CN101941893B - Method for synthesizing tripropylene glycol - Google Patents
Method for synthesizing tripropylene glycol Download PDFInfo
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- CN101941893B CN101941893B CN2010102643182A CN201010264318A CN101941893B CN 101941893 B CN101941893 B CN 101941893B CN 2010102643182 A CN2010102643182 A CN 2010102643182A CN 201010264318 A CN201010264318 A CN 201010264318A CN 101941893 B CN101941893 B CN 101941893B
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Abstract
The invention discloses a method for synthesizing tripropylene glycol. The tripropylene glycol is prepared from commercial 1,2-propylene glycol serving as a raw material and propylene oxide serving as a chain extender under the action of triphenylphosphine or barium hydroxide serving as a catalyst under the conditions of certain temperature and certain pressure, wherein the molar ratio of the 1,2-propylene glycol to the propylene oxide to the catalyst is 1:1.4:0.02-2.2:0.0005:0.02. The method has the characteristics of simple preparation, high product quality, high tripropylene glycol content and light color.
Description
Technical field
The present invention relates to a kind of synthetic method of tripropylene glycol, relate in particular to that a kind of content height, superpolymer content are low, lighter color, the measured tripropylene glycol synthesis method of matter, belong to technical field of organic compound synthesis.
Background technology
Tripropylene glycol (TPG), it is one of important source material of radiation curing (coating, printing ink) tri (propylene glycol) diacrylate (TPGDA) monomer, its mode of production has: be that raw material carries out hydration reaction and produces 1 with propylene oxide and water, the 2-propylene glycol, propylene oxide: water=1: 2.9 (mol ratio), high temperature more than 160 ℃, 3～4Mpa pressure.This severe reaction conditions, energy consumption of reaction is higher, can only obtain 40% 1, the 2-aqueous solution of propylene glycol needs through thickening, rectifying, receive 1,2-propylene glycol after, receive by product again.The high boiling fraction tripropylene glycol, the production yield is lower, and the product colour jaundice.Tripropylene glycol with this technology gained prepares the tri (propylene glycol) diacrylate monomer, and monomeric ester content is low, and about 90～92%.Low with this monomer production coating surface hardness, the monomer color is dark, can not satisfy the requirement of high-grade paint and printing ink.
Adopt 1,2-propylene glycol and propylene oxide to react under potassium hydroxide catalyst catalysis, three's mol ratio is 1,2-propylene glycol: propylene oxide: catalyzer=1: 2～2.5: 0.0002.This method, because potassium hydroxide is active high, the products obtained therefrom complicated component contains potassium hydroxide in the resultant, must carry out neutralizing treatment except alkali to it.Neutralization can produce moisture again, and removing moisture has increased production process and cost, and the generation of pollution is arranged.In the product, two contracting thing content have only about 29%, and the superpolymer content more than the tetramer is more, accounts for about 20%.Speed of response was slow when this just caused preparing the tri (propylene glycol) diacrylate monomer, and gained monomeric ester content is lower, has only 90-92%.The jaundice of tripropylene glycol color, colourity are at (black Ceng Danwei) more than No. 70, and tri (propylene glycol) diacrylate monomer colourity can not be used for high-grade light-coloured coating and printing ink at (black Ceng Danwei) more than No. 100.
In order to improve the deficiency of above method, Chinese patent CN1803743 proposes to adopt dimethylaminoethanol to make catalyzer, and suitably strengthens catalyst consumption, makes 1,2-propylene glycol: propylene oxide: catalyst molar ratio=1: 2.5: 0.0003～0.02.Though this method has improved two contracting thing content than aforesaid method, can reach 45～55%, color and luster also descends to some extent and reaches (black Ceng Danwei) 20～No. 30.But two contracting thing content are still lower, and color and luster is also still darker, and dimethylaminoethanol and propylene oxide can react and generate dimethylaminoethanol polyethenoxy ether by product.
In order to overcome the defective that color and luster is dark, content is low, Chinese patent (application number: 200810020084.X) adopted general technology to make the tripropylene glycol crude product, tell tripropylene glycol through rectification under vacuum again, two contracting thing content reach 99%, be up to 99.96%, color and luster≤No. 10 (black Ceng Danwei).But this method energy consumption is big, needs rectifying separation under 130～190 ℃ of temperature, vacuum tightness≤40kpa absolute pressure condition, and the product yield is low, the equipment requirements height, and cost budgeting is many.
