JP5546492B2 - Ethyleneimine polymer aqueous solution and method for producing the same - Google Patents
Ethyleneimine polymer aqueous solution and method for producing the same Download PDFInfo
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- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 title claims description 144
- 229920000642 polymer Polymers 0.000 title claims description 92
- 239000007864 aqueous solution Substances 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002609 medium Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 235000019645 odor Nutrition 0.000 description 23
- 239000002994 raw material Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- IQGWPPQNIZBTBM-UHFFFAOYSA-N 2-aminoethanol;sulfuric acid Chemical compound NCCO.OS(O)(=O)=O IQGWPPQNIZBTBM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、エチレンイミン重合体水溶液およびその製造方法に関するものである。さらに詳しくは、本発明は、エチレンイミンを開環重合させるエチレンイミン重合体水溶液の製造方法、並びに、エチレンイミン重合体水溶液に関するものである。 The present invention relates to an aqueous ethyleneimine polymer solution and a method for producing the same. More specifically, the present invention relates to a method for producing an ethyleneimine polymer aqueous solution for ring-opening polymerization of ethyleneimine, and an ethyleneimine polymer aqueous solution.
ポリエチレンイミンは紙加工剤、接着剤、粘着剤、塗料、インキ、繊維処理剤、凝集分離剤、化粧品、トイレタリー、分散剤などの分野で幅広く利用されている。エチレンイミン重合体は、エチレンイミンを重合開始剤の存在下に重合させて得られるが、無溶媒下での重合では、粘度上の問題から、得られるエチレンイミン重合体の重合度は低い。このため、高重合度のエチレンイミン重合体を得るためには、水性媒体中で重合反応を行い、高分子量のエチレンイミン重合体をその水溶液の形態で得ている。例えば、特許文献１には、水性溶液中でポリハロアルカン重合開始剤の存在下、５５℃から８５℃でエチレンイミン水溶液の沸点の範囲の温度でエチレンイミンを重合させてエチレンイミン重合体水溶液を得る方法が記載されている。 Polyethyleneimine is widely used in fields such as paper processing agents, adhesives, pressure-sensitive adhesives, paints, inks, fiber treatment agents, aggregating and separating agents, cosmetics, toiletries, and dispersing agents. The ethyleneimine polymer is obtained by polymerizing ethyleneimine in the presence of a polymerization initiator. However, in the polymerization in the absence of a solvent, the degree of polymerization of the resulting ethyleneimine polymer is low due to viscosity problems. For this reason, in order to obtain an ethyleneimine polymer having a high degree of polymerization, a polymerization reaction is carried out in an aqueous medium to obtain a high molecular weight ethyleneimine polymer in the form of an aqueous solution thereof. For example, Patent Document 1 discloses that an ethyleneimine polymer aqueous solution is obtained by polymerizing ethyleneimine in an aqueous solution in the presence of a polyhaloalkane polymerization initiator at a temperature ranging from 55 ° C to 85 ° C in the boiling point of the ethyleneimine aqueous solution. A method is described.
特許文献２は、モノエタノールアミンを触媒の存在下に分子内脱水反応させて得られる粗エチレンイミンの水性媒体中でポリハロアルカン重合開始剤、例えば、ジクロロエタンの存在下に８０℃で反応することによりエチレンイミン重合体水溶液が得られることが開示されている。特許文献３には、水性媒体中でエチレンイミンを重合してエチレンイミン重合体水溶液を製造するにあたり、エチレンイミンを８０℃以下の温度で重合させ、次いで１００〜１５０℃の温度で熟成することにより、粘度の経時的変化が少なく品質が安定し、また樹脂分が２０〜７０質量％という高濃度のエチレンイミン重合体水溶液が得られることが開示されている。 Patent Document 2 discloses a reaction in an aqueous medium of crude ethyleneimine obtained by intramolecular dehydration reaction of monoethanolamine in the presence of a catalyst at 80 ° C. in the presence of a polyhaloalkane polymerization initiator, for example, dichloroethane. It is disclosed that an ethyleneimine polymer aqueous solution can be obtained. In Patent Document 3, in the production of an ethyleneimine polymer aqueous solution by polymerizing ethyleneimine in an aqueous medium, ethyleneimine is polymerized at a temperature of 80 ° C. or less, and then aged at a temperature of 100 to 150 ° C. Further, it is disclosed that an aqueous ethyleneimine polymer solution having a high concentration of 20 to 70% by mass with a resin content can be obtained with little change in viscosity with time.
