WO2009154144A1 - Procédé de production de polyamine aromatique - Google Patents

Procédé de production de polyamine aromatique Download PDF

Info

Publication number
WO2009154144A1
WO2009154144A1 PCT/JP2009/060752 JP2009060752W WO2009154144A1 WO 2009154144 A1 WO2009154144 A1 WO 2009154144A1 JP 2009060752 W JP2009060752 W JP 2009060752W WO 2009154144 A1 WO2009154144 A1 WO 2009154144A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
group
ionic liquid
general formula
containing ionic
Prior art date
Application number
PCT/JP2009/060752
Other languages
English (en)
Japanese (ja)
Inventor
隆洋 増田
Original Assignee
日本ポリウレタン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ポリウレタン工業株式会社 filed Critical 日本ポリウレタン工業株式会社
Publication of WO2009154144A1 publication Critical patent/WO2009154144A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton

Definitions

  • the present invention relates to a method for producing an aromatic polyamine.
  • methylene dianiline (MDA) and higher analogs thereof are precursors of methylene diphenyl diisocyanate (MDI) and higher analogs (polymeric MDI, etc.) that are raw materials for plastic production.
  • MDI and its higher analogues are industrially produced in large quantities and are used for the production of polyurethanes.
  • MDI is commonly used in non-foaming applications such as spandex and paints, and mixtures of MDI and its higher analogs are used in foaming applications such as flexible and rigid foams.
  • MDA and its higher analogs are generally produced from aniline and formaldehyde in the presence of a catalyst.
  • hydrochloric acid is used as a catalyst.
  • the neutralization treatment is performed, for example, by a method of adding an equimolar amount or more of base to hydrochloric acid.
  • base inexpensive sodium hydroxide is usually used.
  • a large amount of sodium chloride is generated after neutralization. Therefore, from the viewpoint of protecting the global environment and effectively utilizing energy resources, development of a production method that does not require neutralization of acid after the reaction is desired.
  • Patent Documents 1 to 7 As a method for producing MDA having no acid to be neutralized after the reaction and higher analogs thereof, for example, methods using a solid acid as a catalyst instead of hydrochloric acid have been proposed (Patent Documents 1 to 7 and Non-Patent Documents) 1).
  • the method using a solid acid as described above has various problems in industrial implementation, such as low reactivity and difficulty in sustaining catalytic activity.
  • an object of the present invention is to provide a method for producing an aromatic polyamine which is easy to implement industrially and does not require an acid neutralization treatment.
  • the following general formula (II) is obtained by reacting an aldehyde compound selected from formaldehyde and paraformaldehyde with an amine represented by the following general formula (I) (hereinafter sometimes referred to as “polyamination reaction”). And a production method using an acidic group-containing ionic liquid as a catalyst or a solvent for the above reaction.
  • a 1 represents an organic group or a hydrogen atom
  • a 2 represents an organic group, a hydroxy group, an amino group, a halogen atom or a hydrogen atom
  • q represents a number from 0 to 5.
  • the acidic group-containing ionic liquid functions as an acid catalyst for reacting the aldehyde compound and the amine represented by the general formula (I) by the action of the acidic group, and also functions as a reaction solvent.
  • the acidic group-containing ionic liquid is easy to recycle in the system and does not necessarily require an acid neutralization treatment, which is advantageous in terms of protecting the global environment and effectively using energy resources. Furthermore, the reactivity is high, the reactivity is hardly lowered, and the industrial implementation is easy.
  • the reactivity can be improved as compared with a method using an ion exchange resin having a sulfonic acid group in the molecule as a solid acid. Furthermore, the problem of a decrease in the heat resistance of the resin that occurs when the ion exchange resin is used is unlikely to occur. Compared with the method using zeolite or organic silicate having a protonic acid in the molecule and pores suitable for promoting the reaction as a solid acid, the catalytic activity caused by the amount of moisture and impurities in the reaction raw material Since it is difficult for the decrease to occur, it is not necessary to strictly limit the raw material composition, and it is easy to implement industrially.
