CN101906016B - Rubber seed oil polyalcohol and preparation method thereof - Google Patents
Rubber seed oil polyalcohol and preparation method thereof Download PDFInfo
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Abstract
The invention relates to rubber seed oil polyalcohol and a preparation method thereof. The method comprises the following steps of: mixing rubber seed oil, hydrogen peroxide and a catalyst serving as raw materials in a weight ratio of 1:0.5-1.5:0.01-0.05, putting the mixture into a reaction kettle, stirring the mixture and raising temperature to 50 to 80 DEG C, keeping reaction temperature for 3 to 8 hours, lowering the temperature to 30 DEG C, separating acid water out, washing the mixture with aqueous solution of sodium carbonate until the pH of the mixture is between 5 and 6, washing the mixture to be neutral with saturated sodium chloride and water, and performing pressure reduction and water removal at the temperature of between 50 and 90 DEG C for 2 to 5 hours to obtain epoxy rubberseed oil; and adding the epoxy rubber seed oil, methanol, isopropanol and fluoboric acid into the reaction kettle in a weight ratio of 1:1-5:1-5:0.002-0.01, raising the temperature to 75 to 100 DEG C, performing a reaction for 0.5 to 3 hours, washing the reaction product with the aqueous solution of the sodium carbonate until the pH of the reaction product is between 5 and 6, washing the reaction product to be neutral with water, and performing vacuum pumping at the temperature of between 50 and 120 DEG C for 2 to 5 hours to obtain the rubber seed oil polyalcohol. In the method, the conventional petroleum chemical is replaced by a non-edible plant oil resource, so that the dependence of polyurethane industry on petroleum chemicals is reduced, and the added value of the rubber seed oil is increased.
Description
Technical field
The present invention relates to vegetable oil polyol, specifically a kind of can be for the preparation of rubber seed oil polyalcohol of urethane and preparation method thereof.
Background technology
Along with the worsening shortages of petroleum resources and rising steadily of crude oil price, substituting petroleum resources with natural reproducible resource has become inexorable trend.Vegetables oil is cheap because of it, the characteristics such as plantation, environmental protection and resource recyclability that are easy to get more and more people's extensive concerning day by day, study it and replace petroleum products to come production oligomer polyol and application and development thereof, very important economic worth and scientific meaning are arranged.China's employing epoxy soybean oil and alcohols carry out the open loop addition at catalyst action and prepare the industrialization of soybean oil polyvalent alcohol, and the vegetable oil polyol research work of other kinds also is in the immature stage.
At present, the vegetables oil raw material of preparation polyvalent alcohol mainly contains soybean oil, Viscotrol C, rapeseed oil, peanut oil, plam oil, Oleum Gossypii semen, sweet oil, sunflower seeds wet goods.Major part belongs to edible oil, and it as the industrial chemicals utilization, is existed with the mankind and strive the grain problem.And rubber seed oil is one of important non-edible plant oil, with its raw material as the preparation polyvalent alcohol, not only can avoid the problems referred to above, also can widen the approach that utilizes of rubber seed oil, turns waste into wealth.
US6107433 has introduced use catalyzer fluoroboric acid epoxidized vegetable oil, prepare a kind of method of vegetable oil-based polyols again with alcohol generation hydroxylating under the fluoroboric acid catalytic condition, but prepared polyvalent alcohol hydroxyl value is less than 200mgKOH/g.CN101265157A has introduced a kind of employing catalyzer HZSM-5 or H
3[P (W
3O
10)
4] or SnCl
2Or LiB, epoxy soybean oil, solvent, methyl alcohol, water and catalyzer are reacted by a certain percentage, prepare the method for vegetable oil polyol, but reaction process need be carried out under high pressure.CN101386563A has introduced a kind of method for preparing vegetable oil-based polyols, specifically be that vegetables oil, carboxylic acid and catalyzer urea are mixed, drip aqueous hydrogen peroxide solution simultaneously, after adding, continue reaction for some time, make vegetable oil polyol, the vegetable oil polyol of this method gained can be used for preparing hard polyurethane foam, soft foam material and elastomerics etc.
Summary of the invention
The purpose of this invention is to provide rubber seed oil polyalcohol of a kind of preparation that can be used for urethane and preparation method thereof.
