CN1408694A - Process for synthesizing tripentaerythritol - Google Patents
Process for synthesizing tripentaerythritol Download PDFInfo
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- CN1408694A CN1408694A CN 02136871 CN02136871A CN1408694A CN 1408694 A CN1408694 A CN 1408694A CN 02136871 CN02136871 CN 02136871 CN 02136871 A CN02136871 A CN 02136871A CN 1408694 A CN1408694 A CN 1408694A
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- acetaldehyde
- reaction
- formaldehyde
- tripentaerythritol
- tetramethylolmethane
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Abstract
The synthesizing process of tripentaerythritol is one to drop the mixed solution of acetaldehyde and formaldehyde into the mixture of water, pentaerythritol and/or bipentaerythritol and solid catalyst to perform synthesis reaction. The solid catalyst is one of magnesia, calcium hydroxide, barium hydroxide, RE modified MgO or Al2O3, alkali metal hydroxide or alkali earth metal hydroxide modified MgO or Al2O3. The said process has the features of high tripentaerythritol yield, cheap reactant material, lower reaction temperature and lower power consumption. The solid alkali catalyst may be reused and the process may be performed directly in traditional pentaerythritol producing equipment and has excellent industrial application foreground.
Description
Technical field
The present invention relates to the synthetic method of tripentaerythritol, relating in particular to formaldehyde, acetaldehyde, tetramethylolmethane or dipentaerythritol is raw material, under the effect of solid alkali, and preparation tripentaerythritol method.
Background technology
The purposes of tripentaerythritol increases day by day, and at rosin ester, stabiliser materials, there is important use in fields such as the softening agent of fire retardant material coating, senior lubricant, binder coating, textiles, refrigeration agent, dispersion agent.At present, be not specifically designed to the preparation method of tripentaerythritol, relate to the technology that produces tripentaerythritol and mainly contain following a few class:
(1) to have proposed with the tetramethylolmethane be raw material for patent Jp07165651, Jp07165653, Jp0776541, Jp07258139, Jp188086 and Jp07157450, handle through carboxamide/carbonic ether, under the effect of alkalescence or an acidic catalyst, prepare the method for dipentaerythritol.Contain a spot of tripentaerythritol in the product.
(2) patent USP2462047, EP0462283, Jp04145040 and Jp0616585 have disclosed tetramethylolmethane under the condition that solvent exists, or under the molten state, make catalyzer with strong acid, the method for synthetic dipentaerythritol.Contain a spot of tripentaerythritol in the product.
(3) patent Jp07165652 discloses tetramethylolmethane and 3, and 3-two (methylol) oxa-fourth ring (3,3-bis (hydroxymethyl) oxetane) generates the technology of tripentaerythritol under the katalysis of acid.Contain a spot of tripentaerythritol in the product.
(4) patent Jp09301908, Jp09301909 have proposed to be raw material, under the effect of alkali, to prepare the technology of dipentaerythritol that wherein the synthetic yield of tripentaerythritol is 18.5% with formaldehyde, acetaldehyde, tetramethylolmethane.
The main products of aforesaid method is tetramethylolmethane and dipentaerythritol, tripentaerythritol only is a byproduct, the method reaction conditions that patent Jp07165652 proposed is especially harsh, consumption of organic solvent is big, and be mainly tetramethylolmethane and dipentaerythritol in the product, the efficiency of pcr product of tripentaerythritol is low, only is byproduct.
Summary of the invention
The technical issues that need to address of the present invention are the synthetic methods that disclose a kind of tripentaerythritol, the present invention is a raw material with formaldehyde, acetaldehyde, dipentaerythritol or tetramethylolmethane, under the effect of solid catalyst, carry out the synthetic of tripentaerythritol, its synthesis yield is the highest brings up to 39%, overcoming a large amount of organic solvent and the lower defectives of synthesis yield of severe reaction conditions, needs that prior art exists, and avoided the environmental pollution of using sodium hydroxide liquid to cause.
