US20010014730A1 - Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor - Google Patents

Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor Download PDF

Info

Publication number
US20010014730A1
US20010014730A1 US09/771,704 US77170401A US2001014730A1 US 20010014730 A1 US20010014730 A1 US 20010014730A1 US 77170401 A US77170401 A US 77170401A US 2001014730 A1 US2001014730 A1 US 2001014730A1
Authority
US
United States
Prior art keywords
ethylenimine
polymer
crude
aqueous solution
weight
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
US09/771,704
Other versions
US6451961B2 (en
Inventor
Seiichi Suzuki
Yoshiyuki Onda
Isao Satoh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
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
Priority claimed from JP2000026569A external-priority patent/JP2001213958A/en
Priority claimed from JP2000026572A external-priority patent/JP2001213959A/en
Priority claimed from JP2000083303A external-priority patent/JP2001261820A/en
Priority claimed from JP2000085781A external-priority patent/JP2001270941A/en
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Assigned to NIPPON SHOKUBAI CO., LTD. reassignment NIPPON SHOKUBAI CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ONDA, YOSHIYUKI, SATOH, ISAO, SUZUKI, SEIICHI
Publication of US20010014730A1 publication Critical patent/US20010014730A1/en
Application granted granted Critical
Publication of US6451961B2 publication Critical patent/US6451961B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process