一方、いずれのエチレンイミン重合体水溶液においても毒性や刺激性の強いエチレンイミンや低分子アミン等が含まれるため、エチレンイミン重合体水溶液中の不純物を除去する方法も検討されている。例えば、特許文献４には変性ポリエチレンイミン水溶液を９８℃で加熱し、さらに窒素ガスを吹き込みながら約１６０℃に加熱することにより悪臭を除去する方法が開示されている。また特許文献２に開示の粗エチレンイミンを水性媒体中で重合して得られるエチレンイミン重合体水溶液には未反応のエタノールアミンおよび副生成物として、アンモニア、メチルアミンおよびエチルアミン等の軽質アミン類、アセトニトリル、さらにはアセトアルデヒドなどのケトン類、アセトアルデヒドと原料のモノエタノールアミンとが反応して生成するシッフ塩基などが含まれるため、特許文献５には、粗エチレンイミンを水性媒体中で重合して得られる粗エチレンイミン重合体水溶液を加熱して、水溶液中の水を蒸発除去することにより高純度エチレンイミン重合体水溶液が得られることが開示されている。 On the other hand, since any ethyleneimine polymer aqueous solution contains highly toxic or irritating ethyleneimine, low-molecular amine, or the like, a method for removing impurities in the ethyleneimine polymer aqueous solution has been studied. For example, Patent Document 4 discloses a method for removing malodor by heating a modified polyethyleneimine aqueous solution at 98 ° C. and further heating to about 160 ° C. while blowing nitrogen gas. Further, an ethyleneimine polymer aqueous solution obtained by polymerizing the crude ethyleneimine disclosed in Patent Document 2 in an aqueous medium contains, as unreacted ethanolamine and by-products, light amines such as ammonia, methylamine and ethylamine, Acetaldehyde and further ketones such as acetaldehyde, and Schiff base formed by the reaction of acetaldehyde and the raw material monoethanolamine are included. Thus, Patent Document 5 discloses a polymer obtained by polymerizing crude ethyleneimine in an aqueous medium. It is disclosed that a high-purity ethyleneimine polymer aqueous solution can be obtained by heating the resulting crude ethyleneimine polymer aqueous solution and evaporating and removing water in the aqueous solution.
しかしながら、不純物が除去された高純度エチレンイミン重合体水溶液であっても悪臭や刺激臭、特にアンモニア臭やアミン臭があることから、その刺激臭がエチレンイミン重合体水溶液を取り扱う者に不快感を与え、食品用の包装フィルム用や洗剤用原料などに関連する用途によってはエチレンイミン重合体の使用制限を受けることがあった。そのため作業環境を改善するためにエチレンイミン重合体の製法については改良の余地があった。 However, even a high-purity ethyleneimine polymer aqueous solution from which impurities have been removed has bad odors and pungent odors, particularly ammonia odors and amine odors. In some cases, the use of ethyleneimine polymer may be restricted depending on the use related to food packaging film or detergent raw materials. Therefore, there has been room for improvement in the process for producing the ethyleneimine polymer in order to improve the working environment.
上記問題点に鑑み、本発明は、悪臭や刺激臭の少ないエチレンイミン重合体水溶液であり、さらには工業的に要求される品質基準に適合した高純度エチレンイミン重合体水溶液を提供することを課題としている。本発明はまた、その高純度エチレンイミン重合体水溶液の製造方法を提供することを目的としている。 In view of the above problems, the present invention is an ethyleneimine polymer aqueous solution with less bad odor and pungent odor, and further provides a high-purity ethyleneimine polymer aqueous solution that meets industrially required quality standards. It is said. Another object of the present invention is to provide a method for producing the high-purity ethyleneimine polymer aqueous solution.
本発明者らの研究によれば、前記課題は下記発明により達成できることがわかった。
（１）水性媒体中でエチレンイミンを重合してエチレンイミン重合体水溶液の製造方法であって、反応溶液温度を４５〜８０℃、反応溶液の撹拌を反応液の最終液量（ｍ３）当りの撹拌機の撹拌動力（ｋＷ）の比率（ＰＶ値＝撹拌動力／最終液量）が０．５ｋＷ／ｍ３以上になるようにエチレンイミンを重合させ、かつ重合中の反応熱を除去する熱媒の温度を４０℃以上で行うことを特徴とするエチレンイミン重合体水溶液製造方法。
（２）重合反応後に１００〜１５０℃の温度で熟成することを特徴とする（１）記載のエチレンイミン重合体水溶液製造方法。
（３）反応溶液温度が５０〜７０℃になるようにエチレンイミンを重合させ、次いで１１０〜１４０℃の温度で熟成することを特徴とする（１）または（２）記載のエチレンイミン重合体水溶液製造方法。
（４）エチレンイミンを重合して得られたエチレンイミン重合体水溶液の水をさらに蒸留除去してエチレンイミン重合体水溶液を精製する工程を含むことを特徴とする（１）から（３）のいずれかに記載のエチレンイミン重合体水溶液の製造方法。
（５）エチレンイミンの重合を反応溶液温度が４５〜８０℃、反応溶液の撹拌を反応液の最終液量（ｍ ３ ）当りの撹拌機の撹拌動力（ｋＷ）の比率（ＰＶ値＝撹拌動力／最終液量）が０．５ｋＷ／ｍ ３ 以上になるように行い、かつ重合中の反応熱を除去する熱媒の温度を４０℃以上で行う方法で製造される、臭気度が５００ｐｐｍ以下であることを特徴とするエチレンイミン重合体水溶液。ここで、臭気度とは分析用の管を取り付けた１０００ｍｌの密閉容器にエチレンイミン重合体として１００gを充填し、その容器を６０℃の水浴槽中で３０分保持した後に、容器内の空間部分のガス濃度をアンモニア用ガス検知管で分析用の管を通して測定した値をいう。
According to the studies by the present inventors, it has been found that the above problems can be achieved by the following invention.