Technical scheme of the present invention:
The synthetic method of the said tripentaerythritol of the present invention comprises the steps:
(1) mixing solutions with acetaldehyde and formaldehyde adopts the mode that drips to add in the mixture of entry, tetramethylolmethane and/or dipentaerythritol and solid catalyst, carry out the building-up reactions of tripentaerythritol, temperature of reaction is 10～80 ℃, and the reaction times is 1～15 hour.Its reaction formula is as follows:
When temperature of reaction was higher than 80 ℃, the by product that the reaction of acetaldehyde self-polymerization generates increased, and energy consumption increases; With the concentration difference of material, acetaldehyde transforms required time fully and also changes thereupon.
(2) after the first step reaction finishes, reaction mixture is taken out, add acetaldehyde, formalin remaining in the heat extraction reaction solution, under the hydrogenation catalyst effect, carry out the hydrogenation reduction of aldehyde radical, said hydrogenation catalyst is 2～5wt% gac for Pt content, reacts 1～3 hour.
(3) after reaction finishes, adopt conventional method, from reaction product, collect tripentaerythritol as evaporative crystallization etc.
Said solid base catalyst comprises magnesium oxide, calcium hydroxide, hydrated barta, rare-earth element modified MgO or Al
2O
3, alkali-metal oxyhydroxide or alkaline-earth metal the MgO or the Al of oxyhydroxide modification
2O
3In a kind of.Wherein: the oxyhydroxide of rare earth element, alkali-metal oxyhydroxide or alkaline-earth metal and MgO, Al
2O
3Ratio be 0.5wt%～50wt%.The rare earth element of being addressed comprises praseodymium, lanthanum or cerium.
By in the optimized technical scheme of the present invention, the mol ratio of catalyzer and acetaldehyde is 0.5～10.Be lower than 0.5 o'clock speed of response, long reaction time, the by product that is higher than reaction in 10 o'clock increases.
In the optimized technical scheme of the present invention, in order to improve the yield in three seasons, can in water and mixture of catalysts, add tetramethylolmethane, dipentaerythritol, the dipentaerythritol of adding and the mol ratio of acetaldehyde are controlled between 0.5: 1～2: 1, and the tetramethylolmethane of interpolation and the mol ratio of acetaldehyde are controlled between 0.5～4;
In the preferred scheme of the present invention, the time that drips the mixing solutions of acetaldehyde and formaldehyde in the Xiang Shui and the mixture in two seasons (single cropping) is controlled at the 1/4-1/2 of total reaction time, and is unsuitable too fast, otherwise the by product that the acetaldehyde self-polymerization produces increases.The long reaction of dropping time not exclusively.Lower formaldehyde instantaneous concentration in the maintenance system, dropping can be that continous way also can be a pulsed;
Used formaldehyde is 27～37% the aqueous solution, or the miscellany of polyoxymethylene and water, acetaldehyde is the aqueous solution of 10-60%, dipentaerythritol is other commodity of technical grade, or the thick product of the dipentaerythritol that recycles, or the synthetic product solution after the separation dipentaerythritol;
Under above-mentioned processing condition, the selectivity height of tripentaerythritol, its synthetic yield can reach more than 30%.The tetramethylolmethane yield can be controlled between the 25-75%.The dipentaerythritol yield can be controlled between the 10-25%.Can carry out the control of product yield according to the requirement in market.
The raw material of this technology is cheap, the temperature of reaction less energy-consumption is little, adopt the feeding mode of new formaldehyde by (1): promptly a part of formaldehyde or whole formaldehyde adopt the mode that drips, the solid catalyst that (2) use rare earth element is modified and the MgO and the Al of solid alkali metal or alkaline earth metal hydroxides modification
2O
3Catalyst series; (3) add monopentaerythritol or dipentaerythritol; (4) adopt the two-part reaction to make the yield of tripentaerythritol far above 18% level of similar technology.
