JP4300479B2 - Method for producing free allylamine polymer aqueous solution and free diallylamine polymer aqueous solution - Google Patents
Method for producing free allylamine polymer aqueous solution and free diallylamine polymer aqueous solution Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims description 173
- 239000007864 aqueous solution Substances 0.000 title claims description 114
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 title claims description 61
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 150000003839 salts Chemical class 0.000 claims description 74
- 239000002253 acid Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 37
- 238000011033 desalting Methods 0.000 claims description 34
- 239000007870 radical polymerization initiator Substances 0.000 claims description 32
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 239000003014 ion exchange membrane Substances 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 21
- 238000000909 electrodialysis Methods 0.000 claims description 18
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 4
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000243 solution Substances 0.000 description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 29
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 238000005341 cation exchange Methods 0.000 description 5
- 239000012847 fine chemical Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- -1 allylamine hydrochlorides Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- NZDQGDFGLKTOTA-UHFFFAOYSA-N 2-(3-carbamimidoylhexan-3-yldiazenyl)-2-ethylpentanimidamide Chemical compound N(=NC(CC)(CCC)C(N)=N)C(CC)(CCC)C(N)=N NZDQGDFGLKTOTA-UHFFFAOYSA-N 0.000 description 1
- RQPLYVCUCFVXLT-UHFFFAOYSA-N 2-(3-carbamimidoylpentan-3-yldiazenyl)-2-ethylbutanimidamide Chemical compound N(=NC(CC)(CC)C(N)=N)C(CC)(CC)C(N)=N RQPLYVCUCFVXLT-UHFFFAOYSA-N 0.000 description 1
- PDDPEXCLSVEGPK-UHFFFAOYSA-N 2-(4-carbamimidoylheptan-4-yldiazenyl)-2-propylpentanimidamide Chemical compound N(=NC(CCC)(CCC)C(N)=N)C(CCC)(CCC)C(N)=N PDDPEXCLSVEGPK-UHFFFAOYSA-N 0.000 description 1
- MWQNCDHGERUCLW-UHFFFAOYSA-N 2-[(1-amino-1-imino-2,3-dimethylbutan-2-yl)diazenyl]-2,3-dimethylbutanimidamide Chemical compound CC(C)C(C)(C(N)=N)N=NC(C)(C(C)C)C(N)=N MWQNCDHGERUCLW-UHFFFAOYSA-N 0.000 description 1
- PMWBFXVMQHUSKN-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylbutan-2-yl)diazenyl]-2-methylbutanimidamide Chemical compound CCC(C)(C(N)=N)N=NC(C)(CC)C(N)=N PMWBFXVMQHUSKN-UHFFFAOYSA-N 0.000 description 1
- OJJGEHIFTBYSKM-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpentan-2-yl)diazenyl]-2-methylpentanimidamide Chemical compound CCCC(C)(C(N)=N)N=NC(C)(C(N)=N)CCC OJJGEHIFTBYSKM-UHFFFAOYSA-N 0.000 description 1
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、遊離のアリルアミン類重合体水溶液の製造方法および遊離のジアリルアミン類重合体水溶液に関する。さらに詳しくは、本発明は、ファインケミカル分野などにおいて使用する際、ノンハロゲンであるので使用しやすい遊離のアリルアミン類重合体水溶液を効率よく製造する方法、および従来製造することができなかった安定性に優れる遊離のジアリルアミン類重合体水溶液に関するものである。 The present invention relates to a method for producing a free allylamine polymer aqueous solution and a free diallylamine polymer aqueous solution. More specifically, the present invention is excellent in a method for efficiently producing an aqueous solution of free allylamines that is easy to use because it is non-halogen when used in the field of fine chemicals, and the stability that could not be produced conventionally. The present invention relates to a free diallylamine polymer aqueous solution.
アリルアミン類塩酸塩重合体、例えば、ジアリルアミン類塩酸塩重合体は、近年、モノマーのアリルアミン類塩酸塩を、水溶液中、ラジカル重合触媒の存在下で重合させることにより簡単に製造でき、かつ、水溶性のカチオン系重合体であることから、工業的に製造され、金属保護処理剤、インクジェット記録関連、電子材料等の多様な分野に使用することが提案されている。 In recent years, allylamine hydrochloride polymers such as diallylamine hydrochloride polymers can be easily produced by polymerizing monomeric allylamine hydrochlorides in an aqueous solution in the presence of a radical polymerization catalyst, and are water-soluble. Therefore, it has been proposed to be industrially produced and used in various fields such as metal protective treatment agents, ink jet recording-related, and electronic materials.