  • the acidic group-containing ionic liquid is a zwitterionic reaction product of a polar compound selected from a compound having a trivalent phosphino group and an imidazole compound and a sultone compound selected from 1,3-propane sultone and 1,4-butane sultone.
  • a compound obtained by reacting an ionic compound and an organic sulfonic acid is preferable.
  • Suitable acidic group-containing ionic liquids include compounds represented by the following general formula (1).
  • R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
  • R 5 represents an organic group having 1 or more carbon atoms, and m represents 3 or 4.
  • the acidic group-containing ionic liquid is preferably a compound represented by the following general formula (2).
  • R 6 , R 7 , R 8 and R 9 each independently represents an organic group having 1 or more carbon atoms.
  • n represents 3 or 4.
  • the acidic group-containing ionic liquid represented by the formula (1) or (2) has a high catalytic action and is advantageous for industrial use. Also, it is advantageous in terms of easy synthesis of the acidic group-containing ionic liquid itself.
  • the polyamination reaction is carried out in the presence of the aldehyde compound, the amine represented by the general formula (I) and the acidic group-containing ionic liquid, or the aldehyde compound and the general formula (I)
  • the reaction can be carried out in the coexistence of the amine reaction product and the acidic group-containing ionic liquid.
  • the acidic group-containing ionic liquid functions as a catalyst or a solvent, and a desired aromatic polyamine can be obtained.
  • a hydrophobic organic solvent to the reaction product obtained by this reaction after the polyamination reaction.
  • the acidic group-containing ionic liquid hardly dissolves in the hydrophobic organic solvent, and the aromatic polyamine as the reaction product is hydrophobic. Since it dissolves in the organic solvent side, the acidic group-containing ionic liquid and the aromatic polyamine can be easily separated. In addition, the acidic group-containing ionic liquid thus separated can be recycled and reused.
  • the acidic group-containing ionic liquid is recovered, and the recovered liquid is used as a catalyst for the reaction of the amine represented by the aldehyde compound and the general formula (I) or It can be used as at least part of the solvent.
  • recycling the acidic group-containing ionic liquid is effective in terms of protecting the global environment and effectively using energy resources.
  • the production method of the present invention is a method for producing an aromatic polyamine represented by the following general formula (II) by reacting an aldehyde compound selected from formaldehyde and paraformaldehyde with an amine represented by the following general formula (I): This is a production method using an acidic group-containing ionic liquid as a reaction catalyst or solvent.
  • a 1 represents an organic group or a hydrogen atom
  • a 2 represents an organic group, a hydroxy group, an amino group, a halogen atom or a hydrogen atom
  • the organic group A 1 include an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms, Includes an alkenyl group having 1 to 3 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, and the like.
  • Examples of the organic group as A 2 include an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms); an aryl group having 6 to 12 carbon atoms; Aralkyl group; alkoxy groups such as methoxy group and ethoxy group are exemplified.
  • the halogen atom is A 2, a chlorine atom, a bromine atom or a fluorine atom can be exemplified.
  • a 1 is a hydrogen atom
  • a 2 is a hydrogen atom, a methyl group, and preferably a chlorine atom.
  • Particularly preferred as the compound represented by the formula (I) is aniline.
  • formula (II) the definitions of A 1 and A 2 are as defined above, and q represents a number from 0 to 5. q is preferably 0 to 4, more preferably 0 to 3.
  • preferred A 1 and A 2 are the same as described above. Since aniline is preferred as the compound represented by formula (I), methylene dianiline is preferred as the compound represented by formula (II).
  • aromatic polyamine represented by the formula (II) examples include an aromatic polyamine represented by the following formula (IIa).
  • formula (IIa) the definitions and preferred examples of A 1 , A 2 and q are as defined above.
  • the polyamine reaction is carried out by a formalin method or an aminal method.
  • the formalin method is a method in which an aldehyde compound (formaldehyde or paraformaldehyde), an amine represented by the general formula (I) and an acidic group-containing ionic liquid coexist, and the aminal method is an aldehyde compound ( Formaldehyde or paraformaldehyde), a reaction product of an amine represented by the general formula (I), and an acidic group-containing ionic liquid.
