JP5072472B2 - Method for producing quaternary ammonium salt using intermediate carboxylic acid residue as counter ion - Google Patents
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 41
- 150000001732 carboxylic acid derivatives Chemical group 0.000 title claims description 35
- 150000002500 ions Chemical class 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 halogen ion Chemical class 0.000 claims description 35
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Description
本発明は、水溶性加工油剤、水溶性洗浄剤や水処理剤等の凝集剤、抗乳化剤として有用な中級カルボン酸残基を対イオンとする第4級アンモニウム塩の製造方法に関する。 TECHNICAL FIELD The present invention relates to a method for producing a quaternary ammonium salt having a counter ion as an intermediate carboxylic acid residue useful as a water-soluble processing oil agent, an aggregating agent such as a water-soluble detergent and a water treatment agent, and a demulsifier.
従来から金属、ガラス及びセラミックス等の切削加工、研削加工及び塑性加工等において使用される種々の水溶性加工油剤には、加工機械等に使用される摺動面潤滑油、作動油、グリース等の混入による乳化を防止するために抗乳化剤が添加される。 Conventionally, various water-soluble processing fluids used in cutting, grinding and plastic working of metals, glass and ceramics, etc. include sliding surface lubricants, hydraulic oils, greases, etc. used in processing machines etc. A demulsifier is added to prevent emulsification due to contamination.
出願人は先に、中級カルボン酸残基を対イオンとする第4級アンモニウム塩を提供している(特許文献1)。中級カルボン酸残基を対イオンとする第4級アンモニウム塩は、高い抗乳化性を示し、またハロゲンイオンを含んでいないため、ハロゲンイオンに起因する機械等の金属部品の発錆及び腐食、燃焼時のダイオキシン発生等の問題もなく、抗乳化剤として非常に有用である。 The applicant has previously provided a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion (Patent Document 1). Quaternary ammonium salts with intermediate carboxylic acid residues as counter ions show high demulsibility and do not contain halogen ions, so rusting, corrosion, and burning of metal parts such as machinery caused by halogen ions It is very useful as a demulsifier without problems such as dioxin generation.
中級カルボン酸残基を対イオンとする第4級アンモニウム塩の製造方法としては、特許文献1に、ハロゲンイオンを対イオンとする第4級アンモニウム塩を原料として用い、当該第4級アンモニウム塩のハロゲンイオンを、メタノール、エタノール等の極性溶液中で水酸化カリウム、水酸化ナトリウム等と反応させてハロゲン化カリウム、ハロゲン化ナトリウム等として沈殿除去した後、該処理物に中級カルボン酸を反応させる方法、ならびにハロゲンイオンを対イオンとする第4級アンモニウム塩を陰イオン交換樹脂で処理してハロゲンイオンを水酸化物イオンと交換させた後(展開溶媒:水)、該処理物を中級カルボン酸を用いて中和する方法が記載されている。 As a method for producing a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion, Patent Document 1 discloses that a quaternary ammonium salt having a halogen ion as a counter ion is used as a raw material. A method in which halogen ions are reacted with potassium hydroxide, sodium hydroxide or the like in a polar solution such as methanol or ethanol to precipitate and remove them as potassium halide, sodium halide or the like, and then the treated product is reacted with intermediate carboxylic acid. , And a quaternary ammonium salt having a halogen ion as a counter ion with an anion exchange resin to exchange the halogen ion with a hydroxide ion (developing solvent: water). A method of using and neutralizing is described.
しかし、これらの方法の場合、上記アルカリまたは陰イオン交換樹脂での処理後、中級カルボン酸との反応までの間に、第4級アンモニウムが徐々に分解してしまい、中級カルボン酸残基を対イオンとする第4級アンモニウム塩を収率よく製造することができなかった。また、陰イオン交換樹脂での処理は、コストが高いという問題もある。 However, in these methods, the quaternary ammonium gradually decomposes after the treatment with the alkali or anion exchange resin and before the reaction with the intermediate carboxylic acid, and the intermediate carboxylic acid residue is paired with the intermediate carboxylic acid residue. The quaternary ammonium salt used as an ion could not be produced with good yield. In addition, the treatment with an anion exchange resin has a problem of high cost.