しかしながら、アリルアミン類塩酸塩重合体は、塩素を含むので、セラミックバインダー向けや金属に接触する分野等では腐食性の原因となることが考えられ使いにくい場合もある。また、アリルアミン類塩酸塩重合体などがファインケミカル分野へ使用されることが検討されるに伴い、ノンハロゲンの重合体が要求され始めている。そこで、遊離のアリルアミン類重合体を得るため、アリルアミン類塩酸塩重合体をアルカリ水溶液で中和すると、不溶性物質として析出してきたり、水不溶性のゲル化が起こったりすることがあるため、遊離の重合体を水溶液としては得られないこともあった。その結果、特定のジアリルアミン類重合体のように、遊離型は水溶性でない、あるいは水不溶性のゲル化が起こると結論されていたものもあった。すなわち、あるアリルアミン類重合体は、塩の状態では水溶性で安定であるが、遊離の状態では、水に不溶であると結論付けられていたものも多かった。 However, since the allylamine hydrochloride polymer contains chlorine, it may be corrosive and may be difficult to use in ceramic binders and fields that come into contact with metals. In addition, as the use of allylamine hydrochloride polymers and the like in the fine chemical field has been studied, non-halogen polymers have begun to be required. Therefore, in order to obtain a free allylamine polymer, neutralization of the allylamine hydrochloride polymer with an aqueous alkaline solution may cause precipitation as an insoluble substance or gelation of water insolubles. In some cases, the coalescence cannot be obtained as an aqueous solution. As a result, it has been concluded that the free form is not water-soluble or water-insoluble gelation occurs as in the case of a specific diallylamine polymer. That is, some allylamine polymers have been concluded to be water-soluble and stable in the salt state but insoluble in water in the free state.
本発明は、このような事情のもとで、ファインケミカル分野などにおいて使用する際、ノンハロゲンであるので使用しやすい遊離のアリルアミン類重合体水溶液を効率よく製造する方法、および従来製造することができなかった安定性に優れる遊離のジアリルアミン類重合体水溶液を提供することを目的とするものである。 Under such circumstances, the present invention is a method for efficiently producing a free aqueous solution of a free allylamine polymer that is non-halogen when used in the field of fine chemicals and the like, and cannot be produced conventionally. Another object of the present invention is to provide a free diallylamine polymer aqueous solution having excellent stability.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、アリルアミン類の酸付加塩重合体水溶液を中和しながら脱塩処理することにより、遊離のアリルアミン類重合体水溶液を製造し得ること、特に水媒体中、ラジカル重合開始剤の存在下に、ジアリルアミン類の酸付加塩を、ある範囲の濃度で重合して、分子量が特定の範囲のジアリルアミン類の酸付加塩重合体を製造し、次いでその水溶液を中和しながら脱塩処理することにより、安定性に優れる遊離のジアリルアミン類重合体水溶液が、効率よく得られることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the present inventors have produced a free allylamine polymer aqueous solution by desalting while neutralizing the acid addition salt polymer aqueous solution of allylamines. In particular, in the presence of a radical polymerization initiator in an aqueous medium, an acid addition salt of diallylamine is polymerized in a certain range of concentration to obtain an acid addition salt polymer of diallylamine having a specific molecular weight range. It was found that a free diallylamine polymer aqueous solution having excellent stability can be efficiently obtained by producing and then desalting the aqueous solution while neutralizing the aqueous solution. The present invention has been completed based on such findings.
すなわち、本発明は、
（１） アリルアミン類の酸付加塩重合体水溶液を中和しながら脱塩処理することを特徴とする、遊離のアリルアミン類重合体水溶液の製造方法、
（２） アリルアミン類の酸付加塩重合体が、一般式（Ｉ）
That is, the present invention
(1) A method for producing a free aqueous solution of an allylamine polymer, wherein the desalting treatment is carried out while neutralizing the acid addition salt polymer aqueous solution of allylamines,
(2) An acid addition salt polymer of allylamine is represented by the general formula (I)
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体であり、かつ遊離のアリルアミン類重合体が、一般式（II）
A diallylamine acid addition salt polymer having a repeating unit represented by general formula (II) and having a weight average molecular weight of 400 to 4500
で表される繰り返し単位を有するジアリルアミン類重合体である上記（１）項に記載の方法、
（３） 水媒体中において、ラジカル重合開始剤の存在下、一般式（III）
The method according to item (1), wherein the polymer is a diallylamine polymer having a repeating unit represented by:
(3) General formula (III) in the presence of a radical polymerization initiator in an aqueous medium
で表されるジアリルアミン類の酸付加塩を、濃度５〜３５質量％の状態で重合し、一般式（Ｉ）
The acid addition salt of diallylamines represented by the general formula (I)
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体を製造し、次いでその水溶液を中和しながら脱塩処理することを特徴とする、一般式（II）
A diallylamine acid addition salt polymer having a weight average molecular weight of 400 to 4500 and having a repeating unit represented by the following general formula ( II)
で表される繰り返し単位を有する遊離のジアリルアミン類重合体水溶液の製造方法、
（４） 中和処理と脱塩処理を同時に行う工程を含む上記（１）ないし（３）項のいずれか１項に記載の方法、
（５） 中和処理と脱塩処理を同時に行う工程が、アルカリ水溶液にて連続的に中和しながら、同時に生成する中和塩を連続的に脱塩処理する工程である上記（４）項に記載の方法、
（６） 脱塩処理をイオン交換膜電気透析法で行う上記（５）項に記載の方法、
（７） 一般式（Ｉ）で表される繰り返し単位を有する重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体の製造を、反応系にジアリルアミン類の酸付加塩とラジカル重合開始剤とを連続的にまたは分割して添加しながら重合させることにより行う上記（３）ないし（６）項のいずれか１項に記載の方法、
（８） ラジカル重合開始剤を、ジアリルアミン類の酸付加塩に対し、０．８〜３０モル％の割合で用いる上記（３）ないし（７）項のいずれか１項に記載の方法、
A method for producing a free diallylamine polymer aqueous solution having a repeating unit represented by:
(4) The method according to any one of (1) to (3) above, comprising a step of simultaneously performing neutralization treatment and desalting treatment,
(5) Item (4) above, wherein the step of simultaneously performing the neutralization treatment and the desalting treatment is a step of continuously desalting the neutralized salt produced simultaneously while continuously neutralizing with an alkaline aqueous solution. The method described in
(6) The method according to (5) above, wherein the desalting treatment is performed by an ion exchange membrane electrodialysis method,
(7) Preparation of an acid addition salt polymer of diallylamines having a repeating unit represented by the general formula (I) and a weight average molecular weight of 400 to 4500, and an acid addition salt of a diallylamine and a radical polymerization initiator in the reaction system The method according to any one of the above (3) to (6), which is carried out by polymerizing while continuously or dividedly added,
(8) The method according to any one of (3) to (7) above, wherein the radical polymerization initiator is used at a ratio of 0.8 to 30 mol% with respect to the acid addition salt of diallylamines ,
を提供するものである。
Is to provide.