Definitions

  • the present invention relates to an ethylenimine polymer, an aqueous solution of an ethylenimine polymer, a production process for the same and a purifying process therefor.
  • a part of these catalysts is used for producing ethylenimine in an industrial scale, and an ethylenimine-containing reaction mixture obtained in this reaction is purified through a high degree purifying step and then used for synthesizing various ethylenimine polymers.
  • an ethylenimine-containing reaction mixture obtained by intermolecular dehydration reaction of monoethanolamine are, in addition to intended ethylenimine, unreacted monoethanolamine; oligomers of ethylenimine; aldehydes such as acetaldehyde; heavy impurities such as a Schiff base produced by a reaction of acetaldehyde with monoethanolamine of the raw material; lower amines such as ammonia, methylamine and ethylamine; and acetonitrile. Accordingly, it is recognized that these impurities have to be removed from the above ethylenimine-containing reaction mixture through a high degree purifying step in order to obtain purified ethylenimine which can be used for polymerization reaction.
  • an object of the present invention is to provide an ethylenimine polymer which solves the problems described above on the conventional techniques and which is decreased in a production cost and industrially advantageous, and a production process for the same.
  • an ethylenimine polymer having a performance which is entirely equivalent to those of conventional ethylenimine polymers obtained by using purified ethylenimine for a raw material can be produced by polymerizing crude ethylenimine obtained by a simple distilling operation from an ethylenimine-containing reaction mixture produced by subjecting ethanolamine to intermolecular dehydration reaction, particularly crude ethylenimine having impurity contents which are controlled in specific ranges, and they have come to complete the present invention based on this knowledge.
  • an ethylenimine polymer characterized by being produced by polymerizing crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst.
  • a production process for an ethylenimine polymer characterized by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine.
  • a process itself for producing an ethylenimine polymer by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce an ethylenimine-containing reaction mixture shall not specifically be restricted and can be carried out by a usually well known process.
  • vaporized monoethanolamine is introduced into a catalyst layer as a raw material gas, if necessary, after suitably diluting this with inert gas such as nitrogen or after adding thereto ammonia, steam or hydrogen for the purpose to inhibit side reactions.
  • the reaction pressure may be any of atmospheric pressure, reduced pressure and elevated pressure.
  • the reaction temperature falls usually in a range of 300 to 500° C.
  • a space velocity of the raw material gas is varied depending on a concentration of monoethanolamine and the kind of the catalyst used and therefore can not absolutely be specified, and it falls usually in a range of 50 to 5000 h ⁇ 1 .
  • the catalyst to be used shall not specifically be restricted as well, and the catalysts described in the above patent publications can be used. Among them, suitably used are catalysts described in Japanese Patent Publications No. 13699/1993, 13700/1993, 76344/1993, 87301/1993, 76343/1993, 55498/1993 and 16905/1993.
  • the ethylenimine-containing reaction mixture obtained by the gas phase intermolecular dehydration reaction described above is collected by means of a scavenger or condensed as it is and collected.
  • An amine compound is suited as the scavenger, and particularly monoethanolamine is the most preferable since it is also the raw material. Mainly ethylenimine, unreacted monoethanolamine and moisture are contained in the ethylenimine-containing reaction mixture.
  • Contained as by-products are lower amines such as ammonia, methylamine and ethylamine; acetonitrile; aldehydes such as acetaldehyde; Schiff bases produced by a reaction of acetaldehyde with monoethanolamine which is the raw material.
  • lower amines such as ammonia, methylamine and ethylamine
  • acetonitrile aldehydes
  • aldehydes such as acetaldehyde
  • Schiff bases produced by a reaction of acetaldehyde with monoethanolamine which is the raw material.
  • an ethylenimine polymer by polymerizing crude ethylenimine which is obtained by subjecting the ethylenimine-containing reaction mixture described above to a simple distilling operation and in which impurity contents are controlled in specific ranges.
  • Such crude ethylenimine contains, for example, 90% by weight or more, preferably 95 to 99.9% by weight of ethylenimine, and as impurities, less than 1000 ppm (by weight), preferably less than 500 ppm of monoethanolamine, less than 2% by weight, preferably less than 1% by weight in total of lower amines comprising ammonia, methylamine and ethylamine, less than 2% by weight, preferably less than 1% by weight of acetonitrile and less than 1000 ppm (by weight) of water.
  • the ethylenimine-containing reaction mixture is brought into contact with an organic solvent such as toluene and xylene to extract heavy matters contained in the reaction mixture, whereby such crude ethylenimine as described above can be obtained as well.
  • Crude ethylenimine having an ethylenimine content of smaller than 90% by weight and impurity contents exceeding the ranges described above causes the problem that an ethylenimine polymer obtained by polymerization thereof is inferior in performances, and therefore it is not preferred in the present invention.
  • such crude ethylenimine as described above is recovered from the ethylenimine-containing reaction mixture by a simple distilling operation or extracting operation, and then this crude ethylenimine is polymerized to produce an ethylenimine polymer.
  • a process for producing an ethylenimine polymer using crude ethylenimine shall not specifically be restricted, and it can be produced by a process usually used for producing an ethylenimine polymer.
  • the polymerization catalyst and the polymerization conditions can suitably be selected from those usually used for polymerizing ethylenimine.
  • crude ethylenimine can be reacted in the presence of an effective amount of an acid catalyst, for example, hydrochloric acid at 0 to 200° C.
  • an acid catalyst for example, hydrochloric acid at 0 to 200° C.
  • crude ethylenimine may be addition-polymerized on the basis of an ethylenimine polymer.
  • the ethylenimine polymer of the present invention includes an ethylenimine homopolymer and a copolymer of ethylenimine with a compound copolymerizable with ethylenimine, for example, amines.
  • a production process for such ethylenimine polymers can be referred to Japanese Patent Publications No. 8828/1968 and 33120/1974.
  • the reaction system may be any of a batch system, a semi-batch system and a continuous flow system.
  • the polymer is increased in a viscosity in producing the polymer, and therefore a stirring blade for high viscosity, for example, a max blend blade (manufactured by Sumitomo Heavy Machine Ind. Co., Ltd.) is suitably used for heat removal, dispersion and acceleration of the reaction.
  • a stirring blade for high viscosity for example, a max blend blade (manufactured by Sumitomo Heavy Machine Ind. Co., Ltd.) is suitably used for heat removal, dispersion and acceleration of the reaction.
  • ethylenimine is suitably polymerized under refluxing of ethylenimine by means of a vertical tube type condenser.
  • Lower amines such as ammonia, methylamine and ethylamine and acetonitrile remain in a certain case in the ethylenimine polymer of the present invention obtained by polymerizing in the manner described above.
  • These impurities exert adverse effects (generation of an offensive smell and a reduction in the stability) to a quality of the ethylenimine polymer and therefore are preferably removed as much as possible by a suitable purifying process.
  • such purifying process is provided as well. It is a process characterized by processing the ethylenimine polymer obtained by polymerizing crude ethylenimine by any of the following operations (A), (B) and (C), and the high purity ethylenimine polymer which meets a quality standard industrially required can be obtained by this process:
  • the operation (A) comprises bubbling inert gas into the ethylenimine polymer.
  • inert gas is bubbled into the ethylenimine polymer in the reactor after finishing the polymerization reaction.
  • gas which is inert to amines such as nitrogen gas, helium gas and argon gas, and nitrogen gas is suitably used from an economical point of view.
  • a temperature of the polymer in bubbling does not have to exceed 200° C. and is held preferably in a range of 100 to 180° C.
  • An amount of the inert gas is usually 0.01 to 10 Nl/min, preferably 0.1 to 2 Nl/min.
  • the bubbling time is usually 0.5 to 100 hours, preferably 1 to 20 hours.
  • the operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the preferred pressure in the reactor is 10 to 700 mm Hg.
  • the operation (A) provides the high-purity ethylenimine polymer in which all contents (B) of lower amines and acetonitrile are less than 1 ppm.
  • the operation (B) comprises adding water to the ethyleni- mine polymer, mixing them and then vaporizing and removing water under heating.
  • water is added to the polymer in the reactor and mixed well, and then this mixture is heated to vaporize and remove water.
  • An addition amount of water is usually 1 to 95%by weight, preferably 5 to 30% by weight based on the polymer.
  • a temperature of the polymer does not have to exceed 200° C. and is held preferably in a range of 100 to 150° C.
  • the operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the preferred pressure in the reactor is 10 to 700 mm Hg.
  • the high-purity ethylenimine polymer in which all contents of lower amines and acetonitrile are less than 1 ppm is obtained by vaporizing and removing 15% by weight or more of water added.
  • the operation (C) comprises a combination of the operation (A) and the operation (B), and this can provide the high-purity ethylenimine polymer by shorter operating time.
  • water is added to the polymer, and water is vaporized and removed from this mixture under heating while bubbling inert gas into this mixture.
  • the present inventors have found that the aqueous solution of the high molecular weight ethylenimine polymer having a performance which is entirely equivalent to those of conventional aqueous solutions of ethylenimine polymers obtained by polymerizing purified ethylenimine in an aqueous medium can be produced by polymerizing in an aqueous medium, crude ethylenimine obtained by a simple distilling operation from the ethylenimine-containing reaction mixture produced by subjecting ethanolamine to intermolecular dehydration reaction in the presence of a catalyst, particularly crude ethylenimine having impurity contents which are controlled in the specific ranges described above.
  • the aqueous solution of the ethylenimine polymer characterized by being produced by polymerizing in an aqueous medium, crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst.
  • a production process for an aqueous solution of an ethylenimine polymer characterized by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine in an aqueous medium.
  • a process for polymerizing crude ethylenimine in an aqueous medium to produce the aqueous solution of the high molecular weight ethylenimine polymer shall not specifically be restricted, and it can be produced by a process usually used for producing an ethylenimine polymer in an aqueous medium.