(1) A method for producing an ethyleneimine polymer aqueous solution by polymerizing ethyleneimine in an aqueous medium, wherein the reaction solution temperature is 45 to 80 ° C. , and the reaction solution is stirred per final solution volume (m3). A heating medium that polymerizes ethyleneimine so that the ratio of stirring power (kW) of the stirrer (PV value = stirring power / final liquid amount) is 0.5 kW / m 3 or more and removes heat of reaction during the polymerization. A method for producing an ethyleneimine polymer aqueous solution, wherein the temperature is 40 ° C or higher.
(2) The method for producing an ethyleneimine polymer aqueous solution according to (1), wherein the polymer is aged at a temperature of 100 to 150 ° C. after the polymerization reaction.
(3) The ethyleneimine polymer aqueous solution according to (1) or (2), wherein the ethyleneimine is polymerized so that the reaction solution temperature is 50 to 70 ° C., and then aged at a temperature of 110 to 140 ° C. Production method.
( 4 ) The method according to any one of (1) to ( 3 ), further comprising a step of purifying the ethyleneimine polymer aqueous solution by further removing the water of the ethyleneimine polymer aqueous solution obtained by polymerizing ethyleneimine. A method for producing an aqueous ethyleneimine polymer solution according to claim 1.
( 5 ) Polymerization of ethyleneimine at a reaction solution temperature of 45 to 80 ° C., and stirring of the reaction solution is a ratio of stirring power (kW) of the stirrer per final solution volume (m 3 ) (PV value = stirring power) / Final liquid amount) is 0.5 kW / m 3 or more, and is produced by a method in which the temperature of the heating medium for removing reaction heat during polymerization is 40 ° C. or more, and the odor is 500 ppm or less. An ethyleneimine polymer aqueous solution characterized by being. Here, the odor level is a space portion in a container after 100 g of an ethyleneimine polymer is filled in a 1000 ml sealed container equipped with a tube for analysis, and the container is kept in a water bath at 60 ° C. for 30 minutes. Is a value obtained by measuring the gas concentration through an analysis tube with an ammonia gas detector tube.
本発明によれば、反応後に残存ずる未反応エチレンイミン量を抑制できるので、アンモニア臭、アミン臭がない高純度エチレンイミン重合体水溶液を製造することができる。さらに、本発明の高純度エチレンイミン重合体水溶液は、粘度が経時的に変化が起きないため、品質が安定なエチレンイミン重合体水溶液を得ることができる。 According to the present invention, since the amount of unreacted ethyleneimine remaining after the reaction can be suppressed, a high-purity ethyleneimine polymer aqueous solution free from ammonia odor and amine odor can be produced. Furthermore, since the viscosity of the high-purity ethyleneimine polymer aqueous solution of the present invention does not change with time, an ethyleneimine polymer aqueous solution with stable quality can be obtained.
本発明にかかるエチレンイミン重合体水溶液の製造方法は、水性媒体中でエチレンイミンを重合する際に、反応溶液温度が４５〜８０℃になるようにエチレンイミンを重合させ、かつ重合中の反応熱を除去する熱媒の温度を４０℃以上で行うエチレンイミン重合体水溶液の製造方法である。また、本発明にかかる高純度エチレンイミン重合体水溶液は、臭気度が５００ｐｐｍ以下であるエチレンイミン重合体水溶液である。 In the method for producing an ethyleneimine polymer aqueous solution according to the present invention, when ethyleneimine is polymerized in an aqueous medium, the ethyleneimine is polymerized so that the reaction solution temperature is 45 to 80 ° C., and the reaction heat during the polymerization is obtained. This is a method for producing an aqueous solution of ethyleneimine polymer, wherein the temperature of the heat medium for removing water is 40 ° C. or higher. The high-purity ethyleneimine polymer aqueous solution according to the present invention is an ethyleneimine polymer aqueous solution having an odor degree of 500 ppm or less.
本発明に用いるエチレンイミンには特に制限はなく、例えば、液相でハロゲン化エチルアミンを濃アルカリにより分子内閉環する方法、モノエタノールアミン硫酸エステルを熱濃アルカリにより分子内閉環する方法（以下、液相法ともいう）、あるいはモノエタノールアミンを触媒的気相分子内脱水反応させる方法（以下、気相法ともいう）により得られるエチレンイミンを用いることができる。 The ethyleneimine used in the present invention is not particularly limited, and examples thereof include a method of intramolecular ring closure of halogenated ethylamine with concentrated alkali in a liquid phase, and a method of intramolecular ring closure of monoethanolamine sulfate with hot concentrated alkali (hereinafter, liquid Ethyleneimine obtained by a catalytic gas phase intramolecular dehydration reaction of monoethanolamine (hereinafter also referred to as a gas phase method) can be used.