Summary of the invention
Main purpose of the present invention is to provide a kind of synthetic method of tripropylene glycol, and it is simple to have a preparation, and the products obtained therefrom quality is good, two contracting thing content height, light-colored characteristics.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of synthetic method of tripropylene glycol, with commercially available 1, the 2-propylene glycol is raw material, under triphenylphosphine or hydrated barta catalyst action, again with propylene oxide as chain extension agent, under certain temperature and pressure condition the reaction make tripropylene glycol, three's mol ratio is 1,2-propylene glycol: propylene oxide: catalyzer=1: 1.4: 0.02～2.2: 0.0005: 0.02, its reaction equation is:
Described temperature of reaction is 80～140 ℃.
Described reaction pressure is-0.05～0.45Mpa.
Described hydrated barta catalyzer adopts barium monohydrate or many water hydrated barta.
Described many water hydrated barta preferably adopts barium hydroxide.
Beneficial effect of the present invention is: the present invention has selected hydrated barta or triphenylphosphine as catalyzer, makes reacting balance, controllability good, and selectivity of product improves, and propylene oxide and 1, the 2-propylene glycol polymerization degree reduce, and reaction is carried out to more favourable direction.Products obtained therefrom distributes rationally, and tripropylene glycol content height can reach 48～65%; Three contracting thing content are that 15～25%, four contracting thing content are 0～1.5%.Superpolymer content is low, does not contain the above superpolymer of five contracting propylene glycol substantially; Four contracting content of propylene glycol are also extremely low, and only about 0～1.5%.Be more suitable for synthetic tri (propylene glycol) diacrylate monomer, gained monomeric ester content height reaches 95～99%; Secondly, product color is shallow, can reach (black Ceng Danwei) about 5～No. 10, and preparation monomer color is also shallow, reach 5～No. 20 (black Ceng Danwei), can-for high-grade light-coloured coating and printing ink.The inventive method technology is simple, and disadvantageous impurity is few, energy consumption is low, pollution-free.The inventive method and additive method products obtained therefrom have two important diagnostic characteristicses and difference: product is by the form and aspect stratographic analysis, and superpolymer is few; Of light color, next reactive behavior height, reaction time is short, and about 3 hours, the reaction times can shorten 1/3 at least, is that the technology of preparation tripropylene glycol is simple again, and energy consumption is low.
Embodiment
The preparation of reactor before implementing: with distilled water the 2.5L autoclave is washed several times earlier, till clean, dried reactor, standby after being cooled to 30～60 ℃.
Embodiment 1
In reactor, add 1,2 propylene glycol 500g, barium monohydrate 4.0g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration is warmed up to 85 ℃ after 1 hour and adds propylene oxide 573g, adds reaction after 2 hours, the cooling degassing.Add sulfuric acid 2.1g neutralization, filter discharging, make tripropylene glycol.Reaction pressure is-0.05Mpa.Gas chromatographic analysis: tripropylene glycol content 48.5%, four contracting five propylene glycol can not surveyed.No. 5, range estimation sample color and luster (black Ceng Danwei).
Embodiment 2
In reactor, add 1,2 propylene glycol 500g, barium hydroxide 12.0g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration is warmed up to 100 ℃ after 1 hour and continues to add propylene oxide 690g, and temperature of reaction adds reaction after 2 hours at 100～105 ℃, the cooling degassing.Add sulfuric acid 3.8g neutralization, filter discharging, make tripropylene glycol.Described reaction pressure is 0.45Mpa.Gas chromatographic analysis: tripropylene glycol content 58.6%, four contracting five content of propylene glycol 0.35%.No. 5, range estimation sample color and luster (black Ceng Danwei).
Embodiment 3
In reactor, add 1,2 propylene glycol 500g, barium monohydrate 10.0g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration is warmed up to 120 ℃ after 1 hour and continues to add propylene oxide 800g, and temperature of reaction adds reaction after 2 hours at 120～125 ℃, the cooling degassing.Add sulfuric acid 5.28g neutralization, filter discharging, make tripropylene glycol.Described reaction pressure is 0.1Mpa.Gas chromatographic analysis: tripropylene glycol content 64.5%, four contracting five content of propylene glycol 1.0%.No. 10, range estimation sample color and luster (black Ceng Danwei).