  • the polymerization catalyst and the polymerization conditions can suitably be selected from those usually used for polymerizing ethylenimine.
  • crude ethylenimine can be polymerized in an aqueous medium in the presence of a polyhaloalkane, for example, dichloroethane and dichloropropane (refer to Japanese Patent Publication No. 8828/1968).
  • crude ethylenimine may be polymerized with ⁇ , ⁇ -unsaturated carboxylic acid or an ester thereof in an aqueous medium (refer to Japanese Patent Publication No. 24184/1967). Further, crude ethylenimine may be addition-polymerized based on an ethylenimine polymer.
  • Lower amines such as ammonia, methylamine and ethylamine and acetonitrile remain in a certain case in the aqueous solution of the high molecular weight ethylenimine polymer obtained by polymerizing in the manner described above.
  • These impurities exert adverse effects (generation of an offensive smell and a reduction in the stability) to a quality of the ethylenimine polymer and therefore are preferably removed as much as possible by a suitable purifying process.
  • such purifying process is provided as well. It is a process comprising heating and condensing the aqueous solution of the high molecular weight ethylenimine polymer obtained in the manner described above. To be specific, taken is a means of heating and condensing the aqueous solution of the high molecular weight ethylenimine polymer while stirring at such a temperature that a temperature in the reactor does not exceed 200° C., preferably a temperature falling in a range of 100 to 180° C. after finishing the polymerization reaction.
  • the degree of concentration of the aqueous solution shall not specifically be restricted, and the object can usually be achieved by vaporizing and removing not much more than 10 to 50% by weight of water contained in the aqueous solution of the ethylenimine polymer (the above aqueous solution comprises usually 20 to 50% by weight of the ethylenimine polymer and 80 to 50% by weight of water).
  • the aqueous solution of the high molecular weight ethylenimine polymer having a high purity in which all contents of lower amines and acetonitrile are less than 1 ppm can be obtained by this method.
  • the heating and condensing operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the pressure in the reactor is preferably controlled to 10 to 700 mm Hg.
  • the ethylenimine polymer having a weight average molecular weight of 1,000 to 1,000,000 can simply and readily be obtained even if any of the embodiments is employed.
  • GPC gel permeation chromatography
  • These ethylenimine polymers have a quality which meets industrial standards and therefore are widely used in the fields of, for example, a paper processing agent, an adhesive, a pressure sensitive agent, paint, ink, a fiber processing agent, a coagulating separator, cosmetics, toiletries and a dispersant.
  • a series of Example I relates to a production of the ethylenimine polymer; a series of Example II relates to a purifying process of the ethylenimine polymer; a series of Example III relates to a production of the aqueous solution of the ethylenimine polymer; and a series of Example IV relates to a purifying process of the aqueous solution of the ethylenimine polymer.
  • the units of ppm, % and parts in the respective examples are based on weight unless otherwise described.
  • a stainless steel-made reactor having a minor diameter of 25 mm was charged with one liter of this catalyst and heated to 430° C. by means of a heat transfer medium.
  • Vaporized monoethanolamine was passed through this reactor under conditions of a pressure of 400 mm Hg at an outlet of the reactor and a space velocity of 1000 h ⁇ 1 to carry out continuous reaction.
  • Reaction mixed gas produced by the reaction had a composition of 67.6 volume % of monoethanolamine, 12.7 volume % of ethylenimine, 15.6 volume % of water, 1.34 volume % of acetaldehyde and others of ammonia and dimers.
  • the reaction mixed gas was cooled down to 100° C. and then introduced into a stainless steel-made distilling tower having a minor diameter of 50 mm and a height of 2000 mm.
  • the tower was charged with fillers (Macmafon packings) of 35 mm in a height of 1600 mm, and the reaction mixed liquid described above was introduced into a part having a height of 1 ⁇ 3 from an upper part of the charging tower.
  • the liquid was distilled under a condition of a reflux ratio of 4 to obtain crude ethylenimine from the tower head.
  • This crude ethylenimine had the following contents of ethylenimine and impurities contained therein.
  • a reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 60 parts of ethylenediamine and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1140 parts of the crude ethylenimine described above was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction, whereby an ethylenimine polymer (PEI-1) was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of this PEI-1 were determined by the following methods. The results thereof are shown in Table 1.
  • Viscosity (mPa ⁇ s/25° C.): Determined by means of a B type viscometer.
  • pH A 5% aqueous solution was prepared to determine a pH by means of a pH meter.
  • Resin content (%) The moisture was determined by a
  • Weight average molecular weight Pulran was used as a standard substance to determine the molecular weight by means of GPC.
  • a reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 72 parts of PEI-1 obtained in Example I-2 and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1128 parts of the crude ethylenimine obtained in Example I-1 was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction, whereby an ethylenimine polymer (PEI-2) was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of this PEI-2 were determined in the same manners as in Example I-2.
  • Ethylenimine was produced according to a method described in Example 1 of Japanese Patent Publication No. 55498/1993. That is, monoethanolamine was continuously introduced into a reactor and subjected to gas phase intermolecular dehydration reaction in the presence of a phosphorus-alkaline earth metal base catalyst under conditions of a temperature of 430° C., a reduced pressure of 400 mm Hg and a space velocity of 1000 h ⁇ 1 . The reaction mixture was cooled down to 100° C. at an outlet of the reactor and condensed, and the condensate was introduced into a continuous distilling tower to obtain crude ethylenimine distilled from the tower head. Contained in this crude ethylenimine were 1000 ppm of methylamine, 6000 ppm of ethylamine, 400 ppm of acetonitrile and 400 ppm of water.
  • a reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 60 parts of ethylenediamine and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1140 parts of the crude ethylenimine obtained in Example 11-1 was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction.
  • the ethylenimine polymer thus obtained had a weight average molecular weight of 3610 (determined by gel permeation chromatography (GPC); reduced to pulran) and a viscosity of 6150 (mPa -s/25° C.; B type viscometer). Contained in the ethylenimine polymer were 400 ppm of acetonitrile and 2000 ppm of lower amines such as ammonia.
  • a flask of 2 liter put on an oil bath was charged with 1 kg of the ethylenimine polymer obtained in Example 11-2, and nitrogen gas was bubbled into the polymer at a rate of 0.2 N 1 /min at an atmospheric pressure.
  • a temperature of the polymer was maintained at 120° C. while bubbling. After bubbling for 5 hours, the polymer was analyzed to find that both contents of acetonitrile and lower amines were 1 ppm or less.
  • a stainless steel-made reactor having a minor diameter of 25 mm was charged with one liter of this catalyst and heated to 430° C. by means of a heat transfer medium.
  • Vaporized monoethanolamine was passed through this reactor under conditions of a pressure of 400 mm Hg at an outlet of the reactor and a space velocity of 1000 h ⁇ 1 to carry out continuous reaction.
  • Reaction mixed gas produced by the reaction had a composition of 67.6 volume % of monoethanolamine, 12.7 volume % of ethylenimine, 15.6 volume % of water, 1.34 volume % of acetaldehyde, and the others were ammonia and dimers.
  • the reaction mixed gas described above was cooled down to 100° C. and then introduced into a stainless steel-made distilling tower having a minor diameter of 50 mm and a height of 2000 mm.
  • the tower was charged with fillers (Macmafon packings) of 6.35 mm in a height of 1600 mm, and the reaction mixed liquid described above was introduced into a part having a height of 1 ⁇ 3 from an upper part of the charging tower.
  • the liquid was distilled under a condition of a reflux ratio of 4 to obtain crude ethylenimine from the tower head.
  • This crude ethylenimine had the following contents of ethylenimine and impurities contained therein.
  • a reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 700 parts of water and 10 parts of 1,2-dichloroethane and heated. After elevating the temperature, 300 parts of the crude ethylenimine obtained in Example III-1 was added thereto at 80° C. in 4 hours. After finishing addition, the solution was ripened at 80° C. for 3 hours to complete the reaction, whereby an aqueous solution of an ethylenimine polymer was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of the aqueous solution of the ethylenimine polymer were determined by the following methods. The results thereof are shown in Table 2.
  • Viscosity (mPa ⁇ s/25° C.): Determined by means of a B type viscometer.
  • pH A 5% aqueous solution was prepared to determine a pH by means of a pH meter.
  • Resin content (%) The solution was dried at 150° C. for one hour by means of a hot air dryer, and the balance was set as the resin content.
  • Weight average molecular weight Pulran was used as a standard substance to determine the molecular weight by means of GPC. TABLE 2 pH Resin Weight average Viscosity (5% aqueous content molecular Example (mPa ⁇ s/25° C.) solution) (mass %) weight III-2 275 10.8 30.2 121780
  • a flask reactor of 2 liter equipped with a stirrer, a reflux condenser and a thermometer was charged with 700 parts of water and 10 parts of 1,2-dichloroethane and heated. After elevating the temperature, 300 parts of the crude ethylenimine obtained in Example II-1 described above was added thereto at 80° C. in 4 hours. After finishing addition, the solution was ripened at 80° C. for 3 hours to complete the reaction.
  • the aqueous solution of the ethylenimine polymer thus obtained was analyzed, to result in finding that the polymer had a weight average molecular weight of 121,780 (determined by gel permeation chromatography (GPC); reduced to pulran) and a viscosity of 275 (mPa ⁇ s/25° C.; B type viscometer) and that the impurity contents were 160 ppm of acetonitrile and 800 ppm of lower amines such as ammonia.
  • GPC gel permeation chromatography
  • a flask reactor equipped with a stirrer, an steam-condensing and drawing device and a thermometer which was put on an oil bath was charged with 1000 g of the aqueous solution of the ethylenimine polymer obtained in Example IV-1 and heated at 110° C. at an atmospheric pressure. Distilled water was cut, and when the resin content became 35%, the solution was analyzed. As a result thereof, it was found that acetonitrile had a content of 0.9 ppm and lower amines had a content of 2.0 ppm. Vaporization was further accelerated to condense the solution, and when the resin content reached 40%, the solution was analyzed to result in finding that both of the contents of acetonitrile and lower amines were 1 ppm or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyamides (AREA)