気相法により得られるエチレンイミン原料としては、モノエタノールアミンの触媒的分子内脱水反応により得られるエチレンイミン含有反応混合物を簡単な蒸留操作に供して回収した粗エチレンイミンを重合用の原料とすることができる（特許文献２参照）。粗エチレンイミンを重合する場合は、エチレンイミン重合体（以下、粗エチレンイミン重合体ということもある。）を簡便な精製操作に供して、工業的に要求される品質基準に適合した高純度ポリエチレンイミンを得ることができる（特許文献５参照）。 As the ethyleneimine raw material obtained by the gas phase method, a crude ethyleneimine recovered by subjecting the ethyleneimine-containing reaction mixture obtained by the catalytic intramolecular dehydration reaction of monoethanolamine to a simple distillation operation is used as a raw material for polymerization. (See Patent Document 2). When polymerizing crude ethyleneimine, high-purity polyethylene that conforms to industrially required quality standards by subjecting ethyleneimine polymer (hereinafter sometimes referred to as crude ethyleneimine polymer) to simple purification operations Imine can be obtained (see Patent Document 5).
前記エチレンイミン含有反応混合物を高度に精製して得られる精製エチレンイミンもエチレンイミン重合体水溶液合成の原料として利用することができる。この場合、前記エチレンイミン含有反応混合物中には、目的物のエチレンイミンのほかに、未反応のモノエタノールアミンや、エチレンイミンのオリゴマー、アセトアルデヒドなどのケトン類、アセトアルデヒドと原料のモノエタノールアミンとが反応して生成するシッフ塩基などの重質不純物や、アンモニア、メチルアミンおよびエチルアミンの軽質アミン類、アセトニトリルなどの軽質不純物が含まれているので、これら不純物を高度の精製工程を経て除去し、しかる後に得られる精製エチレンイミンを重合反応に供するのである。 Purified ethyleneimine obtained by highly purifying the ethyleneimine-containing reaction mixture can also be used as a raw material for the synthesis of an ethyleneimine polymer aqueous solution. In this case, in the ethyleneimine-containing reaction mixture, in addition to the target ethyleneimine, unreacted monoethanolamine, ethyleneimine oligomers, ketones such as acetaldehyde, acetaldehyde and the raw material monoethanolamine It contains heavy impurities such as Schiff base produced by reaction, light amines such as ammonia, methylamine and ethylamine, and acetonitrile, so these impurities are removed through advanced purification steps. The purified ethyleneimine obtained later is subjected to a polymerization reaction.
高度の精製工程を経て得られる精製エチレンイミンを用いてエチレンイミン重合体を製造する技術は、高度の精製工程の実施にともなう生産コストのアップを免れず、工業的に有利とはいえないため、粗エチレンイミンがエチレンイミン原料として好適に用いられる。 The technology for producing an ethyleneimine polymer using purified ethyleneimine obtained through an advanced purification process is not industrially advantageous because it does not escape the increase in production costs associated with the implementation of the advanced purification process. Crude ethyleneimine is suitably used as the ethyleneimine raw material.
重合開始剤としては、エチレンイミンの重合に一般に用いられているものを使用できるが、１，２−ジクロロエタン、１，３−ジクロロプロパン、１，２−ジブロモエタン、クロロホルムなどのポリハロアルカンが好適に用いられる。重合開始剤の使用量は、目的とするエチレンイミン重合体の分子量により適宜選択できる。高分子量エチレンイミン重合体の水溶液を得るためには、エチレンイミンに対して、０．５〜５質量％とするのが好適である。 As the polymerization initiator, those generally used for the polymerization of ethyleneimine can be used, but polyhaloalkanes such as 1,2-dichloroethane, 1,3-dichloropropane, 1,2-dibromoethane, and chloroform are preferably used. Used. The usage-amount of a polymerization initiator can be suitably selected with the molecular weight of the target ethyleneimine polymer. In order to obtain an aqueous solution of a high molecular weight ethyleneimine polymer, the content is preferably 0.5 to 5% by mass with respect to ethyleneimine.
水性媒体としては、通常、水が用いられるが、水溶性有機液体、例えば、メタノール、エタノール、アセトン、ジメチルホルムアミドなどと水との混合物も使用することができる。 As the aqueous medium, water is usually used, but a water-soluble organic liquid, for example, a mixture of methanol, ethanol, acetone, dimethylformamide and the like and water can also be used.
本発明においては、エチレンイミンを重合する際、反応溶液温度を４５〜８０℃、好ましくは５０〜７０℃の温度で行う。８０℃を超える温度では、品質の安定したエチレンイミン重合体水溶液を得ることができない。なお、あまり低い温度では、重合時間が長くなって経済的でない。 In the present invention, when polymerizing ethyleneimine, the reaction solution temperature is 45 to 80 ° C., preferably 50 to 70 ° C. If the temperature exceeds 80 ° C., an ethyleneimine polymer aqueous solution with stable quality cannot be obtained. If the temperature is too low, the polymerization time becomes long and it is not economical.