本発明によれば、ファインケミカル分野などにおいて使用する際、ノンハロゲンであるので使用しやすい遊離のアリルアミン類重合体水溶液を効率よく製造する方法、および従来製造することができなかった安定性に優れる遊離のジアリルアミン類重合体水溶液を提供することができる。 According to the present invention, when used in the field of fine chemicals and the like, a method for efficiently producing a free allylamine polymer aqueous solution that is non-halogen and easy to use, and free stability excellent in stability that could not be produced conventionally. A diallylamine polymer aqueous solution can be provided.
本発明の遊離のアリルアミン類重合体水溶液の製造方法においては、アリルアミン類の酸付加塩重合体水溶液を中和しながら脱塩処理することにより、目的の遊離のアリルアミン類重合体水溶液を製造する。 In the method for producing a free allylamine polymer aqueous solution of the present invention, the desired free allylamine polymer aqueous solution is produced by desalting the neutralized allylamine acid addition salt polymer aqueous solution.
本発明で用いるアリルアミン類の酸付加塩重合体は、アリルアミノ基の付加塩をモノマーの一部として含むモノマーを構成単位として有する重合体であれば特に限定されない。このような重合体としては、モノアリルアミン類の酸付加塩やジアリルアミン類の酸付加塩をモノマーとして少なくとも１種類以上を含む重合体を例示できる。モノアリルアミン類の酸付加塩としては、Ｎ位に炭素数１〜４のアルキル基を１個又は２個含んでもよいモノアリルアミンの酸付加塩が好ましく、また、ジアリルアミン類の酸付加塩としては、Ｎ位に炭素数１〜４のアルキル基を含んでもよいジアリルアミンの酸付加塩が好ましい。酸付加塩としては、塩酸塩、硫酸塩、硝酸塩などを例示することができる。 The acid addition salt polymer of allylamines used in the present invention is not particularly limited as long as it is a polymer having a monomer containing an addition salt of an allylamino group as a part of the monomer as a constituent unit. Examples of such a polymer include a polymer containing at least one kind of acid addition salt of monoallylamine or acid addition salt of diallylamine. The acid addition salt of monoallylamines is preferably an acid addition salt of monoallylamine which may contain one or two alkyl groups having 1 to 4 carbon atoms at the N position, and as acid addition salts of diallylamines, Preferred is an acid addition salt of diallylamine which may contain an alkyl group having 1 to 4 carbon atoms at the N position. Examples of the acid addition salt include hydrochloride, sulfate, nitrate and the like.
本発明において好適なアリルアミン類の酸付加塩重合体は、モノアリルアミン類やジアリルアミン類などのアリルアミン類の酸付加塩を重合して得られるものであり、かつ、その付加塩の重合体の水溶液を、アルカリで中和したときに沈殿が発生したり、ゲル化が起こりやすいが、中和で生じた無機塩等の中和塩を除去して遊離のアリルアミン類重合体にしたときには水に溶けるものが好適である。 Suitable acid addition salt polymers of allylamines in the present invention are obtained by polymerizing acid addition salts of allylamines such as monoallylamines and diallylamines, and an aqueous solution of the addition salt polymer is used. Precipitating or gelation is likely when neutralized with alkali, but it is soluble in water when neutralized salts such as inorganic salts generated by neutralization are removed to make free allylamine polymers. Is preferred.
なお、本発明において、遊離のアリルアミン類重合体とは、アリルアミン類の酸付加塩重合体から、酸付加塩が取れた重合体を指す。この遊離のアリルアミン類重合体は、酸付加塩が、好ましくは９０％以上、より好ましくは９５％以上、特に好ましくは９９％以上取れたものが望ましい。 In the present invention, the free allylamine polymer refers to a polymer obtained by removing an acid addition salt from an acid addition salt polymer of allylamines. The free allylamine polymer preferably has an acid addition salt of preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more.