Abstract

Provided are processes by which an ethylenimine polymer and an aqueous solution thereof can advantageously be produced at low costs in an industrial scale. The ethylenimine polymer can be produced by polymerizing crude ethylenimine obtained by a simple distilling operation from an ethylenimine-containing reaction mixture produced by subjecting ethanolamine to intermolecular dehydration reaction, preferably crude ethylenimine having impurity contents which are controlled in the specific ranges. When the above crude ethylenimine is polymerized in an aqueous medium, capable of being obtained is an aqueous solution of an ethylenimine polymer having a higher molecular weight than that produced by non-solvent polymerization. The ethylenimine polymer can be purified by, for example, adding water thereto, mixing them and then vaporizing and removing water under heating. The aqueous solution of an ethylenimine polymer can be purified by heating and condensing it.

Description

  • The present invention relates to an ethylenimine polymer, an aqueous solution of an ethylenimine polymer, a production process for the same and a purifying process therefor. [0001]
  • It is publicly known that monoethanolamine is subjected to intermolecular dehydration reaction in the presence of a catalyst to obtain ethylenimine. Known as the catalyst are, for example, tantalum base catalysts (U.S. Pat. No. 4,289,656, 4,337,175 and 4,477,591), silicon-alkaline metal and/or alkaline earth metal base catalysts (Japanese Patent Publications No. 13699/1993 and 13700/1993), phosphorus-alkaline metal and/or alkaline earth metal base catalysts (Japanese Patent Publications No. 76344/1993, 87301/1993, 76343/1993, 55498/1993 and 16905/1993), and catalysts prepared by carrying these silicon/phosphorus-alkaline metal/alkaline earth metal base catalyst compositions on molded ceramic carriers (Japanese Patents Laid-Opens No. 132564/1997 and 194455/1997). [0002]
  • A part of these catalysts is used for producing ethylenimine in an industrial scale, and an ethylenimine-containing reaction mixture obtained in this reaction is purified through a high degree purifying step and then used for synthesizing various ethylenimine polymers. To be specific, contained in an ethylenimine-containing reaction mixture obtained by intermolecular dehydration reaction of monoethanolamine are, in addition to intended ethylenimine, unreacted monoethanolamine; oligomers of ethylenimine; aldehydes such as acetaldehyde; heavy impurities such as a Schiff base produced by a reaction of acetaldehyde with monoethanolamine of the raw material; lower amines such as ammonia, methylamine and ethylamine; and acetonitrile. Accordingly, it is recognized that these impurities have to be removed from the above ethylenimine-containing reaction mixture through a high degree purifying step in order to obtain purified ethylenimine which can be used for polymerization reaction. [0003]
  • In conventional techniques, ethylenimine which is purified to such a high degree and therefore is expensive has to be used to produce an ethylenimine polymer, so that the production cost thereof can not be avoided from going up, and they are not necessarily industrially advantageous. [0004]
  • Accordingly, an object of the present invention is to provide an ethylenimine polymer which solves the problems described above on the conventional techniques and which is decreased in a production cost and industrially advantageous, and a production process for the same. [0005]
  • The present inventors have found that an ethylenimine polymer having a performance which is entirely equivalent to those of conventional ethylenimine polymers obtained by using purified ethylenimine for a raw material can be produced by polymerizing crude ethylenimine obtained by a simple distilling operation from an ethylenimine-containing reaction mixture produced by subjecting ethanolamine to intermolecular dehydration reaction, particularly crude ethylenimine having impurity contents which are controlled in specific ranges, and they have come to complete the present invention based on this knowledge. [0006]
  • Thus, according to the present invention, provided is an ethylenimine polymer characterized by being produced by polymerizing crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst. [0007]
  • Further, according to the present invention, provided is a production process for an ethylenimine polymer characterized by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine. [0008]
  • A process itself for producing an ethylenimine polymer by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce an ethylenimine-containing reaction mixture shall not specifically be restricted and can be carried out by a usually well known process. To be specific, vaporized monoethanolamine is introduced into a catalyst layer as a raw material gas, if necessary, after suitably diluting this with inert gas such as nitrogen or after adding thereto ammonia, steam or hydrogen for the purpose to inhibit side reactions. The reaction pressure may be any of atmospheric pressure, reduced pressure and elevated pressure. The reaction temperature falls usually in a range of 300 to 500° C. A space velocity of the raw material gas is varied depending on a concentration of monoethanolamine and the kind of the catalyst used and therefore can not absolutely be specified, and it falls usually in a range of 50 to 5000 h[0009] −1. The catalyst to be used shall not specifically be restricted as well, and the catalysts described in the above patent publications can be used. Among them, suitably used are catalysts described in Japanese Patent Publications No. 13699/1993, 13700/1993, 76344/1993, 87301/1993, 76343/1993, 55498/1993 and 16905/1993.
  • The ethylenimine-containing reaction mixture obtained by the gas phase intermolecular dehydration reaction described above is collected by means of a scavenger or condensed as it is and collected. An amine compound is suited as the scavenger, and particularly monoethanolamine is the most preferable since it is also the raw material. Mainly ethylenimine, unreacted monoethanolamine and moisture are contained in the ethylenimine-containing reaction mixture. Contained as by-products are lower amines such as ammonia, methylamine and ethylamine; acetonitrile; aldehydes such as acetaldehyde; Schiff bases produced by a reaction of acetaldehyde with monoethanolamine which is the raw material. [0010]
  • In the present invention, preferably produced is an ethylenimine polymer by polymerizing crude ethylenimine which is obtained by subjecting the ethylenimine-containing reaction mixture described above to a simple distilling operation and in which impurity contents are controlled in specific ranges. Such crude ethylenimine contains, for example, 90% by weight or more, preferably 95 to 99.9% by weight of ethylenimine, and as impurities, less than 1000 ppm (by weight), preferably less than 500 ppm of monoethanolamine, less than 2% by weight, preferably less than 1% by weight in total of lower amines comprising ammonia, methylamine and ethylamine, less than 2% by weight, preferably less than 1% by weight of acetonitrile and less than 1000 ppm (by weight) of water. [0011]
  • In addition to the above, the ethylenimine-containing reaction mixture is brought into contact with an organic solvent such as toluene and xylene to extract heavy matters contained in the reaction mixture, whereby such crude ethylenimine as described above can be obtained as well. [0012]
  • Crude ethylenimine having an ethylenimine content of smaller than 90% by weight and impurity contents exceeding the ranges described above causes the problem that an ethylenimine polymer obtained by polymerization thereof is inferior in performances, and therefore it is not preferred in the present invention. [0013]
  • In the present invention, such crude ethylenimine as described above is recovered from the ethylenimine-containing reaction mixture by a simple distilling operation or extracting operation, and then this crude ethylenimine is polymerized to produce an ethylenimine polymer. [0014]
  • A process for producing an ethylenimine polymer using crude ethylenimine shall not specifically be restricted, and it can be produced by a process usually used for producing an ethylenimine polymer. The polymerization catalyst and the polymerization conditions can suitably be selected from those usually used for polymerizing ethylenimine. For example, crude ethylenimine can be reacted in the presence of an effective amount of an acid catalyst, for example, hydrochloric acid at 0 to 200° C. (Japanese Patent Publication No. 33120/1074, Japanese Patent Publication (through PCT) No. 501757/2000 and the like). Further, crude ethylenimine may be addition-polymerized on the basis of an ethylenimine polymer. The ethylenimine polymer of the present invention includes an ethylenimine homopolymer and a copolymer of ethylenimine with a compound copolymerizable with ethylenimine, for example, amines. A production process for such ethylenimine polymers can be referred to Japanese Patent Publications No. 8828/1968 and 33120/1974. [0015]
  • The reaction system may be any of a batch system, a semi-batch system and a continuous flow system. In the case of a batch system, the polymer is increased in a viscosity in producing the polymer, and therefore a stirring blade for high viscosity, for example, a max blend blade (manufactured by Sumitomo Heavy Machine Ind. Co., Ltd.) is suitably used for heat removal, dispersion and acceleration of the reaction. Further, in order to make heat removal efficient, ethylenimine is suitably polymerized under refluxing of ethylenimine by means of a vertical tube type condenser. [0016]
  • Lower amines such as ammonia, methylamine and ethylamine and acetonitrile remain in a certain case in the ethylenimine polymer of the present invention obtained by polymerizing in the manner described above. These impurities exert adverse effects (generation of an offensive smell and a reduction in the stability) to a quality of the ethylenimine polymer and therefore are preferably removed as much as possible by a suitable purifying process. [0017]
  • Further, according to the present invention, such purifying process is provided as well. It is a process characterized by processing the ethylenimine polymer obtained by polymerizing crude ethylenimine by any of the following operations (A), (B) and (C), and the high purity ethylenimine polymer which meets a quality standard industrially required can be obtained by this process: [0018]
  • A: bubbling inert gas into the ethylenimine polymer B: adding water to the ethylenimine polymer, mixing them and then vaporizing and removing water under heating C: adding water to the ethylenimine polymer, mixing them and then vaporizing and removing water by heating while bubbling inert gas into the ethylenimine polymer. [0019]