かかる状況の下、より高収率かつ低コストで中級カルボン酸残基を対イオンとする第4級アンモニウム塩を製造する方法の開発が強く望まれている。
本発明の課題は、中級カルボン酸残基を対イオンとする第4級アンモニウム塩を高収率かつ低コストで製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for producing a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion in a high yield and at a low cost.
本発明者は、上記従来技術の問題点に鑑み鋭意検討を行った結果、ハロゲンイオンを対イオンとする第4級アンモニウム塩及び中級カルボン酸と無機アルカリとの塩を極性溶媒中で反応させると、第4級アンモニウムの分解を抑制しつつ、ハロゲンイオンを中級カルボン酸残基で置換することでき、中級カルボン酸残基を対イオンとする第4級アンモニウム塩を高収率で製造できることを見出した。本発明は、係る新しい知見に基づくものである。 As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventors have reacted a quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid and an inorganic alkali in a polar solvent. And found that a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion can be produced in a high yield, while the halogen ion can be substituted with an intermediate carboxylic acid residue while inhibiting the decomposition of the quaternary ammonium. It was. The present invention is based on such new knowledge.
従って、本発明は、以下の方法を提供する:
項1.ハロゲンイオンを対イオンとする第4級アンモニウム塩及び中級カルボン酸と無機アルカリとの塩を極性溶媒中で反応させて、ハロゲンイオンを中級カルボン酸残基で置換することを特徴とする、中級カルボン酸残基を対イオンとする第4級アンモニウム塩の製造方法。
項2.前記反応で生成する無機アルカリのハロゲン化物を除去する工程をさらに含む、項1に記載の方法。
項3.ハロゲンイオンを対イオンとする第4級アンモニウム塩が下記の重合物(A)〜(F)の少なくとも1種とハロゲンイオンとの塩である、項1または2に記載の方法:
(A)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩の重合物、
(B)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を少なくとも1個有するビニル系単量体もしくはその塩との共重合物、
(C)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を有さない重合可能な単量体との共重合物、
(D)ポリアルキレンポリアミンとジハロゲン化エチルエーテルとの重縮合物の4級化アンモニウム塩、
(E)ポリアルキレンポリアミンとジハロアルカンとの共重合物の4級化アンモニウム塩及び
(F)アルキレンジアミンとエポキシ化合物との重縮合物の4級化アンモニウム塩。
Accordingly, the present invention provides the following methods:
Item 1. A quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid and an inorganic alkali are reacted in a polar solvent to replace the halogen ion with an intermediate carboxylic acid residue. And a method for producing a quaternary ammonium salt using a intermediate carboxylic acid residue as a counter ion.
Item 2. The method according to Item 1, further comprising a step of removing an inorganic alkali halide produced in the reaction.
Item 3. The method according to Item 1 or 2, wherein the quaternary ammonium salt having a halogen ion as a counter ion is a salt of at least one of the following polymers (A) to (F) and a halogen ion:
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom,
(B) Copolymerization of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a vinyl monomer having at least one basic nitrogen atom or cationic nitrogen atom or a salt thereof. object,
(C) a copolymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom,
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) A quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane and (F) a quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound.
本発明の方法は、第4級アンモニウムの分解が抑制されるため、高収率で中級カルボン酸残基を対イオンとする第4級アンモニウム塩を製造することができる。また、本発明の方法には、高価な設備を必要としないため、低コストで行うことができる。 Since the decomposition of quaternary ammonium is suppressed, the method of the present invention can produce a quaternary ammonium salt having a intermediate carboxylic acid residue as a counter ion in high yield. In addition, since the method of the present invention does not require expensive equipment, it can be performed at low cost.