本発明において、中和しながら脱塩処理するとは、脱塩した遊離のアリルアミン類重合体を製造する際、中和を完全に行ってから脱塩をするのではなく、生成する中和塩の存在が少ない状態で脱塩操作を行う方法であれば特に限定しない。例えば、一部中和と脱塩の２つの操作を繰り返す方法や連続中和の状態で脱塩を連続的にを行う工程、すなわち、中和処理と脱塩処理を同時に行う工程を含む方法を例示することができる。通常は、アリルアミン類の酸付加塩重合体の水溶液にアルカリ等を加え、沈殿が生じない程度のｐＨまで、好ましくは沈殿が生じる手前のｐＨまで、より好ましくはｐＨ８〜１０まで、さらに好ましくはｐＨ８．５〜９．８まで一気に中和し、次いで、脱塩した後、さらにそれらの中和と脱塩を同時に行う工程で脱塩することが好ましい。ｐＨ８〜１０以下までは酸付加塩が十分に存在し、十分な水溶性を保ちやすいからである。 In the present invention, the desalting treatment while neutralizing means that when producing a desalted free allylamine polymer, neutralization is not performed after completely neutralizing, but the neutralized salt produced The method is not particularly limited as long as it is a method of performing a desalting operation in a state where the presence is small. For example, a method of repeating two operations of partial neutralization and desalting or a step of continuously performing desalting in a state of continuous neutralization, that is, a method including a step of simultaneously performing neutralization treatment and desalting treatment. It can be illustrated. Usually, an alkali or the like is added to an aqueous solution of an allylamine acid addition salt polymer to a pH at which precipitation does not occur, preferably to a pH before precipitation occurs, more preferably to pH 8 to 10, more preferably pH 8. It is preferable to neutralize at a stretch from 0.5 to 9.8, and then desalting, followed by desalting in the step of carrying out neutralization and desalting at the same time. This is because the acid addition salt is sufficiently present up to pH 8 to 10 or less and it is easy to maintain sufficient water solubility.
中和処理と脱塩処理を同時に行う工程としては、水酸化ナトリウム、水酸化カリウム等のアルカリ水溶液にて連続的に中和しながら、同時に生成する中和塩を連続的に脱塩することが好ましい。このような状態で脱塩することにより、中和反応の系内では、無機塩等の中和塩が少なくなり遊離の重合体が析出したり、水不溶性のゲル化が起こったりすることを防止することができる。 As a step of performing the neutralization treatment and the desalting treatment at the same time, the neutralized salt produced simultaneously can be continuously desalted while continuously neutralizing with an aqueous alkali solution such as sodium hydroxide or potassium hydroxide. preferable. By desalting in such a state, neutralization salts such as inorganic salts are reduced in the neutralization reaction system, preventing free polymer precipitation and water-insoluble gelation. can do.
本発明において脱塩処理は膜透析で脱塩することが好ましく、イオン交換膜電気透析で脱塩することがさらに好ましい。イオン交換膜電気透析法は、カチオン系ポリマーに用いるイオン交換膜電気透析であれば特に限定しないが、特開昭６３−２８６４０５号公報等に記載のイオン交換膜電気透析膜等を用いることができる。 In the present invention, the desalting treatment is preferably desalted by membrane dialysis, and more preferably desalted by ion exchange membrane electrodialysis. The ion exchange membrane electrodialysis method is not particularly limited as long as it is an ion exchange membrane electrodialysis used for a cationic polymer, and an ion exchange membrane electrodialysis membrane described in JP-A-63-286405 can be used. .
このイオン交換膜電気透析法の実施態様を添付図面に従って説明する。図１は、本発明の方法において用いられる電気透析装置の１例の概略図であって、電槽９は、陽イオン交換膜Ｃと陰イオン交換膜Ａとが交互に並行に配列され、膜により区画された希釈室３、濃縮室４および電極室５より成立しており、電槽９の両端の電極室５には、それぞれ陽極と陰極の電極板６が設備されている。原液槽１に投入されたアリルアミン類の酸付加塩重合体水溶液は、ポンプＰ１により電槽９の希釈室３に送られる。本発明においてイオン交換膜電気透析法を用いてアルカリ水溶液にて連続的に中和しながら脱塩する場合は、通常、アルカリ水溶液をイオン交換膜電気透析装置の希釈室に加えるとよい。
An embodiment of the ion exchange membrane electrodialysis method will be described with reference to the accompanying drawings. FIG. 1 is a schematic view of an example of an electrodialysis apparatus used in the method of the present invention. In a battery case 9, a cation exchange membrane C and an anion exchange membrane A are alternately arranged in parallel. The
それにより、アリルアミン類の酸付加塩重合体、例えば、その塩酸塩重合体は、遊離のアリルアミン類重合体に変化するが、その際、中和塩、例えば、塩化ナトリウムは、陽イオン交換膜Ｃを通して濃縮室４へ移動する。この際、アリルアミン類の酸付加塩重合体および遊離のアリルアミン類重合体は陽イオン交換膜Ｃにより遮断され、希釈室３には中和塩等が除去された重合体がそのまま残留する。その際、遊離のアリルアミン類重合体は、中和塩等の無機物が少ないので、不溶化したりすることが妨げられる。一方、濃縮液槽２及び電極室５には、濃縮液たる電解液が投入され１〜２質量％程度のＮａＣｌ溶液または、Ｎａ２ＳＯ４溶液等が一般的に用いられるが、これらに限定されず電解質溶液であればいずれを用いてもよい。この濃縮液はポンプＰ２により濃縮室４へ送られる。