  • The operation (A) comprises bubbling inert gas into the ethylenimine polymer. To be specific, inert gas is bubbled into the ethylenimine polymer in the reactor after finishing the polymerization reaction. Used as the inert gas is gas which is inert to amines, such as nitrogen gas, helium gas and argon gas, and nitrogen gas is suitably used from an economical point of view. A temperature of the polymer in bubbling does not have to exceed 200° C. and is held preferably in a range of 100 to 180° C. An amount of the inert gas is usually 0.01 to 10 Nl/min, preferably 0.1 to 2 Nl/min. The bubbling time is usually 0.5 to 100 hours, preferably 1 to 20 hours. The operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the preferred pressure in the reactor is 10 to 700 mm Hg. The operation (A) provides the high-purity ethylenimine polymer in which all contents (B) of lower amines and acetonitrile are less than 1 ppm. [0020]
  • The operation (B) comprises adding water to the ethyleni- mine polymer, mixing them and then vaporizing and removing water under heating. To be specific, after finishing the polymerization reaction, water is added to the polymer in the reactor and mixed well, and then this mixture is heated to vaporize and remove water. An addition amount of water is usually 1 to 95%by weight, preferably 5 to 30% by weight based on the polymer. In vaporizing and removing water, a temperature of the polymer does not have to exceed 200° C. and is held preferably in a range of 100 to 150° C. The operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the preferred pressure in the reactor is 10 to 700 mm Hg. The high-purity ethylenimine polymer in which all contents of lower amines and acetonitrile are less than 1 ppm is obtained by vaporizing and removing 15% by weight or more of water added. [0021]
  • The operation (C) comprises a combination of the operation (A) and the operation (B), and this can provide the high-purity ethylenimine polymer by shorter operating time. To be specific, after finishing the polymerization reaction, water is added to the polymer, and water is vaporized and removed from this mixture under heating while bubbling inert gas into this mixture. [0022]
  • The ethylenimine polymer obtained by subjecting ethylenimine to non-solvent polymerization in the presence of an acid catalyst has been described above. In the non-solvent polymerization method, however, it is difficult to obtain a polymer having a high molecular weight because of a problem on a viscosity. Accordingly, desired is a process for producing an ethylenimine polymer having a higher molecular weight. Proposed as one of such processes is a process for producing an aqueous solution of an ethylenimine polymer having a high molecular weight by polymerizing highly purified ethylenimine in an aqueous medium (Japanese Patent Publication No. 8828/1968). However, this process requires a high degree purifying step of ethylenimine and therefore can not be avoided from increasing in a production cost, so that it is not necessarily industrially advantageous. [0023]
  • The present inventors have found that the aqueous solution of the high molecular weight ethylenimine polymer having a performance which is entirely equivalent to those of conventional aqueous solutions of ethylenimine polymers obtained by polymerizing purified ethylenimine in an aqueous medium can be produced by polymerizing in an aqueous medium, crude ethylenimine obtained by a simple distilling operation from the ethylenimine-containing reaction mixture produced by subjecting ethanolamine to intermolecular dehydration reaction in the presence of a catalyst, particularly crude ethylenimine having impurity contents which are controlled in the specific ranges described above. [0024]
  • Thus, according to the present invention, provided is the aqueous solution of the ethylenimine polymer characterized by being produced by polymerizing in an aqueous medium, crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst. [0025]
  • Further, according to the present invention, provided is a production process for an aqueous solution of an ethylenimine polymer characterized by subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine in an aqueous medium. [0026]
  • A process for polymerizing crude ethylenimine in an aqueous medium to produce the aqueous solution of the high molecular weight ethylenimine polymer shall not specifically be restricted, and it can be produced by a process usually used for producing an ethylenimine polymer in an aqueous medium. The polymerization catalyst and the polymerization conditions can suitably be selected from those usually used for polymerizing ethylenimine. To be specific, crude ethylenimine can be polymerized in an aqueous medium in the presence of a polyhaloalkane, for example, dichloroethane and dichloropropane (refer to Japanese Patent Publication No. 8828/1968). Or, crude ethylenimine may be polymerized with α,β-unsaturated carboxylic acid or an ester thereof in an aqueous medium (refer to Japanese Patent Publication No. 24184/1967). Further, crude ethylenimine may be addition-polymerized based on an ethylenimine polymer. [0027]
  • Lower amines such as ammonia, methylamine and ethylamine and acetonitrile remain in a certain case in the aqueous solution of the high molecular weight ethylenimine polymer obtained by polymerizing in the manner described above. These impurities exert adverse effects (generation of an offensive smell and a reduction in the stability) to a quality of the ethylenimine polymer and therefore are preferably removed as much as possible by a suitable purifying process. [0028]
  • Further, according to the present invention, such purifying process is provided as well. It is a process comprising heating and condensing the aqueous solution of the high molecular weight ethylenimine polymer obtained in the manner described above. To be specific, taken is a means of heating and condensing the aqueous solution of the high molecular weight ethylenimine polymer while stirring at such a temperature that a temperature in the reactor does not exceed 200° C., preferably a temperature falling in a range of 100 to 180° C. after finishing the polymerization reaction. The degree of concentration of the aqueous solution shall not specifically be restricted, and the object can usually be achieved by vaporizing and removing not much more than 10 to 50% by weight of water contained in the aqueous solution of the ethylenimine polymer (the above aqueous solution comprises usually 20 to 50% by weight of the ethylenimine polymer and 80 to 50% by weight of water). The aqueous solution of the high molecular weight ethylenimine polymer having a high purity in which all contents of lower amines and acetonitrile are less than 1 ppm can be obtained by this method. The heating and condensing operation may be carried out either at atmospheric pressure or under reduced pressure, and when it is carried out under reduced pressure, the pressure in the reactor is preferably controlled to 10 to 700 mm Hg. [0029]
  • Various embodiments of the present invention have been explained above, and according to the present invention, the ethylenimine polymer having a weight average molecular weight of 1,000 to 1,000,000 (determined by gel permeation chromatography (GPC); reduced to pulran) can simply and readily be obtained even if any of the embodiments is employed. These ethylenimine polymers have a quality which meets industrial standards and therefore are widely used in the fields of, for example, a paper processing agent, an adhesive, a pressure sensitive agent, paint, ink, a fiber processing agent, a coagulating separator, cosmetics, toiletries and a dispersant. [0030]
  • The present invention shall more specifically be explained below with reference to examples. A series of Example I relates to a production of the ethylenimine polymer; a series of Example II relates to a purifying process of the ethylenimine polymer; a series of Example III relates to a production of the aqueous solution of the ethylenimine polymer; and a series of Example IV relates to a purifying process of the aqueous solution of the ethylenimine polymer. The units of ppm, % and parts in the respective examples are based on weight unless otherwise described. [0031]
    • EXAMPLE I-1
  • (Production of Crude Ethylenimine) [0032]
  • Dissolved in 2.4 liter of water was 900 g of aluminum sulfate (9 hydrates), and a solution prepared by dissolving 357.6 g of triammnium phosphate in 2.4 liter of water was added to this solution while stirring. The resulting precipitate was filtered and washed with water, and then it was kneaded well together with 73.6 g of barium oxide and 100 ml of water. The resulting clayish matter was molded into a pellet form having a major diameter of about 5 mm and a length of about 5 mm, and the pellets were dried and then baked at 1000° C. for 2 hours to obtain a catalyst having a composition of Al[0033] 1P1B0.2 in terms of an atomic ratio excluding oxygen.
  • A stainless steel-made reactor having a minor diameter of 25 mm was charged with one liter of this catalyst and heated to 430° C. by means of a heat transfer medium. Vaporized monoethanolamine was passed through this reactor under conditions of a pressure of 400 mm Hg at an outlet of the reactor and a space velocity of 1000 h[0034] −1 to carry out continuous reaction. Reaction mixed gas produced by the reaction had a composition of 67.6 volume % of monoethanolamine, 12.7 volume % of ethylenimine, 15.6 volume % of water, 1.34 volume % of acetaldehyde and others of ammonia and dimers.
  • The reaction mixed gas was cooled down to 100° C. and then introduced into a stainless steel-made distilling tower having a minor diameter of 50 mm and a height of 2000 mm. The tower was charged with fillers (Macmafon packings) of 35 mm in a height of 1600 mm, and the reaction mixed liquid described above was introduced into a part having a height of ⅓ from an upper part of the charging tower. The liquid was distilled under a condition of a reflux ratio of 4 to obtain crude ethylenimine from the tower head. [0035]
  • This crude ethylenimine had the following contents of ethylenimine and impurities contained therein. [0036]
  • Ethylenimine: 98.5% [0037]
  • Monoethanolamine: 400 ppm [0038]
  • Lower amines in total: 9000 ppm [0039]
  • Methylamine: 1000 ppm [0040]
  • Ethylamine: 6000 ppm [0041]
  • Ammonia: 2000 ppm [0042]
  • Acetonitrile: 400 ppm [0043]
  • Water: 400 ppm [0044]
    • EXAMPLE I-2
  • (Production of Ethylenimine Polymer) [0045]
