
Reaction, and the reaction efficiency of material is thus substantially increased, side reaction is reduced, to the maximum extent to guarantee the purity of product.
In this application, it will be mixed to get premix in catalyst and 1,2-PD first, by premix and epoxy
After propane is input in reactor, since the microchannel internal diameter in reactor is smaller, 1,2-PD can be obtained with propylene oxide
To timely mixing, the synchronous catalyst entered with 1,2-PD due to being pre-mixed uniformly, in 1,2-PD
In the mixed process of propylene oxide, it can react simultaneously, accelerate reaction speed, highly shortened the reaction time,
Efficiently avoid the generation of side reaction.
To be further ensured that going on smoothly for reaction, the microchannel internal diameter of micro passage reaction is 0.01~1.0mm, micro- logical
Road length is 0.1~3.0m, and micro passage reaction is made of steel alloy, can specifically be closed using stainless steel, titanium alloy or nickel
Gold is made.Under the limitation of above-mentioned condition, the fast reaction between material is made to be effectively guaranteed, to be product two
The purity of contracting tripropylene glycol improves more efficiently guarantee.
Further, the catalyst is at least one in 1,2-PD sodium, 1,2-PD potassium or 1,2-PD barium
Kind, the molar ratio of 1,2-PD and catalyst is 1:0.0001~0.01.
When using above-mentioned catalyst, occur proton exchange between alcohol end group, the chain that metal ion increases from one is to other
When chain tra nsfer, preferentially it is transferred on the short chain of chain, so that the polyether polyol molecular weight distribution generated is narrow, the pair in product
Product is less.
The preparation method of above-mentioned catalyst: 1,2- propylene glycol and alkali metal containing material are thrown according to molar ratio 1:0.5~1.5
Enter in closed reactor, be kept stirring, 70~120 DEG C, heat preservation 0.5~3h after, 40~80 DEG C, vacuum degree -0.090~-
It is kept for 0.5~2 hour, is made under 0.095MPa；Wherein the molal quantity of alkali metal containing material is in terms of the molal quantity of alkali metal element
It calculates；
The alkali metal containing material is at least one of material containing potassium, material containing sodium and material containing potassium.
Preferably, the alkali metal containing material is sodium hydroxide, potassium hydroxide, barium hydroxide, sodium oxide molybdena, potassium oxide, oxygen
Change any one of barium, sodium, potassium, sodium hydride, hydrofining, sodium methoxide, potassium methoxide or two or more mixtures.
The moisture content in catalyst that above-mentioned preparation method obtains is lower, and catalytic activity is higher, and usage amount is lower.
Content >=99.5wt% of tripropylene glycol in the said goods.
The technology of the present invention can greatly improve raw material mixing efficiency, reduce the generation of side reaction, two contractings 3 the third two in product
Alcohol content >=99.5%, the black Zeng Danwei in color≤5 reduce the energy consumption of rectifying separation, reduce manufacturing cost.
Specific embodiment
Embodiment 1
0.002 mole of catalyst 1,2-PD potassium is added in 1 mole of 1,2-PD, is uniformly mixed stand-by.It will be upper
1,2-PD and propylene oxide containing catalyst are stated, is continuously passed through micro passage reaction with metering pump respectively, 1,2-PD,
1:2 is matched propylene oxide in molar ratio, and reaction temperature is 60 DEG C, reaction pressure 3.0MPa, after stopping 0.2S, then through stripping tower
Low-boiling-point substance is removed, product is obtained, wherein 99.6wt% containing tripropylene glycol, the black Zeng Danwei of color 2.It is micro- logical in the present embodiment
Road reactor specifically uses stainless steel to make, and wherein microchannel internal diameter is 0.05mm, micro-tunnel length 1.0m.
The preparation of 1,2- propylene glycol potassium: 1,2- propylene glycol and potassium hydroxide are put into closed reactor according to molar ratio 1:1
In, it is kept stirring, is kept for 1 hour, be made after 80 DEG C of temperature, heat preservation 2h, then at 60 DEG C, vacuum degree -0.093MPa.