Thereby, the acid addition salt polymer of allylamines, for example, the hydrochloride polymer thereof is converted into a free allylamines polymer, and in this case, the neutralized salt, for example, sodium chloride is converted into the cation exchange membrane C. To the concentrating
この原液、濃縮液、および電極液をそれぞれ、希釈室、濃縮室、電極室へ循環させ、電極板６に直流電圧を印加することにより、原液槽１に投入された重合体水溶液からは、中和により生成する塩化ナトリウム等の中和塩等が透析除去され、濃縮液中に透析された中和塩は濃縮液槽２に濃縮されることにより、ついには、原液槽１には、中和が完了したアリルアミン類重合体水溶液が、濃縮液槽２には中和塩が濃縮貯蔵されることになる。かくして、中和塩等が除去された遊離のアリルアミン類重合体水溶液を得ることができる。なお、７は原液経路、８は濃縮液経路である。
The stock solution, the concentrate, and the electrode solution are circulated to the dilution chamber, the concentrate chamber, and the electrode chamber, respectively, and by applying a DC voltage to the electrode plate 6, the polymer aqueous solution introduced into the
本発明に用いられる陽イオン交換膜及び陰イオン交換膜は一般的なイオン交換膜（例えば旭硝子社製ＣＭＶ，ＡＭＶ等）でよく、特殊なイオン交換膜を用いる必要はあえてない。またこれらのイオン交換膜を装着させる電気透析槽も、市販されているものでよく、膜間隔、室数、室内透過等を特別に設定する必要はない。 The cation exchange membrane and anion exchange membrane used in the present invention may be general ion exchange membranes (for example, CMV and AMV manufactured by Asahi Glass Co., Ltd.), and it is not necessary to use special ion exchange membranes. Also, electrodialysis tanks to which these ion exchange membranes are attached may be commercially available, and it is not necessary to specifically set the membrane spacing, the number of chambers, indoor permeation, and the like.
本発明の方法においては、アリルアミン類の酸付加塩重合体としては、例えば一般式（Ｉ） In the method of the present invention, as the acid addition salt polymer of allylamines, for example, the general formula (I)
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体が好ましく、特にＮ−メチルジアリルアミン塩酸塩重合体が好適である。Ｘで示される酸残基としては、塩化物イオン、臭化物イオン、硝酸イオン、硫酸イオンなどが挙げられる。
The acid addition salt polymer of diallylamines having a repeating unit represented by the formula (1) and having a weight average molecular weight of 400 to 4500 is preferred, and N-methyldiallylamine hydrochloride polymer is particularly preferred. Examples of the acid residue represented by X include chloride ion, bromide ion, nitrate ion, sulfate ion and the like.
したがって、本発明においては、製造される遊離のアリルアミン類重合体としては、一般式（II） Therefore, in the present invention, the produced free allylamine polymers include those represented by the general formula (II)
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類重合体が好ましく挙げられ、特にＮ−メチルジアリルアミン重合体が好適である。
A diallylamine polymer having a weight average molecular weight of 400 to 4500 and having a repeating unit represented by the formula is preferred, and an N-methyldiallylamine polymer is particularly preferred.
なお、本発明における遊離のアリルアミン類重合体の分子量は、遊離のアリルアミン類重合体を塩酸塩にして、ゲルパーミエーション・クロマトグラフィー（ＧＰＣ）で測定した重量平均分子量をいう。 The molecular weight of the free allylamine polymer in the present invention refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using the free allylamine polymer as a hydrochloride.
前記一般式（II）で表される遊離のジアリルアミン類重合体のうち、遊離のＮ−メチルジアリルアミン重合体は、本発明者らの検討によると、長い間、種々の方法でも、水溶液としては得られなかった。また、従来、一般式（II）で表される遊離の重合体のうち、遊離のジアリルアミン重合体を、本発明者らの検討によると、ジアリルアミン塩酸塩重合体をアルカリで中和して製造しようとすると不溶性のゲルが生成しやすく、水溶液で安定した遊離のジアリルアミン重合体を得ることはできにくかった。 Among the free diallylamine polymers represented by the general formula (II), free N-methyl diallylamine polymer has been obtained as an aqueous solution by various methods for a long time according to the study by the present inventors. I couldn't. Conventionally, among the free polymers represented by the general formula (II), according to the study by the present inventors, a free diallylamine polymer is produced by neutralizing a diallylamine hydrochloride polymer with an alkali. As a result, an insoluble gel was easily formed, and it was difficult to obtain a free diallylamine polymer that was stable in an aqueous solution.
