CN1721060A - Ultrafine oxide catalyst for preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester - Google Patents
Ultrafine oxide catalyst for preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester Download PDFInfo
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- CN1721060A CN1721060A CN 200510021147 CN200510021147A CN1721060A CN 1721060 A CN1721060 A CN 1721060A CN 200510021147 CN200510021147 CN 200510021147 CN 200510021147 A CN200510021147 A CN 200510021147A CN 1721060 A CN1721060 A CN 1721060A
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Abstract
The present invention relates to ultra-fine oxide accelerating agent for diphenylmethane bicarbomates to decompose and prepare diphenylmethane diisocyanate. The accelerating agent is ultra-fine oxide of metals or non-metal of IB, IIB, IIIA and IVA in periodic table of elements, or their composite ultra-fine oxide. It is simple to operate and can be used repeatedly, and both the conversion rate of raw material and productivity are high.
Description
Technical field:
The present invention is a kind of ultrafine oxide catalyst that diphenyl methane diamino formic ether (MDC) decomposes preparation '-diphenylmethane diisocyanate (MDI) that is used for, this ultrafine oxide catalyst is metal or nonmetallic superfine oxide and their the composite superfine oxide of IB, IIB, IIIA, IVA in the periodic table of elements, belongs to the applied catalysis field.
Technical background:
MDI is a kind of important source material for preparing polyurethane, by its polyurethane products of preparing at aspects such as elasticity, wearability, percentage elongations all than being the superior performance of the polyurethane products of raw material with other isocyanates, (Lee allows to be widely used in the manufacturing of micro-pore elastomer, thermoplastics type's elastomer, casting type elastomer, artificial leather, synthetic leather, adhesive, coating, sealant etc., MDI series of products and application thereof, polyurethane industrial, 1995,4:24～27).Present industrial production MDI still adopts phosgenation, be that aniline and formaldehyde condensation reaction are prepared diphenylmethane diamine earlier, and then and phosgene reaction, obtain thick MDI, rectification and purification obtains MDI series of products (Wang Yanji, Zhao Xinqiang, green catalysis process and technology, Chemical Industry Press, 2002:116～117).Along with the reinforcement of people's environmental consciousness, prepare phenyl urethan from nitrobenzene or aniline, obtain MDC with formolite reaction again, this product removes the focus that process for cleanly preparing that methyl alcohol generates MDI becomes research in the presence of catalyst.Employing zinc chloride such as Koichi is made catalyst in US4307029, carries out the MDI that the MDC decomposition reaction obtains 46.1%wt under the normal pressure.In US4294774, when N such as Thomas, accelerine made solvent and catalyst, the MDI yield was 46mol%.In US4349484, Harder etc. are that MDC is decomposed in the reactor pressurization with the quartz ampoule of filling the zinc bits, obtain the MDI of 76.5mol%.In US4547322, employing zinc such as Tomonari or aluminium Raschig ring are filler, and when carrying out MDC pressurization decomposition reaction in the vertical reaction tube of stainless steel, MDI accounts for the 89.2%wt of total isocyanates.More than have following shortcoming in the reaction: productive rate was higher when (1) adopted the tubular reactor compressive reaction, but pipeline stops up easily behind the long reaction; (2) productive rate that reacts in the tank reactor under the normal pressure is not high.
Summary of the invention:
The object of the present invention is achieved like this, and adopting the described superfine oxide of claims is catalyst, under nitrogen protection, carries out the heterogeneous catalysis decomposition reaction of MDC, preparation MDI.
Aforesaid ultrafine oxide catalyst is the superfine oxide of copper, zinc, aluminium, silicon and nickel of IB, IIB, IIIA, IVA in the periodic table of elements or the composite superfine oxide of wherein any two kinds of oxides; The superfine oxide of copper, zinc, aluminium, silicon, nickel is: zinc oxide, cupric oxide, aluminium oxide, silica, nickel oxide; The composite superfine oxide is mainly: zinc oxide-silica, its mol ratio are 1: 1～100; Zinc oxide-aluminium oxide, its mol ratio are 1: 1～100; Cupric oxide-aluminium oxide, its mol ratio are 1: 1～100; Cupric oxide-silica, its mol ratio are 1: 1～100.