  • A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 60 parts of ethylenediamine and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1140 parts of the crude ethylenimine described above was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction, whereby an ethylenimine polymer (PEI-1) was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of this PEI-1 were determined by the following methods. The results thereof are shown in Table 1. [0046]
  • Viscosity (mPa·s/25° C.): Determined by means of a B type viscometer. [0047]
  • pH: A 5% aqueous solution was prepared to determine a pH by means of a pH meter. [0048]
  • Resin content (%): The moisture was determined by a [0049]
  • Karl Fisher method, and the balance was set as the resin content. [0050]
  • Weight average molecular weight: Pulran was used as a standard substance to determine the molecular weight by means of GPC. [0051]
    • EXAMPLE I-3
  • (Production of Ethylenimine Polymer) [0052]
  • A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 72 parts of PEI-1 obtained in Example I-2 and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1128 parts of the crude ethylenimine obtained in Example I-1 was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction, whereby an ethylenimine polymer (PEI-2) was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of this PEI-2 were determined in the same manners as in Example I-2. The results thereof are shown in Table 1. [0053]
    TABLE 1
    pH Resin Weight average
    Viscosity (5% aqueous content molecular
    Example (mPa · s/25° C.) solution) (mass %) weight
    I-2 6150 11.1 99.7 3610
    (PEI-1)
    I-3 86600 11.3 99.8 16560
    (PEI-2)
    • Example II-1
  • (Production of Crude Ethylenimine) [0054]
  • Ethylenimine was produced according to a method described in Example 1 of Japanese Patent Publication No. 55498/1993. That is, monoethanolamine was continuously introduced into a reactor and subjected to gas phase intermolecular dehydration reaction in the presence of a phosphorus-alkaline earth metal base catalyst under conditions of a temperature of 430° C., a reduced pressure of 400 mm Hg and a space velocity of 1000 h[0055] −1. The reaction mixture was cooled down to 100° C. at an outlet of the reactor and condensed, and the condensate was introduced into a continuous distilling tower to obtain crude ethylenimine distilled from the tower head. Contained in this crude ethylenimine were 1000 ppm of methylamine, 6000 ppm of ethylamine, 400 ppm of acetonitrile and 400 ppm of water.
    • EXAMPLE II-2
  • (Production of Ethylenimine Polymer) [0056]
  • A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 60 parts of ethylenediamine and 17 parts of 35% hydrochloric acid and heated. After elevating the temperature, 1140 parts of the crude ethylenimine obtained in Example 11-1 was added thereto at 100 to 120° C. in 10 hours under refluxing. After finishing addition, the solution was ripened at 100 to 120° C. for 2 hours to complete the reaction. The ethylenimine polymer thus obtained had a weight average molecular weight of 3610 (determined by gel permeation chromatography (GPC); reduced to pulran) and a viscosity of 6150 (mPa -s/25° C.; B type viscometer). Contained in the ethylenimine polymer were 400 ppm of acetonitrile and 2000 ppm of lower amines such as ammonia. [0057]
    • EXAMPLE II-3
  • (Purifying of Ethylenimine Polymer) [0058]
  • A flask of 2 liter put on an oil bath was charged with 1 kg of the ethylenimine polymer obtained in Example 11-2, and nitrogen gas was bubbled into the polymer at a rate of 0.2 N[0059] 1/min at an atmospheric pressure. A temperature of the polymer was maintained at 120° C. while bubbling. After bubbling for 5 hours, the polymer was analyzed to find that both contents of acetonitrile and lower amines were 1 ppm or less.
    • EXAMPLE II-4
  • (Purifying of Ethylenimine Polymer) [0060]
  • After adding 0.2 kg of water to 1 kg of the ethylenimine polymer obtained in Example II-2, it was charged into a flask of 2 liter put on an oil bath and heated at an atmospheric pressure under nitrogen atmosphere to vaporize and remove water. The temperature of the oil bath was maintained at 105° C. during this operation. After heated and vaporized for 10 hours, the polymer was analyzed to find that both contents of acetonitrile and lower amines were 1 ppm or less and the water content was 14%. [0061]
    • EXAMPLE II-5
  • (Purifying of Ethylenimine Polymer) [0062]
  • After adding 0.2 kg of water to 1 kg of the ethylenimine polymer obtained in Example II-2, it was charged into a flask of 2 liter put on an oil bath and heated while bubbling nitrogen gas into the polymer at a rate of 0.2 Nl/min at an atmospheric pressure to vaporize and remove water. The temperature of the oil bath was maintained at 105° C. during this operation. After heated and bubbled for 8 hours, the polymer was analyzed to find that both contents of acetonitrile lower amines were 1 ppm or less and the water content was 14%. [0063]
    • EXAMPLE II-6
  • (Purifying of Ethylenimine Polymer) [0064]
  • After adding 0.2 kg of water to 1 kg of the ethylenimine polymer obtained in Example II-2, it was charged into a flask of 2 liter put on an oil bath, and nitrogen gas was bubbled into the polymer at a rate of 0.2 Nl/min at an atmospheric pressure. The polymer mixture was slowly heated from 90° C. up to 127° C. in 3 hours to vaporize and remove water. After heated and bubbled for 3 hours, the polymer was analyzed to find that both contents of acetonitrile and lower amines were 1 ppm or less and the water content was 10%. [0065]
    • EXAMPLE III-1
  • (Production of Crude Ethylenimine) [0066]
  • Dissolved in 2.4 liter of water was 900 g of aluminum sulfate (9 hydrates), and a solution prepared by dissolving 357.6 g of triammnium phosphate in 2.4 liter of water was added to this solution while stirring. The resulting precipitate was filtered and washed with water and then, it was kneaded well together with 73.6 g of barium oxide and 100 ml of water. The resulting clayish matter was molded into a pellet form having a major diameter of about 5 mm and a length of about 5 mm, and the pellets were dried and then baked at 1000° C. for 2 hours to obtain a catalyst having a composition of Al[0067] 1P1B0.2 in terms of an atomic ratio excluding oxygen.
  • A stainless steel-made reactor having a minor diameter of 25 mm was charged with one liter of this catalyst and heated to 430° C. by means of a heat transfer medium. Vaporized monoethanolamine was passed through this reactor under conditions of a pressure of 400 mm Hg at an outlet of the reactor and a space velocity of 1000 h[0068] −1 to carry out continuous reaction. Reaction mixed gas produced by the reaction had a composition of 67.6 volume % of monoethanolamine, 12.7 volume % of ethylenimine, 15.6 volume % of water, 1.34 volume % of acetaldehyde, and the others were ammonia and dimers.
  • The reaction mixed gas described above was cooled down to 100° C. and then introduced into a stainless steel-made distilling tower having a minor diameter of 50 mm and a height of 2000 mm. The tower was charged with fillers (Macmafon packings) of 6.35 mm in a height of 1600 mm, and the reaction mixed liquid described above was introduced into a part having a height of ⅓ from an upper part of the charging tower. The liquid was distilled under a condition of a reflux ratio of 4 to obtain crude ethylenimine from the tower head. [0069]
  • This crude ethylenimine had the following contents of ethylenimine and impurities contained therein. [0070]
  • Ethylenimine: 98.5% [0071]
  • Monoethanolamine: 400 ppm [0072]
  • Lower amines in total: 9000 ppm [0073]
  • Methylamine: 1000 ppm [0074]
  • Ethylamine: 6000 ppm [0075]
  • Ammonia: 2000 ppm [0076]
  • Acetonitrile: 400 ppm [0077]
  • Water: 400 ppm [0078]
    • EXAMPLE III-2
  • (Production of Aqueous Solution of Ethylenimine Polymer) [0079]
  • A reactor equipped with a stirrer, a reflux condenser and a thermometer was charged with 700 parts of water and 10 parts of 1,2-dichloroethane and heated. After elevating the temperature, 300 parts of the crude ethylenimine obtained in Example III-1 was added thereto at 80° C. in 4 hours. After finishing addition, the solution was ripened at 80° C. for 3 hours to complete the reaction, whereby an aqueous solution of an ethylenimine polymer was obtained. After cooling down, a viscosity, a pH, a resin content and a weight average molecular weight of the aqueous solution of the ethylenimine polymer were determined by the following methods. The results thereof are shown in Table 2. [0080]
  • Viscosity (mPa·s/25° C.): Determined by means of a B type viscometer. [0081]
  • pH: A 5% aqueous solution was prepared to determine a pH by means of a pH meter. [0082]
  • Resin content (%): The solution was dried at 150° C. for one hour by means of a hot air dryer, and the balance was set as the resin content. [0083]
  • Weight average molecular weight: Pulran was used as a standard substance to determine the molecular weight by means of GPC. [0084]
    TABLE 2
    pH Resin Weight average
    Viscosity (5% aqueous content molecular
    Example (mPa · s/25° C.) solution) (mass %) weight
    III-2 275 10.8 30.2 121780
    • EXAMPLE IV-1
  • (Production of Aqueous Solution of Ethylenimine Polymer) [0085]
  • A flask reactor of 2 liter equipped with a stirrer, a reflux condenser and a thermometer was charged with 700 parts of water and 10 parts of 1,2-dichloroethane and heated. After elevating the temperature, 300 parts of the crude ethylenimine obtained in Example II-1 described above was added thereto at 80° C. in 4 hours. After finishing addition, the solution was ripened at 80° C. for 3 hours to complete the reaction. The aqueous solution of the ethylenimine polymer thus obtained was analyzed, to result in finding that the polymer had a weight average molecular weight of 121,780 (determined by gel permeation chromatography (GPC); reduced to pulran) and a viscosity of 275 (mPa·s/25° C.; B type viscometer) and that the impurity contents were 160 ppm of acetonitrile and 800 ppm of lower amines such as ammonia. [0086]
    • EXAMPLE IV-2
  • (Purifying of Aqueous Solution of Ethylenimine Polymer) [0087]
  • A flask reactor equipped with a stirrer, an steam-condensing and drawing device and a thermometer which was put on an oil bath was charged with 1000 g of the aqueous solution of the ethylenimine polymer obtained in Example IV-1 and heated at 110° C. at an atmospheric pressure. Distilled water was cut, and when the resin content became 35%, the solution was analyzed. As a result thereof, it was found that acetonitrile had a content of 0.9 ppm and lower amines had a content of 2.0 ppm. Vaporization was further accelerated to condense the solution, and when the resin content reached 40%, the solution was analyzed to result in finding that both of the contents of acetonitrile and lower amines were 1 ppm or less. [0088]