本発明の方法は、(a)ハロゲンイオンを対イオンとする第4級アンモニウム塩と、(b)中級カルボン酸と無機アルカリとの塩とを、極性溶媒中で反応させてハロゲンイオンを中級カルボン酸残基で置換することを特徴とする。 In the method of the present invention, (a) a quaternary ammonium salt having a halogen ion as a counter ion, and (b) a salt of an intermediate carboxylic acid and an inorganic alkali are reacted in a polar solvent to convert the halogen ion to an intermediate carboxyl. It is characterized by substitution with an acid residue.
ハロゲンイオンとしては、フッ化物イオン、塩化物イオン、臭化物イオン、及びヨウ化物イオンが挙げられる。 Halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions.
ハロゲンイオンを対イオンとする第4級アンモニウム塩としては、例えば、下記の重合物(A)〜(F)の少なくとも1種が挙げられる:
(A)カチオン性窒素原子を少なくとも1個(好ましくは1個)有するビニル系単量体の第4級アンモニウム塩の重合物、
(B)カチオン性窒素原子を少なくとも1個(好ましくは1個)有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を少なくとも1個(好ましくは1個)有するビニル系単量体もしくはその塩との共重合物、
(C)カチオン性窒素原子を少なくとも1個(好ましくは1個)有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を有さない重合可能な単量体との共重合物、
(D)ポリアルキレンポリアミンとジハロゲン化エチルエーテルとの重縮合物の4級化アンモニウム塩、
(E)ポリアルキレンポリアミンとジハロアルカンとの共重合物の4級化アンモニウム塩及び
(F)アルキレンジアミンとエポキシ化合物との重縮合物の4級化アンモニウム塩。
Examples of the quaternary ammonium salt having a halogen ion as a counter ion include at least one of the following polymers (A) to (F):
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom,
(B) A quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom and at least one (preferably one) basic nitrogen atom or cationic nitrogen atom. A copolymer with a vinyl monomer or a salt thereof,
(C) a quaternary ammonium salt of a vinyl monomer having at least one (preferably one) cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom Copolymer of
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) A quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane and (F) a quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound.
重合物(A)としては式(1): As the polymer (A), the formula (1):
[式中、R1は水素原子またはメチル基を示し、R2〜R4は各々独立して炭素原子1〜5、好ましくは1〜3のアルキル基を示し、Xはハロゲン原子を示し、nは6〜60000、好ましくは10〜1000の数を示す]
で表されるN,N−ジアルキルアミノエチル(メタ)アクリレート重合物の第4級アンモニウム塩及び式(2):
[Wherein, R 1 represents a hydrogen atom or a methyl group, R 2 to R 4 each independently represents an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms, X represents a halogen atom, and n Represents a number of 6 to 60000, preferably 10 to 1000]
A quaternary ammonium salt of an N, N-dialkylaminoethyl (meth) acrylate polymer represented by formula (2):
[式中、R2、R3、X及びnは前記と同義である]
で表されるジアリルジアルキルアンモニウムハロゲン化物の環化重合物が例示される。
[Wherein R 2 , R 3 , X and n are as defined above]
And cyclized polymers of diallyldialkylammonium halides represented by the formula:
重合物(B)としては式(3): As the polymer (B), the formula (3):
[式中、R1〜R4及びXは前記と同意義であり、R1’は水素原子またはメチル基を示し、oは4〜60000、好ましくは4〜500の数を示し、pは4〜100000、好ましくは4〜500の数を示す]
で表されるN,N−ジアルキルアミノエチル(メタ)アクリレートと(メタ)アクリルアミドとの共重合物の第4級アンモニウム塩及び式(4):
[Wherein R 1 to R 4 and X are as defined above, R 1 ′ represents a hydrogen atom or a methyl group, o represents 4 to 60000, preferably 4 to 500, and p represents 4 To 100000, preferably 4 to 500]
A quaternary ammonium salt of a copolymer of N, N-dialkylaminoethyl (meth) acrylate and (meth) acrylamide represented by formula (4):
[式中、R1〜R3、X、o及びpは前記と同義である]
で表されるジアリルジアルキルアンモニウムハロゲン化物と(メタ)アクリルアミドの共重合物が例示される。
[Wherein, R 1 to R 3 , X, o and p are as defined above]
And a copolymer of (ally) dialkylammonium halide represented by the formula (meth) acrylamide.