This technology solid alkali as a catalyst can recycle, and has eliminated the effect of liquid base sodium hydroxide, can directly carry out on traditional tetramethylolmethane production equipment, has excellent industrial application foreground.
Embodiment
Embodiment 1
In stainless steel cauldron, add MgO7.9g, tetramethylolmethane 11g and water 22g, place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The reaction solution A dropping time is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.After total overall reaction finishes, obtain tripentaerythritol with the crystallization process separation.The yield of reaction product is analyzed resulting solution with liquid phase chromatography.For benchmark calculates the yield of each material, the results are shown in Table 1 with two seasons of acetaldehyde and conversion or the mole number of single cropping (the two seasons conversions of a part are 2 molecules of acetaldehyde, and the conversion of a part single cropping is 1 molecules of acetaldehyde).
Embodiment 2
In stainless steel cauldron, add MgO3.6g, dipentaerythritol 5.5g and water 22g, place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 60min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1
Embodiment 3
Add MgO 3.6g in stainless steel cauldron, tetramethylolmethane 11g and water 22g place 60 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Embodiment 4
Add 10% CeO2/MgO2g in stainless steel cauldron, tetramethylolmethane 11g and water 22g place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Embodiment 5
Add 20% CeO2/MgO2g in stainless steel cauldron, tetramethylolmethane 11g and water 22g place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Embodiment 6
Add 20% SrO/MgO2g in stainless steel cauldron, tetramethylolmethane 11g and water 22g place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Embodiment 7
Add MgO1.2 in stainless steel cauldron, dipentaerythritol 5.5g and water 22g place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 30min.Dropwise the back and continue reaction 90min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Embodiment 8
In stainless steel cauldron, add La
2O
3/ Al
2O
32g, tetramethylolmethane 11g and water 22g place 40 ℃ water-bath; Acetaldehyde solution 15ml with 20% and 37% formalin 27ml are evenly mixed, constitute reaction solution A; Under whipped state, use micro-ram pump, continuous dropwise reaction liquid A in reactor; The dropping time of reaction solution A is 60min.Dropwise the back and continue reaction 60min.After reaction finishes, carry out the hydrogenation reduction of aldehyde radical, atmospheric hydrogenation is two hours under hydrogenation catalyst 3%Pt/C effect.The results are shown in Table 1.
Table 1
| Yield (%) | |||
| Tetramethylolmethane | Dipentaerythritol | Tripentaerythritol | |
| Example 1 | ??27.09 | ??12.36 | ??24.30 |
| Example 2 | ??57.99 | ??4.58 | ??7.86 |
| Example 3 | ??46.22 | ??24.43 | ??29.00 |
| Example 4 | ??59.22 | ??11.51 | ??29.59 |
| Example 5 | ??42.21 | ??11.43 | ??36.01 |
| Example 6 | ??43.76 | ??12.87 | ??39.44 |
| Example 7 | ??75.30 | ??3.89 | ??3.80 |
| Example 8 | ??50.36 | ??13.47 | ??20.87 |
Claims (12)
1. the synthetic method of a tripentaerythritol, it is characterized in that comprising the steps: that the mixing solutions with acetaldehyde and formaldehyde adopts the mode that drips to add entry, tetramethylolmethane or/and react in the mixture of dipentaerythritol and solid base catalyst, after reaction finishes, hydrogenation reaction is 1～3 hour under the hydrogenation catalyst effect, and said hydrogenation catalyst is 2～5wt% gac for Pt content.
2. require described method according to right 1, it is characterized in that, said solid base catalyst comprises magnesium oxide, calcium hydroxide, hydrated barta, rare-earth element modified MgO or Al
2O
3, alkali-metal oxyhydroxide or alkaline-earth metal the MgO or the Al of oxyhydroxide modification
2O
3In a kind of.
3. method according to claim 2 is characterized in that, the oxyhydroxide of rare earth element, alkali-metal oxyhydroxide or alkaline-earth metal and MgO, Al
2O
3Ratio be 0.5wt%～50wt%.