  • the reaction temperature is preferably 60 to 120 ° C. (preferably 65 to 115 ° C., more preferably 70 to 110 ° C.).
  • heat treatment is performed at a temperature lower than 60 ° C., it takes time to complete the rearrangement reaction, and the productivity tends to decrease.
  • productivity is not necessarily increased even if heat treatment is performed at a temperature higher than 120 ° C.
  • the reaction is carried out in the range from normal pressure to a pressure corresponding to the individual vapor pressure of the reaction mixture at the reaction temperature. Since the reaction proceeds sufficiently rapidly within the above pressure range, productivity does not necessarily increase even when the pressure is increased beyond this range.
  • Examples of a method for performing a polyamination reaction by causing an aminal formed from an aldehyde compound and an amine represented by the general formula (I) to coexist with an acidic group-containing ionic liquid include the following methods.
  • the amine represented by the general formula (I) is mixed with the aldehyde compound (formaldehyde or paraformaldehyde) at a molar ratio of 2 times or more, preferably about 3 to 6 times, and condensed at 0 to 40 ° C.
  • the reaction product obtained by the condensation is separated into an aqueous phase and an organic phase.
  • the organic phase is made to coexist with an acidic group containing ionic liquid, the reaction material obtained by condensation is isomerized, and the aromatic polyamine represented by general formula (II) is obtained.
  • the amount of water contained in the organic phase is low, but usually the organic phase obtained by the above operation can be used as it is.
  • the temperature for isomerization is preferably 60 to 120 ° C. (preferably 80 to 115 ° C., more preferably 90 to 110 ° C.).
  • the reaction is carried out in the range from normal pressure to a pressure corresponding to the individual vapor pressure of the reaction mixture at the reaction temperature. Since the reaction proceeds sufficiently rapidly within the above pressure range, productivity does not necessarily increase even when the pressure is increased beyond this range.
  • the acidic group-containing ionic liquid is an ionic liquid having an acidic group in the molecule, and functions as an acid catalyst in the reaction between the aldehyde compound and the amine represented by the general formula (I).
  • the acidic group-containing ionic liquid can be used without particular limitation as long as it is liquid at the time of reaction, but is preferably one having strong acidity, for example, pH 3 or less.
  • the acidic group is not particularly limited as long as it imparts acidity to the acidic group-containing ionic liquid, but from the viewpoint of the strength of acidity, a sulfonic acid group and a carboxylic acid group are preferable.
  • the acidic group-containing ionic liquid can be synthesized by a known method. For example, an N-substituted imidazole compound or triphenylphosphine and 1,3-propane sultone described in “J. Am. Chem., 124, 5962 (2002)” are reacted, and then trifluoromethanesulfonic acid or paratoluenesulfone is reacted. It can also be obtained by a method of reacting an acid or the like.
  • the acidic group-containing ionic liquid is a compound having a trivalent phosphino group or an imidazole compound and 1,3-propane sultone or 1 , 4-butane sultone is preferably a compound obtained by reacting a zwitterionic compound obtained by reaction with organic sulfonic acid.
  • imidazole compound examples include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-isobutylimidazole, 1-phenylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole. 1-ethyl-2-methylimidazole, 1,2,4-trimethylimidazole, 1-ethyl-2,4-dimethylimidazole and 1,2,4,5-tetramethylimidazole.
  • Examples of the compound having a trivalent phosphino group include triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tris (2-methylphenyl) phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, propyldiphenylphosphine. And butyldiphenylphosphine.
  • organic sulfonic acid examples include trifluoromethanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and 10-camphorsulfonic acid.
  • the acidic group-containing ionic liquid is preferably a compound represented by the following general formula (1).
  • a compound represented by (2) is also preferred.
  • R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
  • R 5 represents an organic group having 1 or more carbon atoms, and m represents 3 or 4.