Embodiment 2
0.001 mole of catalyst 1,2-PD potassium is added in 1 mole of 1,2-PD, is uniformly mixed stand-by.It will be upper
1,2-PD and propylene oxide containing catalyst are stated, is continuously passed through micro passage reaction with metering pump respectively, 1,2-PD,
1:2 is matched propylene oxide in molar ratio, and reaction temperature is 70 DEG C, reaction pressure 1.0MPa, after stopping 0.3S, then through stripping tower
Low-boiling-point substance is removed, product is obtained, wherein 99.5wt% containing tripropylene glycol, the black Zeng Danwei of color 2.It is micro- logical in the present embodiment
Road reactor specifically uses titanium alloy to make, and wherein microchannel internal diameter is 0.10mm, micro-tunnel length 1.2m.
The preparation of 1,2-PD potassium: 1,2-PD and hydrofining are put into closed reactor according to molar ratio 1:1,
It is kept stirring, is kept for 1 hour, be made after 100 DEG C of temperature, heat preservation 2h, then at 70 DEG C, vacuum degree -0.093MPa.
Embodiment 3
0.01 mole of catalyst 1,2-PD sodium is added in 1 mole of 1,2-PD, is uniformly mixed stand-by.It will be above-mentioned
1,2-PD and propylene oxide containing catalyst are continuously passed through micro passage reaction, 1,2-PD, ring with metering pump respectively
1:2 is matched Ethylene Oxide in molar ratio, and reaction temperature is 90 DEG C, pressure 1.5MPa, after stopping 0.5S, then is removed through stripping tower low
Object is boiled, product is obtained, wherein 99.8wt% containing tripropylene glycol, the black Zeng Danwei of color 5.In the present embodiment, microchannel plate is answered
Implement body is made of titanium alloy, and wherein microchannel internal diameter is 0.20mm, micro-tunnel length 1.8m.
The preparation of 1,2- propylene glycol sodium: 1,2- propylene glycol and sodium hydroxide are put into closed reactor according to molar ratio 1:1
In, it is kept stirring, is kept for 1 hour, be made after 120 DEG C of temperature, heat preservation 1h, then at 70 DEG C, vacuum degree -0.090MPa.
Embodiment 4
0.005 mole of catalyst 1,2-PD barium is added in 1 mole of 1,2-PD, is uniformly mixed stand-by.It will be upper
1,2-PD and propylene oxide containing catalyst are stated, is continuously passed through micro passage reaction with metering pump respectively, 1,2-PD,
1:2 is matched propylene oxide in molar ratio, and reaction temperature is 80 DEG C, reaction pressure 0.5MPa, after stopping 0.2S, then through stripping tower
Remove low-boiling-point substance, obtain product, wherein 99.7wt% containing tripropylene glycol, the black Zeng Danwei of color 5.It is micro- logical in the present embodiment
Road reactor specifically uses titanium alloy to make, and wherein microchannel internal diameter is 0.50mm, micro-tunnel length 1.0m.
The preparation of 1,2- propylene glycol barium: 1,2- propylene glycol and barium monoxide are put into closed reactor according to molar ratio 1:0.5
In, it is kept stirring, is kept for 2 hours, be made after 110 DEG C of temperature, heat preservation 1h, then at 70 DEG C, vacuum degree -0.090MPa.
Embodiment 5
0.005 mole of catalyst 1,2- propylene glycol sodium and 1,2- propylene glycol potassium 0.001 are added in 1 mole of 1,2- propylene glycol
Mole, it is uniformly mixed stand-by.By above-mentioned 1,2-PD and propylene oxide containing catalyst, continuously it is passed through with metering pump respectively micro-
Channel reactor, 1:2 is matched in molar ratio for 1,2-PD, propylene oxide, and temperature is 90 DEG C, pressure 2.5MPa, is stopped
After 0.5S, then through stripping tower low-boiling-point substance is removed, product is obtained, wherein 99.5wt% containing tripropylene glycol, the black Zeng Dan of color 2
Position.In the present embodiment, micro passage reaction specifically uses titanium alloy to make, and wherein microchannel internal diameter is 0.30mm, and microchannel is long
Degree is 2.0m.
Catalyst 1,2- propylene glycol sodium in the present embodiment is using the preparation method preparation in embodiment 3.1,2- propylene glycol
Potassium is using the preparation method preparation in embodiment 2.