Embodiment 4
In reactor, add 1,2 propylene glycol 500g, triphenylphosphine 7.0g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration continued to add propylene oxide 800g after 1 hour, and temperature of reaction is at 85～90 ℃, add reaction 1h after, the cooling degassing.Cool to 60 ℃ of dischargings, make tripropylene glycol.Described reaction pressure is-0.01Mpa.Gas chromatographic analysis: tripropylene glycol content 65%, four contracting five content of propylene glycol 0.45%.No. 5, range estimation sample color and luster (black Ceng Danwei).
Embodiment 5
In reactor, add 1,2 propylene glycol 500g, triphenylphosphine 3.0g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration is warmed up to 130 ℃ after 1 hour and continues to add propylene oxide 600g, and temperature of reaction adds reaction after 1 hour at 130～135 ℃, the cooling degassing.Cool to 60 ℃ of dischargings, make tripropylene glycol.Described reaction pressure is 0.25Mpa.Gas chromatographic analysis: tripropylene glycol content 62.5%, four contracting five content of propylene glycol 0.3%.No. 5, range estimation sample color and luster (black Ceng Danwei).
Embodiment 6
In reactor, add 1,2 propylene glycol 500g, triphenylphosphine 0.5g, displacement N
2Heat up after three times, temperature to 85 a ℃ dehydration is warmed up to 140 ℃ after 1 hour and continues to add propylene oxide 570g, and temperature of reaction adds reaction after 1 hour at 135～140 ℃, the cooling degassing.Cool to 60 ℃ of dischargings, make tripropylene glycol.Described reaction pressure is-0.25Mpa.Gas chromatographic analysis: tripropylene glycol content 52.0%, four contracting five propylene glycol can not surveyed.No. 5, range estimation sample color and luster (black Ceng Danwei).
The prepared tripropylene glycol of the various embodiments described above after tested, specific targets are as follows:
| Embodiment | Two contracting thing content (%) | Four contracting thing content (%) | Color and luster (black Ceng Danwei) |
| 1 | 48.5 | 0 | 5 |
| 2 | 58.6 | 0.35 | 5 |
| 3 | 64.5 | 1.0 | 10 |
| 4 | 65 | 0.45 | 10 |
| 5 | 62.5 | 0.3 | 5 |
| 6 | 52.0 | 0 | 5 |
Claims (1)
1. the synthetic method of a tripropylene glycol, it is characterized in that: with commercially available 1, the 2-propylene glycol is raw material, under triphenylphosphine or hydrated barta catalyst action, again with propylene oxide as chain extension agent, reaction makes tripropylene glycol under certain temperature and pressure condition, and three's mol ratio is 1,2-propylene glycol: propylene oxide: catalyzer=1: 1.4: 0.02～2.2: 0.0005: 0.02; Its reaction equation is:
Described temperature of reaction is 80～140 ℃; Described reaction pressure is-0.05～0.45Mpa; Described hydrated barta catalyzer adopts barium monohydrate or many water hydrated barta; Described many water hydrated barta adopts barium hydroxide.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102295538A (en) * | 2011-08-25 | 2011-12-28 | 浙江皇马化工集团有限公司 | Synthesizing method of phenoxyl ethanol |
| CN102775280A (en) * | 2012-08-09 | 2012-11-14 | 铜陵金泰化工实业有限责任公司 | New method for preparing tripropylene glycol |
| CN106397134B (en) * | 2016-08-31 | 2018-11-27 | 浙江皇马科技股份有限公司 | A kind of preparation method of bis-hydroxypropyl neopentyl glycol ether |
| CN106397135B (en) * | 2016-08-31 | 2018-11-27 | 浙江皇马科技股份有限公司 | A kind of preparation method of hydroxypropylation pentaerythrite ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239917A (en) * | 1979-07-02 | 1980-12-16 | Conoco, Inc. | Barium oxide catalyzed ethoxylation |
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239917A (en) * | 1979-07-02 | 1980-12-16 | Conoco, Inc. | Barium oxide catalyzed ethoxylation |
| CN101250093A (en) * | 2008-03-22 | 2008-08-27 | 江苏三木集团 | Preparation method of tripropylene glycol |
Non-Patent Citations (4)
| Title |
|---|
| 三苯基膦及其应用;谭国华;《化工时刊》;19940315(第3期);全文 * |
| 乌云高娃等.有关合成丙二醇醚催化剂方面的进展.《西北纺织工学院学报》.1999,第13卷(第4期), |
| 有关合成丙二醇醚催化剂方面的进展;乌云高娃等;《西北纺织工学院学报》;19991230;第13卷(第4期);全文 * |
| 谭国华.三苯基膦及其应用.《化工时刊》.1994,(第3期), |
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