  • R 6 to R 9 each independently represents an organic group having 1 or more carbon atoms.
  • n represents 3 or 4.
  • Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 2- A butyl group and a 1-butyl group are mentioned.
  • Examples of the organic group having 1 or more carbon atoms include a trifluoromethyl group, a methyl group, an ethyl group, a 4-methylphenyl group, a phenyl group, and a 10-camphor group.
  • Examples of the compound represented by the general formula (1) include 3-methyl-1- (propyl-3-sulfonyl) imidazolium trifluoromethanesulfonate, 3-butyl-1- (butyl-4-sulfonyl) imidazo Examples include trifluoromethanesulfonate, 3-methyl-1- (butyl-4-sulfonyl) imidazolium, trifluoromethanesulfonate, and 3-methyl-1- (propyl-3-sulfonyl) imidazolium toluenesulfonate. .
  • Examples of the compound represented by the general formula (2) include triphenyl (propyl-3-sulfonyl) phosphonium trifluoromethanesulfonate.
  • the amount of the acidic group-containing ionic liquid used is preferably 0.1 to 1.0 in terms of a molar ratio with respect to the amount of amine represented by the general formula (I) used as a raw material, More preferably, 0.8 is more preferable.
  • the amount used is less than 0.1, the transfer reaction tends to be slow. In addition, since the reaction proceeds sufficiently quickly when the amount used is 1, even if the amount used is larger than 1, the productivity improvement effect is small.
  • Acidic group-containing ionic liquids are hardly soluble in hydrophobic organic solvents, and aromatic polyamines, which are reaction products, dissolve on the hydrophobic organic solvent side, so hydrophobic organic solvents are added to the reaction solution. By doing so, the acidic group-containing ionic liquid and the aromatic polyamine which is a reaction product can be easily separated.
  • the acidic group-containing ionic liquid is recovered, and the recovered liquid is converted into an aldehyde compound (formaldehyde or paraformaldehyde) and an amine represented by the general formula (I). It can also be used as at least a part of the catalyst or the solvent in the above reaction. Even when the acidic group-containing ionic liquid is collected a plurality of times, the reaction rate decreases little and can be reused without any problem.
  • the hydrophobic organic solvent may be any commonly used solvent, for example, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorotoluene, chlorobenzene and dichlorobenzene, butyl acetate and amyl acetate. And esters such as methyl isobutyl ketone, and toluene, xylene, chlorotoluene, chlorobenzene, and dichlorobenzene are particularly preferable.
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as chlorotoluene, chlorobenzene and dichlorobenzene
  • butyl acetate and amyl acetate and amyl acetate.
  • esters such as methyl isobutyl ketone, and toluene, xylene, chlorotoluene, chlorobenzene, and dichlorobenzene are
  • Example 3 [Reaction 1st batch] In a 25 mL two-necked separable flask, 2 g of 3-butyl-1- (butyl-4-sulfonyl) imidazolium trifluoromethanesulfonate, 2 g of a mixture of N, N′-diphenylmethylenediamine and aniline were weighed. . Next, after stirring at a liquid temperature of 100 ° C. for 2 hours, 10 g of toluene was added and further stirred vigorously for 10 minutes. After leaving still for 10 minutes, the upper phase was fractionated, 2 g of ion-exchanged water was mixed therewith and allowed to stand for 10 minutes, and then the upper phase was separated. This solution was evaporated and aniline and toluene were removed under reduced pressure, and then analyzed by liquid chromatography and gas chromatography. Evaluation after analysis was performed in the same manner as in Example 1.
  • Example 4 [Reaction 1st batch] In a 25 mL two-necked separable flask, 2 g of 3-methyl-1- (butyl-4-sulfonyl) imidazolium trifluoromethanesulfonate, 2 g of a mixture of N, N′-diphenylmethylenediamine and aniline was weighed. . Next, after stirring at a liquid temperature of 100 ° C. for 2 hours, 10 g of toluene was added and further stirred vigorously for 10 minutes. The mixture was allowed to stand for 10 minutes, and the upper phase was fractionated. To this, 2 g of ion-exchanged water was mixed, and after standing for 10 minutes, the upper phase was fractionated. This solution was evaporated and aniline and toluene were removed under reduced pressure, and then analyzed by liquid chromatography and gas chromatography. Evaluation after analysis was performed in the same manner as in Example 1.