重合物(C)としては式(5): As the polymer (C), the formula (5):
[式中、R2、R3及びXは前記と同義であり、sは4〜40000、好ましくは4〜500の数を示す]
で表されるジアリルジアルキルアンモニウムハロゲン化物と二酸化硫黄の共重合物が例示される。
[Wherein R 2 , R 3 and X are as defined above, and s represents a number of 4 to 40000, preferably 4 to 500]
And a copolymer of diallyldialkylammonium halide and sulfur dioxide represented by the formula:
重合物(D)としては式(6): As the polymer (D), the formula (6):
[式中、R2〜R4及びXは前記と同意義であり、R5は炭素原子数1〜5、好ましくは1〜3のアルキル基を示し、R6は炭素原子数1〜10、好ましくは1〜6のアルキレン基を示し、tは4〜40000、好ましくは4〜400の数を示す]
で表されるテトラアルキルアルキレンジアミンと2,2−ジクロロアルキルエーテルとの共重合物が例示される。
[Wherein R 2 to R 4 and X are as defined above, R 5 represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and R 6 represents 1 to 10 carbon atoms, Preferably an alkylene group of 1 to 6 is shown, and t is a number of 4 to 40,000, preferably 4 to 400]
A copolymer of a tetraalkylalkylenediamine represented by the formula (2) and 2,2-dichloroalkyl ether is exemplified.
重合物(E)としては式(7): As the polymer (E), the formula (7):
[式中、R2〜R5及びXは前記と同意義であり、R7は炭素原子数1〜4、好ましくは2または3のアルキレン基を示し、R8は炭素原子数2〜10、好ましくは2〜6のアルキレン基を示し、uは10〜100000、好ましくは10〜1000の数を示す]
で表されるアルキレンジクロライドとアルキレンポリアミンの共重合物の第4級アンモニウム塩が例示される。
[Wherein R 2 to R 5 and X are as defined above, R 7 represents an alkylene group having 1 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and R 8 represents 2 to 10 carbon atoms, Preferably it shows 2-6 alkylene groups, u shows the number of 10-100,000, preferably 10-1000]
The quaternary ammonium salt of the copolymer of the alkylene dichloride and alkylene polyamine represented by these is illustrated.
重合物(F)としては式(8): As the polymer (F), the formula (8):
[式中、R2〜R5、R7、X及びuは前記と同義である]
で表されるアルキレンジアミンとエピハロヒドリンとの共重合物の第4級アンモニウム塩が例示される。
[Wherein, R 2 to R 5 , R 7 , X and u are as defined above]
The quaternary ammonium salt of the copolymer of alkylenediamine and epihalohydrin represented by these is illustrated.
上記の重合物(A)〜(F)の平均分子量は300〜10000000、好ましくは300〜100000である。特に好ましい重合物は(A)、(C)及び(D)である。 The average molecular weight of the above polymers (A) to (F) is 300 to 10000000, preferably 300 to 100,000. Particularly preferred polymers are (A), (C) and (D).
本発明において、中級カルボン酸残基とは、炭素原子数6〜12のカルボン酸を意味し、例えば、ヘキサン酸、オクタン酸、ノナン酸、3,5,5トリメチルヘキサン酸、デカン酸、安息香酸、ニトロ安息香酸、t−ブチル安息香酸、アジピン酸、セバシン酸等が挙げられる。 In the present invention, the intermediate carboxylic acid residue means a carboxylic acid having 6 to 12 carbon atoms. For example, hexanoic acid, octanoic acid, nonanoic acid, 3,5,5 trimethylhexanoic acid, decanoic acid, benzoic acid , Nitrobenzoic acid, t-butylbenzoic acid, adipic acid, sebacic acid and the like.