Claims (7)
1. a kind of preparation method of tripropylene glycol, which is characterized in that catalyst is added in 1,2-PD and is uniformly mixed,
Premix is formed, then premix is reacted in metering pump input micro passage reaction respectively with propylene oxide, is reacted
After the degassed tower removing low-boiling-point substance of object, product is made；
1,2- propylene glycol and the molar ratio of propylene oxide are 1:2.
2. preparation method according to claim 1, which is characterized in that the microchannel internal diameter of micro passage reaction be 0.01~
1.0mm, micro-tunnel length are 0.1~3.0m, and micro passage reaction is made of steel alloy.
3. preparation method according to claim 1, which is characterized in that the catalyst is 1,2-PD sodium, 1,2- third
At least one of two potassium alcoholates or 1,2- propylene glycol barium；1,2- propylene glycol and the molar ratio of catalyst are 1:0.0001~0.01.
4. preparation method according to claim 1, which is characterized in that
The catalyst the preparation method comprises the following steps: 1,2- propylene glycol and alkali metal containing material are put into according to molar ratio 1:0.5~1.5
In closed reactor, be kept stirring, 70~120 DEG C, heat preservation 0.5~3h after, then 40~80 DEG C, vacuum degree -0.090~-
It is kept for 0.5~2 hour, is made under 0.095MPa；Wherein the molal quantity of alkali metal containing material is in terms of the molal quantity of alkali metal element
It calculates；
The alkali metal containing material is at least one of material containing potassium, material containing sodium and material containing potassium.
5. the preparation method according to claim 4, which is characterized in that
The alkali metal containing material be sodium hydroxide, potassium hydroxide, barium hydroxide, sodium oxide molybdena, potassium oxide, barium monoxide, sodium, potassium,
Any one of sodium hydride, hydrofining, sodium methoxide, potassium methoxide or two or more mixtures.
6. preparation method according to claim 1, which is characterized in that in micro passage reaction, reaction temperature be 50~
90 DEG C, reaction pressure is 0.01~5MPa, and residence time of material is 0.01s~0.5s.
7. preparation method according to claim 1, which is characterized in that the content of tripropylene glycol in product >=
99.5wt%.
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| CN201810926628.2A CN108947779A (en) | 2018-08-15 | 2018-08-15 | A kind of preparation method of tripropylene glycol |
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| CN201810926628.2A CN108947779A (en) | 2018-08-15 | 2018-08-15 | A kind of preparation method of tripropylene glycol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153796A (en) * | 2019-12-31 | 2020-05-15 | 广东立邦长润发科技材料有限公司 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
| CN111548256A (en) * | 2020-05-19 | 2020-08-18 | 南京林业大学 | Preparation method of chlorohydrin ether |
| CN111574335A (en) * | 2020-05-19 | 2020-08-25 | 南京林业大学 | Propylene glycol oligomer device and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
| WO2015024103A1 (en) * | 2013-08-22 | 2015-02-26 | Shiny Chemical Industrial Co., Ltd., A Taiwan Company | Process for producing propylene glycol methyl ether |
| CN106279664A (en) * | 2016-08-22 | 2017-01-04 | 江苏擎宇化工科技有限公司 | A kind of method using micro passage reaction to produce alcoxylates |
-
2018
- 2018-08-15 CN CN201810926628.2A patent/CN108947779A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
| WO2015024103A1 (en) * | 2013-08-22 | 2015-02-26 | Shiny Chemical Industrial Co., Ltd., A Taiwan Company | Process for producing propylene glycol methyl ether |
| CN106279664A (en) * | 2016-08-22 | 2017-01-04 | 江苏擎宇化工科技有限公司 | A kind of method using micro passage reaction to produce alcoxylates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153796A (en) * | 2019-12-31 | 2020-05-15 | 广东立邦长润发科技材料有限公司 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
| CN111153796B (en) * | 2019-12-31 | 2022-11-25 | 广东立邦长润发科技材料有限公司 | Method for preparing ultraviolet curing reactive diluent from rectification by-product |
| CN111548256A (en) * | 2020-05-19 | 2020-08-18 | 南京林业大学 | Preparation method of chlorohydrin ether |
| CN111574335A (en) * | 2020-05-19 | 2020-08-25 | 南京林业大学 | Propylene glycol oligomer device and preparation method |
| CN111574335B (en) * | 2020-05-19 | 2023-03-17 | 南京林业大学 | Propylene glycol oligomer device and preparation method |
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Application publication date: 20181207 |