Claims (8)

1. An ethylenimine polymer characterized by being produced by polymerizing crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst.
2. The ethylenimine polymer as described in
claim 1
, wherein the above crude ethylenimine contains at least 90% by weight of ethylenimine, and as impurities, less than 1000 ppm (by weight) of monoethanolamine, less than 2% by weight in total of lower amines comprising ammonia, methylamine and ethylamine, less than 2% by weight of acetonitrile and less than 1000 ppm (by weight) of water.
3. A production process for the ethylenimine polymer as described in
claim 1
 or 2, comprising subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine.
4. A process for purifying the ethylenimine polymer produced by the process as described in
claim 3
, characterized by:
(A) bubbling inert gas into the above ethylenimine polymer,
(B) adding water to the ethylenimine polymer, mixing them and then vaporizing and removing water under heating, or
(C) adding water to the ethylenimine polymer, mixing them and then vaporizing and removing water by heating while bubbling inert gas into the ethylenimine polymer.
5. An ethylenimine polymer aqueous solution characterized by being produced by polymerizing in an aqueous medium, crude ethylenimine obtained by intermolecular dehydration reaction of monoethanolamine in the presence of a catalyst.
6. The ethylenimine polymer aqueous solution as described in
claim 5
, wherein the above crude ethylenimine contains at least 90% by weight of ethylenimine, and as impurities, less than 1000 ppm (by weight) of monoethanolamine, less than 2% by weight in total of lower amines comprising ammonia, methylamine and ethylamine, less than 2% by weight of acetonitrile and less than 1000 ppm (by weight) of water.
7. A production process for the ethylenimine polymer aqueous solution as described in
claim 5
 or 6, comprising subjecting monoethanolamine to intermolecular dehydration reaction in the presence of a catalyst to produce crude ethylenimine and then polymerizing this crude ethylenimine in an aqueous medium.
8. A process for purifying the ethylenimine polymer aqueous solution produced by the process as described in
claim 7
, characterized by heating and condensing the above aqueous solution.
US09/771,704 2000-02-03 2001-01-30 Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor Expired - Fee Related US6451961B2 (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2000-026569 2000-02-03
JP2000026569A JP2001213958A (en) 2000-02-03 2000-02-03 Ethyleneimine polymer and its production method
JP2000-026572 2000-02-03
JP2000-26569 2000-02-03
JP2000026572A JP2001213959A (en) 2000-02-03 2000-02-03 Aqueous ethyleneimine polymer solution and its production method
JP2000-083303 2000-03-24
JP2000083303A JP2001261820A (en) 2000-03-24 2000-03-24 Process for purification of ethylene imine polymer
JP2000-085781 2000-03-27
JP2000085781A JP2001270941A (en) 2000-03-27 2000-03-27 Method for purifying aqueous solution of ethylenemine polymer

Publications (2)

Publication Number Publication Date
US20010014730A1 true US20010014730A1 (en) 2001-08-16
US6451961B2 US6451961B2 (en) 2002-09-17

Family

ID=27481000

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/771,704 Expired - Fee Related US6451961B2 (en) 2000-02-03 2001-01-30 Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor

Country Status (2)

Country Link
US (1) US6451961B2 (en)
DE (1) DE10104225B4 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006086492A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
JP2013071967A (en) * 2011-09-27 2013-04-22 Nippon Shokubai Co Ltd Ethyleneimine polymer and method for producing the same
CN105452340A (en) * 2013-08-07 2016-03-30 株式会社日本触媒 Ethyleneimine polymer and production method for same
US10370494B2 (en) 2014-10-17 2019-08-06 Nippon Shokubai Co., Ltd Ethleneimine polymer and method for producing same
CN114213656A (en) * 2022-01-12 2022-03-22 上海健倬生物科技有限公司 Method for preparing polyethyleneimine by novel solid catalyst