従って、中級カルボン酸残基としては、炭素原子数6〜12のカルボン酸、例えば、ヘキサン酸、オクタン酸、ノナン酸、3,5,5トリメチルヘキサン酸、デカン酸、安息香酸、ニトロ安息香酸、t−ブチル安息香酸、アジピン酸、セバシン酸等から誘導されるカルボン酸残基が挙げられる。 Accordingly, as the intermediate carboxylic acid residue, a carboxylic acid having 6 to 12 carbon atoms such as hexanoic acid, octanoic acid, nonanoic acid, 3,5,5 trimethylhexanoic acid, decanoic acid, benzoic acid, nitrobenzoic acid, Examples thereof include carboxylic acid residues derived from t-butylbenzoic acid, adipic acid, sebacic acid and the like.
中級カルボン酸と無機アルカリとの塩は、前記中級カルボン酸を無機アルカリで中和することにより調製しても、市販品を入手して用いてもよい。 The salt of intermediate carboxylic acid and inorganic alkali may be prepared by neutralizing the intermediate carboxylic acid with inorganic alkali, or a commercially available product may be used.
無機アルカリとしては、例えば、水酸化カリウム、水酸化ナトリウム、水酸化リチウム等のアルカリ金属水酸化物が挙げられる。 As an inorganic alkali, alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, are mentioned, for example.
本発明の方法において、中級カルボン酸と無機アルカリとの塩の使用割合は、ハロゲンイオンを対イオンとする第4級アンモニウム塩に対して、中級カルボン酸当量として、1〜3当量、好ましくは1〜2当量である。 In the method of the present invention, the ratio of the salt of the intermediate carboxylic acid and inorganic alkali used is 1 to 3 equivalents, preferably 1 as the intermediate carboxylic acid equivalents with respect to the quaternary ammonium salt having a halogen ion as a counter ion. ~ 2 equivalents.
極性溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、水等が挙げられる。 Examples of the polar solvent include methanol, ethanol, isopropyl alcohol, water, and the like.
メタノール、エタノール、イソプロピルアルコール等に対する高分子の溶解度が著しく小さい実施形態においては、少量の水とこれらの有機溶媒とを混合するのが、最終収率が改善し得るため好ましい。 In embodiments where the solubility of the polymer in methanol, ethanol, isopropyl alcohol, etc. is significantly low, mixing a small amount of water with these organic solvents is preferred because the final yield can be improved.
極性溶媒は、1種単独で又は2種以上混合して使用される。 A polar solvent is used individually by 1 type or in mixture of 2 or more types.
極性溶媒の使用量は、ハロゲンイオンを対イオンとする第4級アンモニウム塩1gに対して、通常0.1〜100ml、好ましくは0.2〜100ml、より好ましくは0.5〜50mlである。 The usage-amount of a polar solvent is 0.1-100 ml normally with respect to 1g of quaternary ammonium salts which make a halogen ion a counter ion, Preferably it is 0.2-100 ml, More preferably, it is 0.5-50 ml.
上記反応の温度は、通常−10〜80℃で、好ましくは0〜40℃である。上記温度範囲で反応させることによって、反応が進行しやすくなり、かつ反応原料及び生成物の分解が抑制される。 The temperature of the reaction is usually −10 to 80 ° C., preferably 0 to 40 ° C. By making it react in the said temperature range, reaction becomes easy to advance and decomposition | disassembly of a reaction raw material and a product is suppressed.
好ましい実施形態において、本発明の方法は、極性溶媒に中級カルボン酸及び無機アルカリを溶解し、当該溶液にハロゲンイオンを対イオンとする第4級アンモニウム塩またはその溶液を添加して反応させることにより行われる。 In a preferred embodiment, the method of the present invention comprises dissolving a intermediate carboxylic acid and an inorganic alkali in a polar solvent, and adding a quaternary ammonium salt having a halogen ion as a counter ion or a solution thereof to the solution to react. Done.