The particle diameter distribution of aforesaid superfine oxide or superfine composite oxide catalyst is 50～500nm.
Aforesaid ultrafine oxide catalyst consumption is 0.01～10% of an atent solvent weight consumption.
Aforesaid atent solvent is dibutyl phthalate, repefral, dioctyl phthalate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate.
Technical solution of the present invention is as follows:
100ml four neck flasks are fixed on the SZCL type digital display intelligent temperature control magnetic stirring apparatus, are fixed with thermometer, temperature-control heat couple, nitrogen ingress pipe and condensation conversion tube on the four-necked bottle.Earlier MDC and catalyst and solvent are joined in the four neck flasks by a certain percentage, feed nitrogen after a period of time, be heated rapidly to reaction temperature and keep a period of time.After reaction finishes, standing demix, separating catalyst and reactant liquor.Then with the di-n-butylamine liquid processing reaction liquid of deriving, the solution of getting after the suitable processing carries out high performance liquid chromatography (HPLC) analysis.After with acetone catalyst being washed out, in 105 ℃ of oven dry down, recycling.
Compared with prior art, when adopting superfine oxide of the present invention to be used for the catalytic decomposition diphenyl methane diamino formic ether to prepare '-diphenylmethane diisocyanate, have simple to operate, ultrafine oxide catalyst separates easily with reactant liquor, reusable, feed stock conversion and the high advantage of purpose product productive rate.
Embodiments of the invention are as follows:
Embodiment 1:
In reactor, add 35 gram MDC and solvent repefrals; add zinc oxide-silica that particle diameter distribution is 50～100nm (the amount of substance ratio is 1: 1) simultaneously; addition is 0.5% of a weight of solvent; under nitrogen protection and stirring condition, reacting liquid temperature is raised to 240 ℃; 40min is carried out in reaction, and standing sedimentation makes catalyst separate with reactant liquor.Reactant liquor is analyzed with HPLC after di-n-butylamine is handled, and the conversion ratio of two MDC is 99.6%, and the productive rate of MDI is 63.1%.After reaction finished, separating catalyst with the acetone washing, was dried stand-by down for 100 ℃ then.
Embodiment 2:
In reactor, add 35 gram MDC and repefrals; add the catalyst that reclaim embodiment 1 reaction back simultaneously; addition is 0.5% of a weight of solvent; under nitrogen protection and stirring condition, reacting liquid temperature is raised to 240 ℃; 40min is carried out in reaction, and standing sedimentation makes catalyst separate with reactant liquor.Reactant liquor is analyzed with HPLC after di-n-butylamine is handled, and the conversion ratio of MDC is 98.8%, and the productive rate of MDI is 61.2%.After reaction finished, separating catalyst with the acetone washing, was dried stand-by down for 100 ℃ then.
Embodiment 3:
In reactor, add 60 gram MDC and solvent repefrals; add the cupric oxide that particle diameter distribution is 150～200nm simultaneously; addition is 3.0% of an atent solvent weight; under nitrogen protection and stirring condition, reactant liquor is warmed up to 250 ℃; 30min is carried out in reaction, and standing sedimentation makes catalyst separate with reactant liquor.Reactant liquor is analyzed with HPLC after di-n-butylamine is handled, and the conversion ratio of MDC is 97.1%, and the productive rate of MDI is 52.5%.After reaction finished, separating catalyst with the acetone washing, was dried stand-by down for 100 ℃ then.
Embodiment 4:
In reactor, add 45 gram MDC and solvent repefrals; add the silica that particle diameter distribution is 100～150nm simultaneously; addition is 2.2% of a weight of solvent; under nitrogen protection and stirring condition, reactant liquor is warmed up to 260 ℃; 20min is carried out in reaction, and standing sedimentation makes catalyst separate with reactant liquor.Reactant liquor is analyzed with HPLC after di-n-butylamine is handled, and the conversion ratio of MDC is 99.1%, and the productive rate of MDI is 52.1%.After reaction finished, separating catalyst with the acetone washing, was dried stand-by down for 100 ℃ then.