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1538261A1 (en) * 2003-12-05 2005-06-08 Ciba Spezialitätenchemie Pfersee GmbH Process for flame-proofing of fibrous products
EP1707665A1 (en) * 2005-03-30 2006-10-04 Huntsman Textile Effects (Germany) GmbH Process for flame-proofing of fibrous materials
DE102005015196A1 (en) * 2005-04-02 2006-10-05 Ciba Spezialitätenchemie Pfersee GmbH Flameproof finishing of fibrous products, useful particularly for materials of high wool or cellulose content, by treatment with a branched polyethyleneimine and a phosphonic acid
CN114713021B (en) * 2022-05-06 2024-03-26 光大环境科技（中国）有限公司 Composite desulfurization and denitrification agent for power plant flue gas purification and preparation method thereof
WO2024180261A2 (en) * 2023-03-02 2024-09-06 Basf Se Environmenal friendly ethylene oxide, propylene oxide and downstream products

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE872269C (en) * 1944-09-05 1953-03-30 Basf Ag Process for stabilizing polyalkyleneimines
US3326895A (en) * 1965-02-15 1967-06-20 Dow Chemical Co Aziridine process
DE1795550A1 (en) * 1965-02-17 1972-01-13 Chemirad Corp Process for the preparation of water-soluble copolymers of alkyleneimines
JPS4933120A (en) 1972-08-02 1974-03-27
JPS5371196A (en) * 1976-12-06 1978-06-24 Mitsubishi Chem Ind Ltd Preparation of purified polyamide
US4337175A (en) 1980-07-14 1982-06-29 The Dow Chemical Company Catalyst for the preparation of ethylenimine
US4289656A (en) 1980-07-17 1981-09-15 The Dow Chemical Company Catalyst for the preparation of ethylenimine
US4477591A (en) 1981-07-09 1984-10-16 The Dow Chemical Company Method for preparing a catalyst for the dehydration of an alkanolamine
DE3852075T2 (en) * 1987-03-12 1995-03-30 Nippon Catalytic Chem Ind METHOD FOR PRODUCING AZIRIDINES.
JPH04217659A (en) * 1990-12-19 1992-08-07 Nippon Shokubai Co Ltd Production of aziridine compound
JPH0513700A (en) 1991-07-03 1993-01-22 Hitachi Ltd Semiconductor integrated circuit and its formation
JPH0513699A (en) 1991-07-04 1993-01-22 Mitsubishi Electric Corp Semiconductor integrated circuit and method for driving the same
JP2934067B2 (en) 1991-07-12 1999-08-16 株式会社イシダ Bag making and packaging machine
JPH0555498A (en) 1991-08-23 1993-03-05 Sony Corp Logic gate circuit using compound semiconductor
JPH0576344A (en) 1991-09-20 1993-03-30 Hitachi Ltd Culture of suspending cell and culture apparatus
JPH0576343A (en) 1991-09-25 1993-03-30 Mitsubishi Heavy Ind Ltd Raceway-type alga-cultivation apparatus
JP2837001B2 (en) 1991-09-30 1998-12-14 三菱重工業株式会社 Pressurized fluidized bed boiler
DE19533662A1 (en) 1995-09-12 1997-03-13 Basf Ag Process for the preparation of aziridines
DE19545874A1 (en) * 1995-12-08 1997-06-12 Basf Ag Process for the continuous production of homopolymers of ethyleneimine
DE19600156A1 (en) 1996-01-04 1997-07-10 Basf Ag Process for the preparation of aziridines

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006086492A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
WO2006086485A1 (en) * 2005-02-08 2006-08-17 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
US20090069501A1 (en) * 2005-02-08 2009-03-12 Basf Aktiengesellschaft Method of making an alkoxylated polyethylenimine product
US7736525B2 (en) 2005-02-08 2010-06-15 Basf Corporation Method of making an alkoxylated polyethylenimine product
US20100216949A1 (en) * 2005-02-08 2010-08-26 Basf Aktiengesellschaft Method Of Making An Alkoxylated Polyethylenimine Product
JP2013071967A (en) * 2011-09-27 2013-04-22 Nippon Shokubai Co Ltd Ethyleneimine polymer and method for producing the same
CN105452340A (en) * 2013-08-07 2016-03-30 株式会社日本触媒 Ethyleneimine polymer and production method for same
EP3031842A1 (en) * 2013-08-07 2016-06-15 Nippon Shokubai Co., Ltd. Ethyleneimine polymer and production method for same
EP3031842A4 (en) * 2013-08-07 2017-03-29 Nippon Shokubai Co., Ltd. Ethyleneimine polymer and production method for same
US9758621B2 (en) 2013-08-07 2017-09-12 Nippon Shokubai Co., Ltd. Ethyleneimine polymer and method for producing the same
US10370494B2 (en) 2014-10-17 2019-08-06 Nippon Shokubai Co., Ltd Ethleneimine polymer and method for producing same
CN114213656A (en) * 2022-01-12 2022-03-22 上海健倬生物科技有限公司 Method for preparing polyethyleneimine by novel solid catalyst

Also Published As

Publication number Publication date
DE10104225B4 (en) 2014-09-11
DE10104225A1 (en) 2001-08-09
US6451961B2 (en) 2002-09-17

Similar Documents

Publication Publication Date Title
US6451961B2 (en) Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor
CN110183402B (en) Nanofiltration membranes and methods of use
JP6192650B2 (en) Method for producing trioxane
KR100715165B1 (en) Method for producing highly reactive polyisobutenes
US6201096B1 (en) Continuous polymerization process for preparing polyamides from omega-aminonitriles
Hashimoto et al. Synthesis and Polymerization of an Optically Active Bicyclic Oxalactam. A Novel Hydrophilic Polyamide Membrane Prepared from (+)-(1R, 5S)-8-Oxa-6-azabicyclo [3.2. 1] octan-7-one
KR100785986B1 (en) Process for making nylon 6,6
JP2001213958A (en) Ethyleneimine polymer and its production method
US5393856A (en) Liquid phase and aqueous solutions of poly(vinyl methyl ether) from highly purified vinyl methyl ether monomer
CA1184937A (en) Process for purifying an aqueous solution of acrylamide
KR20040030642A (en) Process for the production of nylon 6
CA2362510A1 (en) Method for producing polyamide 6 of a low extract content, high viscosity stability and low remonomerization rate
JP2001270941A (en) Method for purifying aqueous solution of ethylenemine polymer
US6569988B1 (en) Method for the production of polyamides
EP0208307A1 (en) Polyoxyalkylene carbazole adduct and method for production thereof
US4412061A (en) Process for the preparation of a polyamide from unsaturated nitrile, lactam and water
TWI339212B (en) Preparation of tetrahydrofuran copolymers
JP2003055450A (en) Low odor polyamine polyether polyol and its manufacturing method
JP2001213959A (en) Aqueous ethyleneimine polymer solution and its production method
US4138546A (en) Catalyst preparation for the polymerization of pyrrolidone
US4405777A (en) Preparation of a polyamide from lactam, ammonium salt of unsaturated acid and unsaturated nitrile
CA1136799A (en) Polymerization of 2-pyrrolidone with alkali metal pyrrolidonates and quaternary ammonium salts
EP0114452B1 (en) Process for the preparation of a polyamide
US3597396A (en) Stabilization of polyoxymethylenes
Fey et al. Ring‐Opening Polymerization of the Cyclic Ester Amide Derived from Adipic Anhydride and 1‐Amino‐6‐hexanol in Melt and in Solution

Legal Events

Date Code Title Description
AS Assignment

Owner name: NIPPON SHOKUBAI CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SUZUKI, SEIICHI;ONDA, YOSHIYUKI;SATOH, ISAO;REEL/FRAME:011489/0552

Effective date: 20010115

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20140917