  • Example 1 For 60 minutes while dehydrating. It left still for 10 minutes and fractionated the upper phase and the lower phase (ionic liquid phase). 4 g of ion exchange water was mixed with the upper phase and allowed to stand for 10 minutes, and then the upper phase and the lower phase (aqueous phase) were separated. The upper phase solution was evaporated, aniline and toluene were removed under reduced pressure, and then analyzed by liquid chromatography and gas chromatography. Evaluation after analysis was performed in the same manner as in Example 1.
  • Comparative Example 1 General Condensation Example In a 25 mL two-necked separable flask, 10 g of a mixed solution of N, N′-diphenylmethylenediamine and aniline and 4.7 g of 35% hydrochloric acid aqueous solution (manufactured by Nippon Polyurethane Co., Ltd.) were weighed. . Next, the mixture was stirred at a liquid temperature of 100 ° C. for 2 hours. Next, 10 g of a 24% aqueous sodium hydroxide solution (sodium hydroxide manufactured by Tosoh Corporation was diluted with ion-exchanged water) was neutralized, extracted and separated, and the upper phase was separated.
  • a 24% aqueous sodium hydroxide solution sodium hydroxide manufactured by Tosoh Corporation was diluted with ion-exchanged water
  • Example 2 This was mixed with 2 g of ion exchange water and allowed to stand for 10 minutes, and then the upper phase was collected. This solution was evaporated and aniline and toluene were removed under reduced pressure, and then analyzed by liquid chromatography and gas chromatography. Evaluation after analysis was performed in the same manner as in Example 1.
  • reaction 2nd to 3rd batch 2 g of a mixed solution of N, N′-diphenylmethylenediamine and aniline was added to the lower phase (ionic liquid phase) of the previous batch. Next, after stirring at a liquid temperature of 100 ° C. for 7 hours, 10 g of toluene was added and stirred vigorously for 10 minutes. After standing for 10 minutes, the upper phase was separated, 2 g of ion-exchanged water was mixed therewith, and allowed to stand for 10 minutes, and then the upper phase was separated. This solution was evaporated and aniline and toluene were removed under reduced pressure, and then analyzed by liquid chromatography and gas chromatography.
  • Examples 1 to 5 are examples in which a mixture of N, N′-diphenylmethylenediamine and aniline was used as a starting material, and the reaction was performed in the presence of an ionic liquid having a sulfonic acid group (—SO 3 H) in the molecule.
  • an ionic liquid having a sulfonic acid group —SO 3 H
  • the reaction batch was repeated 10 or 20 times, the reaction proceeded without any problem.
  • it since it formed an ionic liquid and a salt and was not extracted in toluene until the 2nd batch of reaction, it describes about the analytical value after the 3rd batch of reaction.
  • Comparative Example 1 is a method for producing and purifying general MDA and its higher analogs, but sodium chloride was by-produced in the post-treatment step after the reaction.
  • Comparative Example 2 is an example in which zeolite, which is said to show good reaction performance, was used as a catalyst, but the production rate of MDA and its higher analogs decreased after the second batch of reaction.
  • Comparative Example 3 is an example in which a mixture of N, N′-diphenylmethylenediamine and aniline was used as a starting material, and the reaction was performed in the presence of an ionic liquid having no sulfonic acid group (—SO 3 H) in the molecule.
  • an ionic liquid having no sulfonic acid group (—SO 3 H) in the molecule was used as a starting material, and the reaction was performed in the presence of an ionic liquid having no sulfonic acid group (—SO 3 H) in the molecule.
  • MDA and its higher analogs were not obtained at all.
  • the method for producing an aromatic polyamine of the present invention can be employed, for example, as a method for producing MDA and its higher analogs that do not necessarily require neutralization treatment of acid and restriction of raw material composition.
  • the MDA and its higher analogs are useful as raw materials for polyisocyanates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de polyamine aromatique de formule générale (II) par la réaction entre un composé aldéhyde et une amine de formule générale (I). Selon le procédé de production, un liquide ionique contenant un groupe acide est utilisé comme catalyseur ou solvant pour la réaction. Dans les formules A1 et A2 représentent chacun un groupe organique ou analogue, et q représente un nombre de 0 à 5.
PCT/JP2009/060752 2008-06-17 2009-06-12 Procédé de production de polyamine aromatique WO2009154144A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-158365 2008-06-17
JP2008158365A JP2009298755A (ja) 2008-06-17 2008-06-17 芳香族ポリアミンの製造方法