しかし、本発明の製造方法を用い、かつ、原料のジアリルアミン類の酸付加塩重合体、例えばＮ−メチルジアリルアミン塩酸塩重合体の重量平均分子量を４００〜４５００、好ましくは５００〜４２００、さらに好ましくは６００〜３８００の範囲に限定し、中和の際、塩濃度を少なくしながら脱塩することにより、遊離のジアリルアミン類重合体水溶液を得ることができる。また、この製造方法は、重合反応から目的のジアリルアミン類重合体水溶液、例えば、Ｎ−メチルジアリルアミン重合体水溶液を得ることまで、全工程を、水溶液の状態で行えるので、工業的に有利に適用できる。 However, the weight average molecular weight of the acid addition salt polymer of diallylamines as a raw material, for example, N-methyldiallylamine hydrochloride polymer, is 400 to 4500, preferably 500 to 4200, more preferably using the production method of the present invention. By limiting to the range of 600 to 3800 and desalting while reducing the salt concentration during neutralization, a free diallylamine polymer aqueous solution can be obtained. Moreover, since this manufacturing method can perform all processes in the state of aqueous solution until it obtains the target diallylamine polymer aqueous solution, for example, N-methyl diallylamine polymer aqueous solution, from a polymerization reaction, it can be applied industrially advantageously. .
遊離のＮ−メチルジアリルアミン重合体は、重量平均分子量が４５００を超えると、水溶液として得ることができにくい。また、重量平均分子量４００〜４５００の遊離のＮ−メチルジアリルアミン重合体の水溶液は、塩化ナトリウムのような中和塩が存在すると水溶液として得にくいことがある。また、遊離のジアリルアミン重合体は、重量平均分子量が４５００を超えると、水不溶性のゲルが発生し水溶液の状態で長時間保存しにくいことがある。
また、重量平均分子量４００〜４５００の遊離のジアリルアミン類重合体の水溶液は、塩化ナトリウムのような中和塩が存在すると水溶液として得にくいことがある。
When the weight average molecular weight exceeds 4500, it is difficult to obtain a free N-methyldiallylamine polymer as an aqueous solution. In addition, an aqueous solution of a free N-methyldiallylamine polymer having a weight average molecular weight of 400 to 4500 may be difficult to obtain as an aqueous solution in the presence of a neutralized salt such as sodium chloride. Further, when the free diallylamine polymer has a weight average molecular weight exceeding 4500, a water-insoluble gel is generated, and it may be difficult to store in a state of an aqueous solution for a long time.
In addition, an aqueous solution of a free diallylamine polymer having a weight average molecular weight of 400 to 4500 may be difficult to obtain as an aqueous solution in the presence of a neutralized salt such as sodium chloride.
本発明はまた、前記一般式（II）で表される繰り返し単位を有する、重量平均分子量が４００〜４５００の遊離のジアリルアミン類重合体水溶液をも提供する。
この重合体水溶液における遊離のジアリルアミン類重合体（乾燥重合体）中の中和塩、例えば、塩化ナトリウム等の灰分は、好ましくは５質量％以下、より好ましくは３質量％以下、さらに好ましくは１質量％以下、特に好ましくは実質的にゼロ、すなわち、０．５質量％以下がよい。
The present invention also provides a free diallylamine polymer aqueous solution having a repeating unit represented by the general formula (II) and having a weight average molecular weight of 400 to 4500.
The neutralized salt in the free diallylamine polymer (dry polymer) in this aqueous polymer solution, for example, ash such as sodium chloride, is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1%. The mass% or less, particularly preferably substantially zero, that is, 0.5 mass% or less is good.
次に、遊離のジアリルアミン類重合体水溶液の具体的な製造方法について説明する。
まず、水媒体中において、ラジカル重合開始剤の存在下、一般式（III）
Next, a specific method for producing a free diallylamine polymer aqueous solution will be described.
First, in the presence of a radical polymerization initiator in an aqueous medium, the general formula (III)
で表されるジアリルアミン類の酸付加塩を、濃度５〜３５質量％の状態で重合し、前記一般式（Ｉ）で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体を製造する。
Of the diallylamines having a weight average molecular weight of 400 to 4500 having a repeating unit represented by the general formula (I). An acid addition salt polymer is produced.
ジアリルアミン類の酸付加塩の濃度は、５〜３５質量％、好ましくは８〜３０質量％、より好ましくは１０〜２５質量％である。モノマー濃度が高すぎると重量平均分子量は大きくなりやすく、モノマー濃度が低すぎると重合が進みにくい。
用いるラジカル重合開始剤は、Ｎ−メチルジアリルアミン酸付加塩重合体を得る場合、モノマーに対し、１．２〜３０モル％が好ましく、１．８〜２０モル％がさらに好ましく、２．５〜１５モル％が特に好ましい。
また、ジアリルアミン酸付加塩重合体を得る場合、用いるラジカル重合開始剤は、モノマーに対し、０．８〜２０モル％が好ましく、１．０〜１２モル％がさらに好ましく、１．５〜８モル％が特に好ましい。
The concentration of the acid addition salt of diallylamine is 5 to 35% by mass, preferably 8 to 30% by mass, and more preferably 10 to 25% by mass. If the monomer concentration is too high, the weight average molecular weight tends to increase, and if the monomer concentration is too low, the polymerization is difficult to proceed.
The radical polymerization initiator to be used is preferably 1.2 to 30 mol%, more preferably 1.8 to 20 mol%, more preferably 2.5 to 15 with respect to the monomer when obtaining an N-methyldiallylamine acid addition salt polymer. Mole% is particularly preferred.