本発明において、反応熱を除去するために用いる熱媒は４０℃以上に維持しながら重合を行うのが良い。好ましくは４５℃以上、より好ましくは５０℃以上である。前記熱媒の温度を維持することにより、エチレンイミンの反応中に反応溶液が局部的に高粘度になることが抑制され、高効率の撹拌により局部滞留がなく均一な重合をさせることができるため、エチレンイミンの反応が均一かつ効率的に行うことができるようになる。熱媒としては、温水、水蒸気または加熱したオイル等が使用でき、工業的には温水および水蒸気が好適に用いられる。 In the present invention, it is preferable to carry out the polymerization while maintaining the heating medium used for removing reaction heat at 40 ° C. or higher. Preferably it is 45 degreeC or more, More preferably, it is 50 degreeC or more. By maintaining the temperature of the heating medium, it is possible to suppress the reaction solution from becoming locally highly viscous during the reaction of ethyleneimine, and uniform polymerization can be achieved without local retention by highly efficient stirring. The reaction of ethyleneimine can be performed uniformly and efficiently. As the heat medium, warm water, steam, heated oil or the like can be used, and warm water and steam are preferably used industrially.
本発明においては、エチレンイミンの重合終了後、好ましくは供給したエチレンイミンの９５％以上が消費された後、反応液を１００〜１５０℃、好ましくは１１０〜１４０℃に昇温して、この温度範囲で熟成させる。１００℃より低い温度では、品質の安定したエチレンイミン重合体水溶液を得ることができない。また、１５０℃より高い温度では、生成したエチレンイミン重合体の熱分解が起こり、高分子量の重合体が得られないこともある。熟成時間は、通常、１〜２０時間であり、好ましくは２〜１０時間である。また、反応液を熟成温度まで昇温する時間は、通常、０．２〜５時間であり、好ましくは０．５〜３時間である。 In the present invention, after completion of the polymerization of ethyleneimine, preferably after 95% or more of the supplied ethyleneimine has been consumed, the reaction solution is heated to 100 to 150 ° C., preferably 110 to 140 ° C. Aging in range. When the temperature is lower than 100 ° C., an ethyleneimine polymer aqueous solution with stable quality cannot be obtained. Further, at a temperature higher than 150 ° C., the produced ethyleneimine polymer may be thermally decomposed, and a high molecular weight polymer may not be obtained. The aging time is usually 1 to 20 hours, preferably 2 to 10 hours. The time for raising the temperature of the reaction solution to the aging temperature is usually 0.2 to 5 hours, preferably 0.5 to 3 hours.
本発明におけるエチレンイミンの重合反応の際、重合開始剤およびエチレンイミンは一括して添加してもよいが、発熱反応であるため、温度制御しながらそれぞれ連続的に供給するのがよい。 In the polymerization reaction of ethyleneimine in the present invention, the polymerization initiator and ethyleneimine may be added all at once, but since they are exothermic reactions, it is preferable to supply them continuously while controlling the temperature.
重合反応は常圧、加圧のいずれでもよく、通常、０〜１０ＭＰａＧ、好ましくは０〜２ＭＰａＧで行う。反応液の熟成は、通常、０．０５〜１０ＭＰａＧ、好ましくは０．０５〜１ＭＰａＧの加圧下に行うのがよい。 The polymerization reaction may be performed under normal pressure or increased pressure, and is usually performed at 0 to 10 MPaG, preferably 0 to 2 MPaG. Aging of the reaction solution is usually carried out under a pressure of 0.05 to 10 MPaG, preferably 0.05 to 1 MPaG.
重合反応および熟成処理は、回分式（バッチ式）、半回分式、連続流通式などいずれの反応形式によっても行うことができる。連続流通式のように連続的にエチレンイミン重合体水溶液を製造する場合は管型反応器等が用いられ、回分式反応の場合は反応器等が使用される。本発明に用いる反応器としては、温度計、撹拌機、冷却装置等を備えた円筒型反応器が好適に用いられる。 The polymerization reaction and the aging treatment can be performed by any reaction system such as a batch system (batch system), a semi-batch system, and a continuous flow system. In the case of continuously producing an ethyleneimine polymer aqueous solution as in the continuous flow method, a tubular reactor or the like is used, and in the case of a batch reaction, a reactor or the like is used. As the reactor used in the present invention, a cylindrical reactor equipped with a thermometer, a stirrer, a cooling device and the like is preferably used.
回分式反応の場合、重合反応の際に、重合物の粘度が高くなるため、除熱、拡散、反応促進のため撹拌機として、工業的にはパドル翼や高粘度用撹拌翼、例えばマックスブレンド翼（住友重機械工業（株）製）などが用いられ、好適にはマックスブレンド翼である。また重合により発生した反応熱を除去できるように熱媒を流すための冷却装置が付いた反応器、例えば外部ジャケット付反応器などが好適に用いられる。ジャケット式除熱の効率化を図るため縦チューブ型冷却器を用いることもでき、エチレンイミンを還流下で重合するのが好適である。 In the case of batch reaction, the viscosity of the polymer is increased during the polymerization reaction, so as a stirrer for heat removal, diffusion, and reaction promotion, industrially paddle blades and high viscosity stirring blades such as Max Blend A wing (manufactured by Sumitomo Heavy Industries, Ltd.) or the like is used, and a max blend wing is preferable. A reactor equipped with a cooling device for flowing a heat medium so that reaction heat generated by the polymerization can be removed, such as a reactor with an external jacket, is preferably used. In order to increase the efficiency of jacket-type heat removal, a vertical tube type cooler can be used, and it is preferable to polymerize ethyleneimine under reflux.