上記反応において、第4級アンモニウム塩のハロゲンイオンは中級カルボン酸で置換されて、中級カルボン酸残基を対イオンとする第4級アンモニウム塩が得られ、ハロゲンイオンは無機アルカリと塩を形成し、無機アルカリのハロゲン化物として析出、沈殿する。 In the above reaction, the halogen ion of the quaternary ammonium salt is substituted with a intermediate carboxylic acid to obtain a quaternary ammonium salt having the intermediate carboxylic acid residue as a counter ion, and the halogen ion forms a salt with an inorganic alkali. And precipitated as inorganic alkali halides.
上記反応式で得られる目的化合物は、反応混合物を、例えば、冷却した後、濾過、濃縮、抽出等の単離操作によって粗反応生成物を分離し、カラムクロマトグラフィー、再結晶等の通常の精製操作によって、反応混合物から単離精製することができる。 The target compound obtained by the above reaction formula can be obtained by cooling the reaction mixture, for example, and then separating the crude reaction product by an isolation operation such as filtration, concentration, extraction, etc., and performing normal purification such as column chromatography and recrystallization. By the operation, it can be isolated and purified from the reaction mixture.
好ましい実施形態において、本発明の方法は、上記反応により得られた無機アルカリのハロゲン化物を反応混合物より除去する工程を含む。 In a preferred embodiment, the method of the present invention includes a step of removing the inorganic alkali halide obtained by the above reaction from the reaction mixture.
無機アルカリのハロゲン化物の除去方法は、当該分野において通常用いられる方法を広く使用することができ、例えば、濾過、遠心分離等が挙げられる。 As a method for removing the halide of inorganic alkali, a method commonly used in the art can be widely used, and examples thereof include filtration and centrifugation.
実施例1
メタノール40mlを100mlビーカーに入れ、水酸化カリウム4.4gを加え溶解し、25℃になるまで放冷した。次いで、3,5,5トリメチルヘキサン酸10.8gを加え、撹拌しながら25℃になるまで放冷した。その後、下記の式(9)の化合物[ポリエチレンポリアミンとジクロロエチルエーテルとの共重合物の4級化物(分子量:約1500、塩素含有量:18重量%、60%水溶液)]10.0gを加え10分間撹拌した。25℃まで冷却後、懸濁液をG4のグラスフィルターで濾過し、塩化カリウムの沈殿を分離した。ろ液のメタノールをロータリーエバポレーターを用いて減圧留去し、下記の式(10)の第4級アンモニウム塩化合物を18.5g得た(水分を含む)。収率は、このとき除去された塩化カリウム重量3.2gから計算して、85%という結果を得た。
Example 1
40 ml of methanol was put into a 100 ml beaker, 4.4 g of potassium hydroxide was added and dissolved, and the mixture was allowed to cool to 25 ° C. Next, 10.8 g of 3,5,5 trimethylhexanoic acid was added and allowed to cool to 25 ° C. with stirring. Thereafter, 10.0 g of a compound of the following formula (9) [quaternized product of a copolymer of polyethylene polyamine and dichloroethyl ether (molecular weight: about 1500, chlorine content: 18% by weight, 60% aqueous solution)] was added. Stir for 10 minutes. After cooling to 25 ° C., the suspension was filtered through a G4 glass filter to separate the potassium chloride precipitate. The filtrate methanol was distilled off under reduced pressure using a rotary evaporator to obtain 18.5 g of a quaternary ammonium salt compound of the following formula (10) (including water). The yield was calculated from the weight of potassium chloride removed at this time of 3.2 g, and a result of 85% was obtained.
[式中、vは約6である。] [Wherein v is about 6. ]
[式中、vは約6である。]
化合物(10)の物性を表1に示す。
[Wherein v is about 6. ]
Table 1 shows the physical properties of the compound (10).