Moreover, when obtaining a diallylamic acid addition salt polymer, the radical polymerization initiator used is preferably 0.8 to 20 mol%, more preferably 1.0 to 12 mol%, more preferably 1.5 to 8 mol, based on the monomer. % Is particularly preferred.
ラジカル重合開始剤としては、特に制限はなく、従来ジアリルアミン類の酸付加塩重合体の重合に使用される公知の重合開始剤の中から、任意のものを適宜選択して用いることができる。このようなラジカル重合開始剤としては、過硫酸塩系ラジカル重合開始剤や、分子中にアゾ基を有するラジカル重合開始剤などを好ましく挙げることができる。前記過硫酸塩系ラジカル重合開始剤としては、例えば過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウムなどが挙げられ、これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 There is no restriction | limiting in particular as a radical polymerization initiator, From the well-known polymerization initiator conventionally used for superposition | polymerization of the acid addition salt polymer of diallylamines, arbitrary things can be selected suitably and can be used. Preferred examples of such radical polymerization initiators include persulfate radical polymerization initiators and radical polymerization initiators having an azo group in the molecule. Examples of the persulfate-based radical polymerization initiator include ammonium persulfate, potassium persulfate, and sodium persulfate, and these may be used alone or in combination of two or more. .
一方、分子中にアゾ基を有するラジカル重合開始剤としては、分子中にアゾ基とカチオン性窒素を有する化合物が好適である。このような化合物の例としては、２，２’−アゾビス（２−アミジノプロパン）、２，２’−アゾビス（２−アミジノブタン）、２，２’−アゾビス（２−アミジノペンタン）、２，２’−アゾビス（２−アミジノ−３−メチルブタン）、３，３’−アゾビス（３−アミジノペンタン）、３，３’−アゾビス（３−アミジノヘキサン）、３，３’−アゾビス（３−アミジノ−４−メチルペンタン）、４，４’−アゾビス（４−アミジノヘプタン）などの付加塩が挙げられる。ここで、付加塩としては、例えば塩酸塩、硫酸塩、リン酸塩、アルキル硫酸塩、ｐ−トルエンスルホン酸塩、ギ酸塩、酢酸塩、プロピオン酸塩などの無機酸付加塩または有機酸付加塩を挙げることができる。これらのアゾ系ラジカル重合開始剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 On the other hand, the radical polymerization initiator having an azo group in the molecule is preferably a compound having an azo group and cationic nitrogen in the molecule. Examples of such compounds are 2,2′-azobis (2-amidinopropane), 2,2′-azobis (2-amidinobutane), 2,2′-azobis (2-amidinopentane), 2,2 '-Azobis (2-amidino-3-methylbutane), 3,3'-azobis (3-amidinopentane), 3,3'-azobis (3-amidinohexane), 3,3'-azobis (3-amidino- Addition salts such as 4-methylpentane) and 4,4′-azobis (4-amidinoheptane). Here, examples of the addition salt include inorganic acid addition salts or organic acid addition salts such as hydrochloride, sulfate, phosphate, alkyl sulfate, p-toluenesulfonate, formate, acetate, and propionate. Can be mentioned. One of these azo radical polymerization initiators may be used alone, or two or more thereof may be used in combination.
そのうち、分子量が多少大きくても水溶性の遊離のジアリルアミン類重合体を、水溶性で得ることができやすい点から２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等の分子中にアゾ基とカチオン性窒素を有する化合物が好ましい。 Among them, water-soluble free diallylamine polymers can be obtained in a water-soluble form even if the molecular weight is somewhat large, so that azobenzene is present in the molecule such as 2,2′-azobis (2-amidinopropane) dihydrochloride. Compounds having a group and cationic nitrogen are preferred.
ジアリルアミン類の酸付加塩をラジカル重合開始剤の存在下で重合させる場合は、水に対し、モノマーとラジカル重合開始剤を一括添加したり、そのいずれをも連続添加したり、分割添加したりして重合することができる。添加の方法は、水にモノマーとラジカル重合開始剤を連続添加したり分割添加したりすることが、用いるラジカル重合開始剤を少なくすることができるので好ましい。 When the acid addition salt of diallylamine is polymerized in the presence of a radical polymerization initiator, the monomer and radical polymerization initiator are added to water all at once, or both of them are added continuously or dividedly. Can be polymerized. As the method of addition, it is preferable to continuously add the monomer and the radical polymerization initiator to water or to add them in portions because the radical polymerization initiator to be used can be reduced.
重合温度は、５０〜９５℃が好ましく、５５〜９０℃がさらに好ましく、６０〜８５℃が特に好ましい。重合時間は、重合スケール、モノマーとラジカル重合開始剤の添加方法、重合温度により適当に選択される。 The polymerization temperature is preferably 50 to 95 ° C, more preferably 55 to 90 ° C, and particularly preferably 60 to 85 ° C. The polymerization time is appropriately selected depending on the polymerization scale, the method of adding the monomer and radical polymerization initiator, and the polymerization temperature.