本発明においては、反応液の最終液量（ｍ３）当りの撹拌動力（ｋＷ）で表わされる値、すなわちＰＶ値（撹拌動力／最終液量）を０．５ｋＷ／ｍ３以上で行うのが良く、好ましくは、２ｋＷ／ｍ３以上が好ましい。尚、１０ｋＷ／ｍ３超えるとエネルギーコストが高くなり経済的でない。 In the present invention, the value represented by the stirring power (kW) per final liquid volume (m 3 ) of the reaction liquid, that is, the PV value (stirring power / final liquid volume) is 0.5 kW / m 3 or more. Good, preferably 2 kW / m 3 or more. If it exceeds 10 kW / m 3 , the energy cost increases and it is not economical.
本発明の製法において好ましい形態は、得られたエチレンイミン重合体水溶液の水や水溶性有機液体をさらに蒸発除去してエチレンイミン重合体水溶液を精製する工程を含む形態である。具体的には、例えば、重合反応終了後、反応器内温度が２００℃を超えない温度、好ましくは１００〜１８０℃の範囲の温度で撹拌下にエチレンイミン重合体水溶液から水分を蒸発除去する。水分の蒸発除去の程度（水溶液の濃縮の程度）については特に制限はないが、通常、エチレンイミン重合体水溶液中のエチレンイミン重合体の濃度（樹脂分）は３０〜５０質量％であるので、エチレンイミン重合体水溶液中の水の１０〜５０質量％程度を蒸発除去すればよい。これにより、気相法で得られた粗エチレンイミン原料を使用する場合は軽質アミン類、アセトニトリルの含有量がともに１ｐｐｍ以下の高純度エチレンイミン重合体水溶液を得ることができる。 A preferred form in the production method of the present invention is a form including a step of purifying the ethyleneimine polymer aqueous solution by further evaporating and removing water and water-soluble organic liquid of the obtained ethyleneimine polymer aqueous solution. Specifically, for example, after completion of the polymerization reaction, water is evaporated and removed from the ethyleneimine polymer aqueous solution with stirring at a temperature at which the temperature in the reactor does not exceed 200 ° C., preferably in the range of 100 to 180 ° C. Although there is no particular limitation on the degree of moisture removal by evaporation (degree of concentration of aqueous solution), since the concentration of ethyleneimine polymer (resin content) in the ethyleneimine polymer aqueous solution is usually 30 to 50% by mass, What is necessary is just to evaporate and remove about 10-50 mass% of water in the ethyleneimine polymer aqueous solution. Thereby, when the crude ethyleneimine raw material obtained by the vapor phase method is used, a high-purity ethyleneimine polymer aqueous solution in which both the content of light amines and acetonitrile is 1 ppm or less can be obtained.
なお、蒸発操作は常圧または減圧のいずれでもよいが、減圧下で行う場合には、反応器内圧力を１０〜７００ｍｍＨｇにするのが好ましい。 The evaporation operation may be carried out at normal pressure or reduced pressure, but when carried out under reduced pressure, the pressure in the reactor is preferably 10 to 700 mmHg.
本発明の方法によって得られるエチレンイミン重合体水溶液は、臭気度が５００ｐｐｍ以下のエチレンイミン重合体である。好ましくは、４００ｐｐｍ以下、より好ましくは３００ｐｐｍ以下である。臭気度が５００ｐｐｍを超えるとアンモニア臭、アミン臭を感じ、１０００ｐｐｍを超えると作業環境において不快感が生じる場合がある。ここで、臭気度は実施例に記載の方法により定義される指標である。 The aqueous ethyleneimine polymer solution obtained by the method of the present invention is an ethyleneimine polymer having an odor degree of 500 ppm or less. Preferably, it is 400 ppm or less, more preferably 300 ppm or less. If the odor level exceeds 500 ppm, an ammonia odor or amine odor may be felt, and if it exceeds 1000 ppm, discomfort may occur in the work environment. Here, the odor degree is an index defined by the method described in the examples.
本発明の方法によればエチレンイミン重合体水溶液は、保存中の経時変化が少ない安定したエチレンイミン重合体水溶液が得られる。特に、粘度変化の少ないエチレンイミン重合体水溶液である。 According to the method of the present invention, an ethyleneimine polymer aqueous solution can be obtained as a stable ethyleneimine polymer aqueous solution with little change over time during storage. In particular, it is an ethyleneimine polymer aqueous solution with little viscosity change.