比較例
メタノール40mlを100mlビーカーに入れ、水酸化カリウム4.4gを加え溶解し、25℃になるまで放冷した。次いで、式(9)の化合物[ポリエチレンポリアミンとジクロロエチルエーテルとの共重合物の4級化物(分子量:約1500、塩素含有量:25重量%、60%水溶液)]10.0gを加え10分間撹拌した。続いて3,5,5トリメチルヘキサン酸10.8g(塩化物イオンに対して1.5当量)を加え、撹拌しながら25℃になるまで放冷した。その後、25℃まで冷却後、懸濁液をG4のグラスフィルターで濾過し、塩化カリウムの沈殿を分離した。ろ液のメタノールをロータリーエバポレーターを用いて減圧留去した。
Comparative Example 40 ml of methanol was placed in a 100 ml beaker, 4.4 g of potassium hydroxide was added and dissolved, and the mixture was allowed to cool to 25 ° C. Next, 10.0 g of a compound of the formula (9) [quaternized product of a copolymer of polyethylene polyamine and dichloroethyl ether (molecular weight: about 1500, chlorine content: 25% by weight, 60% aqueous solution)] was added for 10 minutes. Stir. Subsequently, 10.8 g of 3,5,5 trimethylhexanoic acid (1.5 equivalents relative to chloride ions) was added, and the mixture was allowed to cool to 25 ° C. with stirring. Then, after cooling to 25 ° C., the suspension was filtered through a G4 glass filter to separate potassium chloride precipitate. The methanol in the filtrate was distilled off under reduced pressure using a rotary evaporator.
上記手法では、目的とする化合物である式(10)の化合物を得ることができず、分解物の式(11)の化合物と3,5,5トリメチルヘキサン酸の混合物が得られた。 In the above method, the target compound of formula (10) could not be obtained, and a mixture of the decomposed compound of formula (11) and 3,5,5 trimethylhexanoic acid was obtained.
化合物(11)の物性を表2に示す。 Table 2 shows the physical properties of the compound (11).
実施例2
出発原料として式(12)
Example 2
Formula (12) as starting material
[式中、wは約180である。]
で表される化合物[N,N−ジアルキルアミノエチル(メタ)アクリレート重合物の第4級アンモニウム塩]を用い、実施例1と同様の操作をすることにより、式(12)の化合物の分解を抑制しつつ、式(13)
[Wherein w is about 180. ]
The compound of the formula (12) is decomposed by the same operation as in Example 1 using the compound represented by the formula [quaternary ammonium salt of N, N-dialkylaminoethyl (meth) acrylate polymer]. Equation (13) while suppressing
[式中、wは約180である。]
で表される第4級アンモニウム塩化合物を得ることができた。
[Wherein w is about 180. ]
The quaternary ammonium salt compound represented by this was able to be obtained.
実施例3
出発原料として式(14)
Example 3
Formula (14) as starting material
[式中、xは約250である。]
で表される化合物[ジアリルジアルキルアンモニウムハロゲン化物の環化重合物]を用い、実施例1と同様の操作をすることにより、式(14)の化合物の分解を抑制しつつ、式(15)
[Wherein x is about 250. ]
And a compound represented by formula (15) while suppressing decomposition of the compound of formula (14) by performing the same operation as in Example 1 using the compound [cyclized polymer of diallyldialkylammonium halide].
[式中、xは約250である。]
で表される第4級アンモニウム塩化合物を得ることができた。
[Wherein x is about 250. ]
The quaternary ammonium salt compound represented by this was able to be obtained.