Embodiment 5:
In reactor, add 30 gram MDC and solvent repefrals; add the zinc oxide that particle diameter distribution is 250～300nm simultaneously; addition is 0.5% of a weight of solvent; under nitrogen protection and stirring condition, reactant liquor is warmed up to 280 ℃; 40min is carried out in reaction, and standing sedimentation makes catalyst separate with reactant liquor.Reactant liquor is analyzed with HPLC after di-n-butylamine is handled, and the conversion ratio of MDC is 99.5%, and the productive rate of MDI is 57.0%.After reaction finished, separating catalyst with the acetone washing, was dried stand-by down for 100 ℃ then.
Claims (4)
1. ultrafine oxide catalyst that is used for preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester, it is characterized in that: described superfine oxide is copper, zinc, aluminium, silicon, the superfine oxide of nickel or the composite superfine oxide of wherein any two kinds of oxides of IB, IIB, IIIA, IVA in the periodic table of elements; The superfine oxide of copper, zinc, aluminium, silicon, nickel is: zinc oxide, cupric oxide, aluminium oxide, silica, nickel oxide; The composite superfine oxide is mainly: zinc oxide-silica, its mol ratio are 1: 1～100; Zinc oxide-aluminium oxide, its mol ratio are 1: 1～100; Cupric oxide-aluminium oxide, its mol ratio are 1: 1～100; Cupric oxide-silica, its mol ratio are 1: 1～100.
2. according to right 1 described a kind of composite superfine oxide catalyst that is used for the superfine oxide of preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester or wherein any two kinds of oxides, it is characterized in that: the particle diameter distribution of this superfine oxide is 50～500nm, and the particle diameter distribution of composite superfine oxide is 50～500nm.
3. the diphenyl methane diamino formic ether catalytic decomposition prepares '-diphenylmethane diisocyanate and is characterised in that: with described superfine oxide of claim 1 or superfine composite oxide is catalyst, catalyst amount is 0.01～10% of an atent solvent quality, reaction temperature is 150～300 ℃, and the atent solvent consumption is 10～100 times of diphenyl methane diamino formic ether quality.
4. according to right 3 described atent solvents, it is characterized in that: atent solvent is dibutyl phthalate, repefral, dioctyl phthalate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510021147 CN1721060A (en) | 2005-06-23 | 2005-06-23 | Ultrafine oxide catalyst for preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester |
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| CN 200510021147 CN1721060A (en) | 2005-06-23 | 2005-06-23 | Ultrafine oxide catalyst for preparing diphenylmethane diisocyanates by decomposition of diphenylmethane dicarbamic acid ester |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772240A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparation of methylene diphenyl diisocyanate (MDI) |
| JP2016196498A (en) * | 2011-07-13 | 2016-11-24 | 宇部興産株式会社 | Method for producing isocyanate compound |
| CN110423208A (en) * | 2019-08-15 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method of '-diphenylmethane diisocyanate |
| CN112574067A (en) * | 2021-02-24 | 2021-03-30 | 富海(东营)新材料科技有限公司 | Method for preparing high-purity m-xylylene diisocyanate without phosgene |
| CN113413922A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院成都有机化学有限公司 | Heterogeneous catalyst for hydrogen production by formic acid liquid phase decomposition and preparation method thereof |
-
2005
- 2005-06-23 CN CN 200510021147 patent/CN1721060A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016196498A (en) * | 2011-07-13 | 2016-11-24 | 宇部興産株式会社 | Method for producing isocyanate compound |
| CN103772240A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparation of methylene diphenyl diisocyanate (MDI) |
| CN103772240B (en) * | 2012-10-24 | 2015-05-13 | 中国石油化工股份有限公司 | Method for preparation of methylene diphenyl diisocyanate (MDI) |
| CN110423208A (en) * | 2019-08-15 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method of '-diphenylmethane diisocyanate |
| CN112574067A (en) * | 2021-02-24 | 2021-03-30 | 富海(东营)新材料科技有限公司 | Method for preparing high-purity m-xylylene diisocyanate without phosgene |
| CN113413922A (en) * | 2021-07-19 | 2021-09-21 | 中国科学院成都有机化学有限公司 | Heterogeneous catalyst for hydrogen production by formic acid liquid phase decomposition and preparation method thereof |
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