本発明の方法によって得られるエチレンイミン重合体水溶液の樹脂分（濃度）は、通常、２０〜７０質量％である。好ましくは４０〜６０質量％である。また、エチレンイミン重合体の平均重量分子量は１，０００〜１，０００，０００（ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）測定、プルラン換算）である。 The resin content (concentration) of the aqueous ethyleneimine polymer solution obtained by the method of the present invention is usually 20 to 70% by mass. Preferably it is 40-60 mass%. Further, the average weight molecular weight of the ethyleneimine polymer is 1,000 to 1,000,000 (gel permeation chromatography (GPC) measurement, pullulan conversion).
以下、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらの実施例のみに限定されるものではない。なお、以下ことわりのない場合、「％」は「質量％」を、「ｐｐｍ」は「容積ｐｐｍ」をそれぞれ示すものとする。
＜臭気度の測定方法＞
分析用の管を取り付けた１０００ｍｌの密閉容器にエチレンイミン重合体水溶液１００gを充填し、その容器を６０℃の水浴槽中で３０分保持した後に、容器内の空間部分のガス濃度をアンモニア用ガス検知管で分析用の管を通して測定した値をいう。前記アンモニア用ガス検知管（例えば、ガステック社製３Ｍ）の測定範囲は１０〜１０００ｐｐｍ範囲のものを用いる。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” indicates “mass%” and “ppm” indicates “volume ppm”.
<Odor measurement method>
A 1000 ml sealed container equipped with an analytical tube is filled with 100 g of an ethyleneimine polymer aqueous solution, and the container is held in a 60 ° C. water bath for 30 minutes, and then the gas concentration in the space in the container is adjusted to the gas for ammonia. This is the value measured by the detector tube through the tube for analysis. The measurement range of the gas detector tube for ammonia (for example, 3M manufactured by Gastec Corporation) is 10 to 1000 ppm.
＜エチレンイミン重合体水溶液の調製＞
実施例１
撹拌装置、温度計、エチレンイミンおよび重合開始剤仕込管を備えた容積２リットル（以下、Ｌとも表す）の耐圧反応器を熱媒の温水を６０℃にした水浴槽中に置いた。反応器に水１２００ｇを仕込み、反応溶液温度を５５℃に加熱した後、エチレンイミン８００ｇおよび１，２−ジクロロエタン１３．２ｇ（対エチレンイミン１．６５質量％）を反応温度が８０℃になるように保ちながら、反応器にフィードした。その後、水槽の水温を調節しながら反応温度を７０℃で４時間撹拌したところ、原料エチレンイミンの９８％が反応していた。この間の反応液温度と水浴槽の熱媒温度の差を１０〜２０℃に維持した。
<Preparation of aqueous ethyleneimine polymer solution>
Example 1
A pressure-resistant reactor having a volume of 2 liters (hereinafter also referred to as L) equipped with a stirrer, a thermometer, ethyleneimine and a polymerization initiator feeding tube was placed in a water bath in which the hot water of the heating medium was 60 ° C. After charging 1200 g of water into the reactor and heating the reaction solution temperature to 55 ° C., 800 g of ethyleneimine and 13.2 g of 1,2-dichloroethane (1.65% by mass of ethyleneimine) were adjusted so that the reaction temperature became 80 ° C. And fed to the reactor. Then, when the reaction temperature was stirred at 70 ° C. for 4 hours while adjusting the water temperature in the water tank, 98% of the raw material ethyleneimine had reacted. The difference between the reaction liquid temperature and the heat medium temperature of the water bath during this period was maintained at 10 to 20 ° C.
その後、水槽をオイル槽に変更し反応液の温度を１２０℃まで３０分で昇温し、温度１２０℃、圧力０．１ＭＰａＧで５時間熟成した。１２０℃に昇温直後の反応液の粘度は５０００ｍＰａ・ｓ／２５℃に達した。熟成中の粘度の変化は見られなかった。エチレンイミン重合体水溶液中の残存エチレンイミンは１ｐｐｍ以下であり、得られたエチレンイミン重合体水溶液中の臭気度は３００ｐｐｍであった。
尚、ＰＶ値（撹拌動力（ｋＷ）／最終液量（ｍ３）は２．０ｋＷ／ｍ３で行った。
Thereafter, the water tank was changed to an oil tank, and the temperature of the reaction solution was raised to 120 ° C. in 30 minutes, followed by aging at 120 ° C. and a pressure of 0.1 MPaG for 5 hours. The viscosity of the reaction solution immediately after raising the temperature to 120 ° C. reached 5000 mPa · s / 25 ° C. There was no change in viscosity during aging. The residual ethyleneimine in the ethyleneimine polymer aqueous solution was 1 ppm or less, and the odor degree in the obtained ethyleneimine polymer aqueous solution was 300 ppm.
The PV value (stirring power (kW) / final liquid amount (m 3 ) was 2.0 kW / m 3 .