Technical scheme of the present invention is:
(1) in rubber seed oil: hydrogen peroxide: the catalyst weight ratio is that 1: 0.5～1.5: 0.01～0.05 ratio is mixed raw material and put into reactor, stirring is warming up to 50～80 ℃, kept temperature of reaction 3～8 hours, reaction finishes, and is cooled to 30 ℃, isolates sour water, earlier with aqueous sodium carbonate reaction product being washed till pH is 5-6, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 50～90 ℃ of temperature dewatered 2～5 hours, made epoxy rubber seed oil;
(2) set by step (1) epoxy rubber seed oil of making: methyl alcohol: Virahol: the fluoroboric acid weight ratio is that 1: 1～5: 1～5: 0.002～0.01 ratio is put into reactor, be warming up to 75～100 ℃, keep temperature of reaction after 0.5～3 hour, be that reaction product is washed till pH is 5-6 for 5% aqueous sodium carbonate with mass percent, wash with water again to neutrality, vacuumized 2～5 hours under 50～120 ℃ of temperature, make rubber seed oil polyalcohol.
The described catalyzer of step (1) is a kind of in the following catalyzer: heteropolyacid; Wolframic acid-organic acid catalyst, the two ratio are 1: 0.5～1.5; Peroxide phosphotungstic acid quaternary-base metal catalysts, the two ratio are 1: 1～3; Peroxide phospho-molybdic acid quaternary ammonium salt-base metal catalysts, the two ratio are 1: 1～3.
Described heteropolyacid is a kind of in wolframic acid, phospho-wolframic acid, the phospho-molybdic acid.
Organic acid is a kind of in sulfonic acid Whitfield's ointment, oxalic acid, the Whitfield's ointment in described wolframic acid-organic acid catalyst.
Basic metal in described peroxide phosphotungstic acid quaternary-base metal catalysts, the peroxide phospho-molybdic acid quaternary ammonium salt-base metal catalysts is a kind of in Sodium phosphate dibasic, the SODIUM PHOSPHATE, MONOBASIC.
The present invention has the following advantages compared with the prior art:
Replace traditional petroleum chemicals with natural reproducible, non-edible plant oil resource, can reduce polyurethane industrial to the dependence of petroleum chemicals, meet the Sustainable development requirement.Rubber seed oil for the preparation of the industrial chemicals polyvalent alcohol, can be improved the value added of rubber seed oil, and alleviate the pressure to the petrochemical industry resource.
Embodiment
The present invention is as follows to the testing method of prepared epoxy rubber seed oil ring oxygen value and rubber seed oil polyalcohol acid number and hydroxyl value:
(1) mensuration of oxirane value: press GB/T1677-2008 and survey oxirane value
(2) mensuration of acid number: press GB/T12008.5-89 and survey acid number
(3) mensuration of hydroxyl value: press GB/T12008.3-2009 and survey hydroxyl value
Embodiment 1
(1) be that (down with) hydrogen peroxide of 30%, 0.25g wolframic acid (or 20g rubber seed oil, 30g hydrogen peroxide, 1g phospho-molybdic acid or 20g rubber seed oil, 16g hydrogen peroxide, 0.4g phospho-wolframic acid) are put into reactor with 20g rubber seed oil, 5g mass percentage concentration, stirring is warming up to 50 ℃, kept temperature of reaction 5 hours, isolating sour water, is earlier (down together) NaCO of 5% with mass percentage concentration
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 90 ℃ of temperature dewatered 2 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 40g methyl alcohol, 40g Virahol and the 0.2g fluoroboric acid that step (1) are made are put into reactor, heat up 75 ℃, keep temperature of reaction 1 hour, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 2 hours under 70 ℃ of temperature, makes rubber seed oil polyalcohol.
Record:
The oxirane value of the epoxy rubber seed oil of wolframic acid catalytic preparation is 5.1%, and the hydroxyl value of rubber seed oil polyalcohol is 205mgKOH/g;
The oxirane value of the epoxy rubber seed oil of phospho-molybdic acid catalytic preparation is 5.3%, and the rubber seed oil polyalcohol hydroxyl value is 213mgKOH/g;
The oxirane value of the epoxy rubber seed oil of catalysis of phosphotungstic acid preparation is 5.7%, and the rubber seed oil polyalcohol hydroxyl value is 227mgKOH/g.