実施例4
出発原料として式(16)
Example 4
Formula (16) as starting material
[式中、yは約12である。]
で表される化合物[ジアリルジアルキルアンモニウムハロゲン化物と二酸化硫黄の共重合物]を用い、実施例1と同様の操作をすることにより、式(16)の化合物の分解を抑制しつつ、式(17)
[Wherein y is about 12. ]
And a compound represented by the formula (17), a copolymer of diallyldialkylammonium halide and sulfur dioxide, by the same operation as in Example 1, while suppressing the decomposition of the compound of formula (16), )
[式中、yは約12である。]
で表される第4級アンモニウム塩化合物を得ることができる。
[Wherein y is about 12. ]
The quaternary ammonium salt compound represented by these can be obtained.
本発明の方法によって得られた中級カルボン酸残基を対イオンとする第4級アンモニウム塩は、ハロゲンを含有していないため、金属部品への錆や腐食を生じることなく、また、ダイオキシンの発生が無い油分離剤、凝集沈殿剤として特に有用であり、水溶性加工油剤、水溶性洗浄剤、水処理剤等の分野において利用できる。 Since the quaternary ammonium salt obtained by the method of the present invention with the intermediate carboxylic acid residue as a counter ion does not contain a halogen, it does not cause rust and corrosion to metal parts and generates dioxins. It is particularly useful as an oil separating agent and a coagulating precipitant, and can be used in the fields of water-soluble processing oils, water-soluble cleaning agents, water treatment agents and the like.
Claims (2)
ハロゲンイオンを対イオンとする第4級アンモニウム塩が下記の重合物(A)〜(F)の少なくとも1種とハロゲンイオンとの塩である、方法:
(A)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩の重合物、
(B)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を少なくとも1個有するビニル系単量体もしくはその塩との共重合物、
(C)カチオン性窒素原子を少なくとも1個有するビニル系単量体の第4級アンモニウム塩と塩基性窒素原子もしくはカチオン性窒素原子を有さない重合可能な単量体との共重合物、
(D)ポリアルキレンポリアミンとジハロゲン化エチルエーテルとの重縮合物の4級化アンモニウム塩、
(E)ポリアルキレンポリアミンとジハロアルカンとの共重合物の4級化アンモニウム塩及び
(F)アルキレンジアミンとエポキシ化合物との重縮合物の4級化アンモニウム塩。 A reaction between a quaternary ammonium salt having a halogen ion as a counter ion and a salt of an intermediate carboxylic acid having 6 to 12 carbon atoms and an inorganic alkali in a polar solvent, and replacing the halogen ion with an intermediate carboxylic acid residue. A method for producing a quaternary ammonium salt characterized by having an intermediate carboxylic acid residue as a counter ion ,
A method in which the quaternary ammonium salt having a halogen ion as a counter ion is a salt of at least one of the following polymers (A) to (F) and a halogen ion:
(A) a polymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom,
(B) Copolymerization of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a vinyl monomer having at least one basic nitrogen atom or cationic nitrogen atom or a salt thereof. object,
(C) a copolymer of a quaternary ammonium salt of a vinyl monomer having at least one cationic nitrogen atom and a polymerizable monomer having no basic nitrogen atom or no cationic nitrogen atom,
(D) quaternized ammonium salt of polycondensate of polyalkylene polyamine and dihalogenated ethyl ether,
(E) a quaternized ammonium salt of a copolymer of a polyalkylene polyamine and a dihaloalkane;
(F) A quaternized ammonium salt of a polycondensate of an alkylene diamine and an epoxy compound .
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JP3920976B2 (en) * | 1997-12-18 | 2007-05-30 | 株式会社ネオス | Water-soluble processing oil |
FR2846970B1 (en) * | 2002-11-08 | 2006-08-11 | Desarrollo Del Grafting S L | METHOD FOR SURFACE TREATMENT BY PHOTOPOLYMERIZATION TO OBTAIN BIOCIDAL PROPERTIES |
JP4781119B2 (en) * | 2006-02-02 | 2011-09-28 | 株式会社ネオス | New surfactant |
JP2008096920A (en) * | 2006-10-16 | 2008-04-24 | Ricoh Co Ltd | Diffractive optical element and its manufacturing method |
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