4. method according to claim 3 is characterized in that rare earth element comprises lanthanum, cerium or praseodymium.
5. method according to claim 1 is characterized in that, the mol ratio of solid base catalyst and acetaldehyde is 0.5～10.
6. method according to claim 1 is characterized in that, adds tetramethylolmethane or dipentaerythritol in the mixture of water and solid base catalyst.
7. method according to claim 6 is characterized in that, the tetramethylolmethane of interpolation and the mol ratio of acetaldehyde are 0.5: 1～3: 1, and the dipentaerythritol of interpolation and the mol ratio of acetaldehyde are 0.5: 1～1.5: 1.
8. method according to claim 1 is characterized in that, the dropping time that drips the mixing solutions of acetaldehyde and formaldehyde in the mixture of water and solid base catalyst is controlled at the 1/4-2/3 of total reaction time.
9. according to each described method of claim 1～8, it is characterized in that, drip into continous way or for pulsed.
10. method according to claim 1 is characterized in that the weight ratio between water and the solid base catalyst is: 10～0.1.
11. method according to claim 1 is characterized in that, the mol ratio of formaldehyde and acetaldehyde is 3.5～7.0: 1, and acetaldehyde is mixed with 1/3～1 of formaldehyde total amount earlier, and residual formaldehyde adds in reaction process.
12. method according to claim 1 is characterized in that, temperature of reaction is 10～80 ℃, and the reaction times is 1～15 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021368716A CN100398504C (en) | 2002-09-06 | 2002-09-06 | Process for synthesizing tripentaerythritol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021368716A CN100398504C (en) | 2002-09-06 | 2002-09-06 | Process for synthesizing tripentaerythritol |
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| Publication Number | Publication Date |
|---|---|
| CN1408694A true CN1408694A (en) | 2003-04-09 |
| CN100398504C CN100398504C (en) | 2008-07-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603795A (en) * | 2018-12-13 | 2019-04-12 | 万华化学集团股份有限公司 | Solid base catalyst and the production technology for preparing 4- (2- furyl)-3- butene-2 -one |
| CN113845403A (en) * | 2021-11-30 | 2021-12-28 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propylene glycol and pentaerythritol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3791959B2 (en) * | 1996-05-08 | 2006-06-28 | 三井化学株式会社 | Method for producing dipentaerythritol |
| JP3791960B2 (en) * | 1996-05-14 | 2006-06-28 | 三井化学株式会社 | Method for producing dipentaerythritol |
-
2002
- 2002-09-06 CN CNB021368716A patent/CN100398504C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603795A (en) * | 2018-12-13 | 2019-04-12 | 万华化学集团股份有限公司 | Solid base catalyst and the production technology for preparing 4- (2- furyl)-3- butene-2 -one |
| CN109603795B (en) * | 2018-12-13 | 2022-01-07 | 万华化学集团股份有限公司 | Solid base catalyst and production process for preparing 4- (2-furyl) -3-butylene-2-ketone |
| CN113845403A (en) * | 2021-11-30 | 2021-12-28 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propylene glycol and pentaerythritol |
| CN113845403B (en) * | 2021-11-30 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation method for co-production of 2-methyl-1, 3-propanediol and pentaerythritol |
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| Publication number | Publication date |
|---|---|
| CN100398504C (en) | 2008-07-02 |
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|---|---|---|---|
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jiangsu Ruiyang Chemical Co., Ltd. Assignor: East China University of Science and Technology Contract fulfillment period: 2008.12.8 to 2013.12.7 contract change Contract record no.: 2009320000310 Denomination of invention: Process for synthesizing tripentaerythritol Granted publication date: 20080702 License type: Exclusive license Record date: 2009.3.10 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.12.8 TO 2013.12.7; CHANGE OF CONTRACT Name of requester: JIANGSU RUIYANG CHEMICAL INDUSTRY CO., LTD. Effective date: 20090310 |
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Granted publication date: 20080702 Termination date: 20120906 |