Embodiment 2
(1) the 20g rubber seed oil is put into reactor, stirring is warming up to 60 ℃, in rubber seed oil: hydrogen peroxide: the catalyst weight ratio is 1: 0.5: 0.03 ratio, be 10g hydrogen peroxide, 0.4g wolframic acid, 0.2g sulfonic acid Whitfield's ointment, drip hydrogen peroxide and mixture of catalysts by constant pressure funnel, in 2 hours, slowly dropwise, after dripping, kept temperature of reaction 4 hours, and separated and use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 50 ℃ of temperature dewatered 5 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 30g methyl alcohol, 60g Virahol and the 0.1g fluoroboric acid that step (1) are made are put into reactor, heat up 80 ℃, keep temperature of reaction 3 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 4 hours under 60 ℃ of temperature, makes rubber seed oil polyalcohol.
The oxirane value that records epoxy rubber seed oil is 7.0%, and the hydroxyl value of rubber seed oil polyalcohol is 232mgKOH/g.
Embodiment 3
(1) 20g rubber seed oil, 16g hydrogen peroxide, 0.2g wolframic acid, 0.3g Whitfield's ointment are put into reactor, stir and be warming up to 70 ℃, kept temperature of reaction 3 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 55 ℃ of temperature dewatered 5 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 60g methyl alcohol, 60g Virahol and the 0.14g phosphoric acid that step (1) are made are put into reactor, heat up 90 ℃, keep temperature of reaction 0.5 hour, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 5 hours under 50 ℃ of temperature, makes rubber seed oil polyalcohol.
The oxirane value that records epoxy rubber seed oil is 6.7%, and the hydroxyl value of rubber seed oil polyalcohol is 230mgKOH/g.
Embodiment 4
(1) the 20g rubber seed oil is put into reactor, stirring is warming up to 50 ℃, in rubber seed oil: hydrogen peroxide: the catalyst weight ratio is 1: 0.9: 0.04 ratio, be 18g hydrogen peroxide, 0.4g wolframic acid, 0.4g oxalic acid, drip hydrogen peroxide and mixture of catalysts by constant pressure funnel, in 2 hours, slowly dropwise, kept temperature of reaction 8 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 70 ℃ of temperature dewatered 3 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 50g methyl alcohol, 50g Virahol and the 0.2g fluoroboric acid that step (1) are made are put into reactor, heat up 80 ℃, keep temperature of reaction 2 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 3 hours under 70 ℃ of temperature, makes rubber seed oil polyalcohol.
The oxirane value that records epoxy rubber seed oil is 6.1%, and the hydroxyl value of rubber seed oil polyalcohol is 218mgKOH/g.
Embodiment 5
(1) 20g rubber seed oil, 14g hydrogen peroxide, 0.3g peroxide phosphotungstic acid quaternary, 0.3g Sodium phosphate dibasic are put into reactor, stir and be warming up to 50 ℃, kept temperature of reaction 3 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 85 ℃ of temperature dewatered 2.5 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 50g methyl alcohol, 50g Virahol and the 0.16g fluoroboric acid that step (1) are made are put into reactor, heat up 90 ℃, keep temperature of reaction 1 hour, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 5 hours under 55 ℃ of temperature, makes rubber seed oil polyalcohol.
The oxirane value that records epoxy rubber seed oil is 7.8%, and the hydroxyl value of rubber seed oil polyalcohol is 277mgKOH/g.
Embodiment 6
(1) 20g rubber seed oil, 24g hydrogen peroxide, 0.2g peroxide phospho-molybdic acid quaternary ammonium salt, 0.6g SODIUM PHOSPHATE, MONOBASIC are put into reactor, stir and be warming up to 80 ℃, kept temperature of reaction 3.5 hours, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 70 ℃ of temperature dewatered 4 hours, made epoxy rubber seed oil.
(2) the 20g epoxy rubber seed oil, 50g methyl alcohol, 50g Virahol and the 0.12g fluoroboric acid that step (1) are made are put into reactor, heat up 80 ℃, keep temperature of reaction 1 hour, isolate sour water, use NaCO earlier
3It is 5-6 that the aqueous solution is washed till pH with reaction product, washes with water to neutrality again, vacuumizes 5 hours under 70 ℃ of temperature, makes rubber seed oil polyalcohol.