Publications (1)

Publication Number Publication Date
WO2009154144A1 true WO2009154144A1 (fr) 2009-12-23

Family

ID=41434059

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/060752 WO2009154144A1 (fr) 2008-06-17 2009-06-12 Procédé de production de polyamine aromatique

Country Status (2)

Country Link
JP (1) JP2009298755A (fr)
WO (1) WO2009154144A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113717305A (zh) * 2021-08-02 2021-11-30 浙江石油化工有限公司 一种钛系聚乙烯催化剂改性的方法
CN113735998A (zh) * 2021-08-02 2021-12-03 浙江石油化工有限公司 一种负载茂金属聚乙烯催化剂的改性方法
CN113773428A (zh) * 2021-08-02 2021-12-10 浙江石油化工有限公司 一种负载茂金属聚乙烯催化剂聚合改性的方法
CN113817089A (zh) * 2021-08-02 2021-12-21 浙江石油化工有限公司 一种用离子液体改性铬系聚乙烯催化剂以及用于共聚的方法
CN113817084A (zh) * 2021-08-02 2021-12-21 浙江石油化工有限公司 一种聚丙烯催化剂改性及其试验方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003062467A (ja) * 2001-08-24 2003-03-04 Central Glass Co Ltd イオン液体組成物
JP2003522748A (ja) * 2000-02-14 2003-07-29 バイエル アクチェンゲゼルシャフト ジアミノジフェニルメタンの製造方法
JP2004300085A (ja) * 2003-03-31 2004-10-28 Mitsui Takeda Chemicals Inc ４，４’−メチレンジアニリンの製造方法
WO2005028446A1 (fr) * 2003-09-18 2005-03-31 Sumitomo Chemical Company, Limited Liquide ionique et procede de reaction utilisant ce liquide
JP2005521750A (ja) * 2002-04-05 2005-07-21 ユニバーシティ オブ サウス アラバマ 官能化されたイオン性液体およびこの使用方法
JP2005521722A (ja) * 2002-03-28 2005-07-21 ハンツマン・インターナショナル・エルエルシー ジアミノジフェニルメタン及びその高級同族体の製造方法
JP2006241139A (ja) * 2005-02-03 2006-09-14 Sumitomo Chemical Co Ltd β−ヒドロキシエーテル類の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10127273A1 (de) * 2001-06-05 2002-12-12 Bayer Ag Verfahren zur Herstellung von Polyaminen der Diphenylmethanreihe in Gegenwart ionischer Flüssigkeiten