上記の方法により得られたエチレンイミン重合体水溶液１０００ｇをオイルバス上の攪拌機、蒸気凝縮抜出し器および温度計を備えたフラスコ反応器に仕込み、常圧にて、１１０℃に加熱して精製を行った。留出水をカットし、樹脂分５０％になったところで、分析した結果、残存するエチレンイミンは１ｐｐｍ以下であった。得られた精製エチレンイミン重合体水溶液中の臭気度は５０ｐｐｍであった。また、精製後の粘度は１７０００ｍＰａ・ｓ／２５℃であった。 1000 g of the ethyleneimine polymer aqueous solution obtained by the above method was charged into a flask reactor equipped with a stirrer, a vapor condensing / extracting device and a thermometer on an oil bath, and purified by heating to 110 ° C. at normal pressure. It was. Distilled water was cut and the resin content reached 50%. As a result of analysis, the remaining ethyleneimine was 1 ppm or less. The odor degree in the obtained purified ethyleneimine polymer aqueous solution was 50 ppm. The viscosity after purification was 17000 mPa · s / 25 ° C.
実施例２
温水温度を４５℃に変更した以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製前後のエチレンイミン重合体水溶液の臭気度はそれぞれ５００および２５０ｐｐｍであった。精製後のエチレンイミン重合体水溶液の樹脂分が５０％になったところで粘度は１６３００ｍＰａ・ｓ／２５℃であった。
実施例３
ＰＶ値（撹拌動力／最終液量）を０．７ｋＷ／ｍ３に変更した以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製前後のエチレンイミン重合体水溶液の臭気度はそれぞれ４５０および１５０ｐｐｍであった。精製後のエチレンイミン重合体水溶液の樹脂分が５０％になったところで粘度は１６８００ｍＰａ・ｓ／２５℃であった。
Example 2
Except having changed the warm water temperature into 45 degreeC, it implemented similarly to Example 1 and obtained ethyleneimine polymer aqueous solution. The odor level of the ethyleneimine polymer aqueous solution before and after purification was 500 and 250 ppm, respectively. When the resin content of the purified ethyleneimine polymer aqueous solution reached 50%, the viscosity was 16300 mPa · s / 25 ° C.
Example 3
The same procedure as in Example 1 was conducted except that the PV value (stirring power / final liquid amount) was changed to 0.7 kW / m 3 to obtain an ethyleneimine polymer aqueous solution. The odor level of the ethyleneimine polymer aqueous solution before and after purification was 450 and 150 ppm, respectively. When the resin content of the purified ethyleneimine polymer aqueous solution reached 50%, the viscosity was 16800 mPa · s / 25 ° C.
比較例１
温水温度を３５℃未満（２５℃）に変更して、ＰＶ値（撹拌動力／最終液量）を０．３ｋＷ／ｍ３で行った以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製前後のエチレンイミン重合体水溶液の臭気度はそれぞれで８００及び６００ｐｐｍあった。精製後のエチレンイミン重合体水溶液の樹脂分が５０％になったところで粘度は１６１００ｍＰａ・ｓ／２５℃であった。
Comparative Example 1
This was carried out in the same manner as in Example 1 except that the hot water temperature was changed to less than 35 ° C. (25 ° C.) and the PV value (stirring power / final liquid amount) was 0.3 kW / m 3. Got. The odor levels of the ethyleneimine polymer aqueous solutions before and after purification were 800 and 600 ppm, respectively. When the resin content of the purified ethyleneimine polymer aqueous solution reached 50%, the viscosity was 16100 mPa · s / 25 ° C.
＜エチレンイミン重合体水溶液の安定性評価＞
実施例１、２、３及び比較例１で得られた精製前のエチレンイミン重合体水溶液を７０℃に保持し、１０日後の経時変化を調べた結果、実施例１及び比較例１で得られた水溶液の粘度は、それぞれ１６９００、１６２５０、１６８００及び１５５００ｍＰａ・ｓ／２５℃であった。
<Stability evaluation of ethyleneimine polymer aqueous solution>
The ethyleneimine polymer aqueous solution before purification obtained in Examples 1, 2, 3 and Comparative Example 1 was maintained at 70 ° C., and the change over time after 10 days was examined. As a result, it was obtained in Example 1 and Comparative Example 1. The aqueous solutions had viscosities of 16900, 16250, 16800, and 15500 mPa · s / 25 ° C., respectively.
実施例１および比較例１から明らかなように、本発明で得られるエチレンイミン重合体水溶液は臭気がないだけでなく、さらに驚くべきことには粘度の経時的な変化がほとんどない、品質の安定なエチレンイミン重合体水溶液を得られることが判明した。 As is clear from Example 1 and Comparative Example 1, the ethyleneimine polymer aqueous solution obtained in the present invention has not only odor but also surprisingly there is almost no change in viscosity over time, and quality stability. It has been found that an aqueous ethyleneimine polymer solution can be obtained.
本発明のエチレンイミン重合体水溶液は、紙加工剤、接着剤、粘着剤、塗料、インキ、繊維処理剤、凝集分離剤、化粧品、トイレタリー、分散剤などの分野で安全に利用することができる。 The aqueous ethyleneimine polymer solution of the present invention can be safely used in fields such as paper processing agents, adhesives, pressure-sensitive adhesives, paints, inks, fiber treatment agents, aggregating / separating agents, cosmetics, toiletries, and dispersing agents.
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