The oxirane value that records epoxy rubber seed oil is 7.4%, and the hydroxyl value of rubber seed oil polyalcohol is 252mgKOH/g.
Claims (2)
1. the preparation method of a rubber seed oil polyalcohol is characterized in that carrying out according to the following steps:
(1) in rubber seed oil: hydrogen peroxide: the catalyst weight ratio is that 1: 0.5～1.5: 0.01～0.05 ratio is mixed raw material and put into reactor, stirring is warming up to 50～80 ℃, kept temperature of reaction 3～8 hours, reaction finishes, and is cooled to 30 ℃, isolates sour water, earlier with aqueous sodium carbonate reaction product being washed till pH is 5-6, again with saturated sodium-chloride, be washed to neutrality, reducing pressure under 50～90 ℃ of temperature dewatered 2～5 hours, made epoxy rubber seed oil;
(2) set by step (1) epoxy rubber seed oil of making: methyl alcohol: Virahol: the fluoroboric acid weight ratio is that 1: 1～5: 1～5: 0.002～0.01 ratio is put into reactor, be warming up to 75～100 ℃, keep temperature of reaction after 0.5～3 hour, with aqueous sodium carbonate reaction product being washed till pH is 5-6, wash with water again to neutrality, vacuumized 2～5 hours under 50～120 ℃ of temperature, make rubber seed oil polyalcohol;
The described catalyzer of step (1) is: heteropolyacid, and wolframic acid-organic acid catalyst, the two ratio is 1: 0.5～1.5; Heteropolyacid is a kind of in phospho-wolframic acid, the phospho-molybdic acid, and organic acid is a kind of in sulfonic acid Whitfield's ointment, oxalic acid, the Whitfield's ointment in wolframic acid-organic acid catalyst.
2. rubber seed oil polyalcohol by the preparation method of the described rubber seed oil polyalcohol of claim 1 preparation.
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| CN 201010215609 CN101906016B (en) | 2010-07-02 | 2010-07-02 | Rubber seed oil polyalcohol and preparation method thereof |
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| CN101906016B true CN101906016B (en) | 2013-08-21 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104003870B (en) * | 2014-06-11 | 2016-06-01 | 西南林业大学 | The preparation method of a kind of vegetable oil-based polyols |
| CN108624381B (en) * | 2018-06-07 | 2020-12-22 | 中国林业科学研究院林产化学工业研究所 | Water-based lubricant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107433A (en) * | 1998-11-06 | 2000-08-22 | Pittsburg State University | Process for the preparation of vegetable oil-based polyols and electroninsulating casting compounds created from vegetable oil-based polyols |
| CN101235021A (en) * | 2008-02-29 | 2008-08-06 | 江南大学 | Method for preparing epoxidized soybean oil or epoxy fatty acid methyl(ethyl) ester by heteropolyacid liquid phase catalysis |
| CN101265157A (en) * | 2008-04-29 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | Method for preparing vegetable oil polyhydric alcohol by using natural reproducible source |
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2010
- 2010-07-02 CN CN 201010215609 patent/CN101906016B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107433A (en) * | 1998-11-06 | 2000-08-22 | Pittsburg State University | Process for the preparation of vegetable oil-based polyols and electroninsulating casting compounds created from vegetable oil-based polyols |
| CN101235021A (en) * | 2008-02-29 | 2008-08-06 | 江南大学 | Method for preparing epoxidized soybean oil or epoxy fatty acid methyl(ethyl) ester by heteropolyacid liquid phase catalysis |
| CN101265157A (en) * | 2008-04-29 | 2008-09-17 | 中国科学院山西煤炭化学研究所 | Method for preparing vegetable oil polyhydric alcohol by using natural reproducible source |
Non-Patent Citations (2)
| Title |
|---|
| 植物油基多元醇的合成及其应用;潘梅娟等;《现代化工》;20071130;第27卷;521-524 * |
| 潘梅娟等.植物油基多元醇的合成及其应用.《现代化工》.2007,第27卷521-524. |
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