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003522748A (ja) * 2000-02-14 2003-07-29 バイエル アクチェンゲゼルシャフト ジアミノジフェニルメタンの製造方法
JP2003062467A (ja) * 2001-08-24 2003-03-04 Central Glass Co Ltd イオン液体組成物
JP2005521722A (ja) * 2002-03-28 2005-07-21 ハンツマン・インターナショナル・エルエルシー ジアミノジフェニルメタン及びその高級同族体の製造方法
JP2005521750A (ja) * 2002-04-05 2005-07-21 ユニバーシティ オブ サウス アラバマ 官能化されたイオン性液体およびこの使用方法
JP2004300085A (ja) * 2003-03-31 2004-10-28 Mitsui Takeda Chemicals Inc ４，４’−メチレンジアニリンの製造方法
WO2005028446A1 (fr) * 2003-09-18 2005-03-31 Sumitomo Chemical Company, Limited Liquide ionique et procede de reaction utilisant ce liquide
JP2006241139A (ja) * 2005-02-03 2006-09-14 Sumitomo Chemical Co Ltd β−ヒドロキシエーテル類の製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113717305A (zh) * 2021-08-02 2021-11-30 浙江石油化工有限公司 一种钛系聚乙烯催化剂改性的方法
CN113735998A (zh) * 2021-08-02 2021-12-03 浙江石油化工有限公司 一种负载茂金属聚乙烯催化剂的改性方法
CN113773428A (zh) * 2021-08-02 2021-12-10 浙江石油化工有限公司 一种负载茂金属聚乙烯催化剂聚合改性的方法
CN113817089A (zh) * 2021-08-02 2021-12-21 浙江石油化工有限公司 一种用离子液体改性铬系聚乙烯催化剂以及用于共聚的方法
CN113817084A (zh) * 2021-08-02 2021-12-21 浙江石油化工有限公司 一种聚丙烯催化剂改性及其试验方法
CN113717305B (zh) * 2021-08-02 2022-12-30 浙江石油化工有限公司 一种钛系聚乙烯催化剂改性的方法
CN113735998B (zh) * 2021-08-02 2022-12-30 浙江石油化工有限公司 一种负载茂金属聚乙烯催化剂的改性方法

Also Published As

Publication number Publication date
JP2009298755A (ja) 2009-12-24

Similar Documents

Publication Publication Date Title
Zhu et al. Direct nucleophilic substitution reaction of alcohols mediated by a zinc-based ionic liquid
WO2009154144A1 (fr) Procédé de production de polyamine aromatique
EP2789668B1 (fr) Composition de formation d'un film antistatique et composé oligomère
JP2008545745A (ja) ジフェニルメタン系ポリイソシアネートの製造法
MXPA02007828A (es) Procedimiento para la fabricacion de diaminodifenilmetanos.
US9868699B2 (en) Process for removing cations from an isophoronenitrile product mixture
KR102329341B1 (ko) 트리아세톤 아민을 제조하는 개선된 방법
CN105408383B (zh) 用于制备多异氰酸酯的方法和所述多异氰酸酯的用途
CN1443796A (zh) 具有低色值的二苯基甲烷系列的聚异氰酸酯的制备方法
CN1232499C (zh) 生产低色值二苯基甲烷多异氰酸酯的方法
CN103874680B (zh) 生产浅色多异氰酸酯的方法
KR20140139579A (ko) 이치환된 카보다이이미드 및 다이프로필렌 트라이아민의 반응에 의한 1,5,7-트라이아자바이사이클로[4.4.0] 데스-5-엔의 제조 방법
JPH02188535A (ja) 任意に置換されていてもよいベンジル―ベンゼン類の製造方法
WO2010004818A1 (fr) Procédé de production de polyisocyanate
JP2012250971A (ja) 芳香族ポリアミンの製造方法
KR101959273B1 (ko) 고과당 옥수수시럽으로부터 5-히드록시메틸-2-푸르푸랄을 제조하는 방법
JP5526497B2 (ja) 芳香族ポリアミンの製造方法
EP1355874B1 (fr) Procede de synthese de melanges de methane diphenyle diamine et de ses homologues superieurs a distribution d'isomeres controlee
US10343966B2 (en) Process for the production of 17-oxabicyclo[14.1.0]heptadec-8-ene
WO2016099408A1 (fr) Procédé d'amélioration de la stabilité d'un catalyseur zéolite devant être utilisé dans la production de cumène par alkylation de benzène avec de l'alcool isopropylique
CN116102433B (zh) 一种季铵盐离子液体及其制备方法和应用
US20190152999A1 (en) Cationic silicon (ii) compounds and method for the production thereof
JP5936352B2 (ja) ジアミノジフェニルアルカンの製造方法
CN118290355A (zh) 双氟磺酰亚胺作为催化剂的应用
JP2013095724A (ja) 芳香族ポリアミンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09766592

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09766592

Country of ref document: EP

Kind code of ref document: A1