次いで、このようにして得られたジアリルアミン類の酸付加塩重合体水溶液を、前述の方法で中和しながら脱塩処理することにより、前記一般式（II）で表される繰り返し単位を有する遊離のジアリルアミン類重合体水溶液が得られる。 Next, the aqueous acid addition salt polymer aqueous solution of diallylamines thus obtained is desalted while neutralizing by the above-described method, so that free radicals having a repeating unit represented by the general formula (II) are obtained. A diallylamine polymer aqueous solution is obtained.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、得られた重合体の重量平均分子量および重合収率は、日立Ｌ−６０００型高速液体クロマトグラフィーを使用し、ＧＰＣ法によって測定した。溶離液流路ポンプは日立Ｌ−６０００、検出器はショーデクスＲＩ ＳＥ−６１示差屈折率検出器、カラムはアサヒパックの水系ゲル濾過タイプのＧＳ−２２０ＨＱ（排除限界分子量３，０００）とＧＳ−６２０ＨＱ（排除限界分子量２００万）とをダブルに接続したものを用いた。サンプルは溶離液で０．５ｇ／１００ｍｌの濃度に調製し、２０μｌを用いた。溶離液には０．４モル／リットルの塩化ナトリウム水溶液を使用した。カラム温度は３０℃で、流速は１．０ｍｌ／分で実施した。標準サンプルとして分子量１０６、１９４、４４０、６００、１４７０、４１００、７１００、１０３００、１２６００、２３０００の１０種のポリエチレングリコールを用いて較正曲線を求め、その較正曲線を基に、重合体の重量平均分子量を求めた。さらにクロマトグラムの各成分のピーク面積から、重合収率を算出した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the weight average molecular weight and polymerization yield of the obtained polymer were measured by GPC method using Hitachi L-6000 type high performance liquid chromatography. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS-620HQ. (Exclusion limit molecular weight 2 million) was used in a double connection. Samples were prepared with an eluent to a concentration of 0.5 g / 100 ml, and 20 μl was used. A 0.4 mol / liter sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was obtained using 10 kinds of polyethylene glycols having molecular weights of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, and 23000 as standard samples, and the weight average molecular weight of the polymer was determined based on the calibration curve. Asked. Furthermore, the polymerization yield was calculated from the peak area of each component of the chromatogram.
実施例１ 遊離のＮ−メチルジアリルアミン重合体水溶液の製造Ｉ
ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩７５．５２ｇ（０．２８モル）を４回に分割して添加し、一方、モノマーとしてＮ−メチルジアリルアミン塩酸塩７３８．２５ｇ（５．０モル）を３回に分割して添加して重合した後、中和・脱塩して標記の重合体水溶液を製造した。以下に詳述する。
（１）Ｎ−メチルジアリルアミン塩酸塩重合体水溶液の製造
まず、撹拌機、ジムロート冷却管、温度計を装備した１０Ｌの４つ口セパラブルフラスコ中に蒸留水２５８２．２０ｇを仕込み、７０℃に加温し、濃度７１．４３質量％のＮ−メチルジアリルアミン塩酸塩水溶液３４４．５１ｇとラジカル重合開始剤の２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩１６．１３ｇを添加し、重合を開始した。重合開始後、１６．１３ｇの２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩を、２時間ごとに２回、反応液に添加した。また、重合開始後、濃度７１．４３質量％のＮ−メチルジアリルアミン塩酸塩水溶液３４４．５１ｇを２時間ごとに２回、反応液に添加しながら、２４時間重合反応を行った。次いで、反応液に２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩２７．１２ｇを一括で添加し、計４８時間の重合を行ない、重量平均分子量３３００のＮ−メチルジアリルアミン塩酸塩重合体水溶液を得た。
（２）遊離のＮ−メチルジアリルアミン重合体水溶液の製造
得られたＮ−メチルジアリルアミン塩酸塩重合体水溶液に濃度２５質量％水酸化ナトリウム水溶液２４１．５０ｇを滴下し一部中和した（なお、この時点で塩酸塩重合体を遊離の重合体にするため、その重合体のモノマーと同じモル量の水酸化ナトリウム水溶液を加えると沈殿が発生し、水溶性の遊離のＮ−メチルジアリルアミン重合体水溶液を得ることはできなかった）。次いで、得られたｐＨ９．５の水溶液を、撹拌機を装備したイオン交換膜電気透析機に仕込み、２５質量％水酸化ナトリウム水溶液５６０．００ｇを連続的に滴下しながら中和と脱塩を少しずつ行いながら電気透析処理した。その結果、濃度１３．４３質量％の遊離のＮ−メチルジアリルアミン重合体水溶液３３４８．１３ｇ（収率８１％）を得た。なお、得られた重合体の灰分は、乾燥重合体に対し０．１６質量％であった。この水溶液は、室温で７日放置しておいても水溶液の状態であり、不溶性のゲル状物質は生成しなかった。
次いで、得られた遊離のＮ−メチルジアリルアミン重合体水溶液の一部をとり、アセトン中に投入することにより白色沈殿をさせ、さらにアセトンで洗浄後、濾別して４０℃で４８時間加熱真空乾燥を行うことで重合体を固体として得た。固体重合体０．１ｇを、種々の溶媒２ｇに対し溶解するかどうか調査した。その結果、この重合体は、水、メタノール、エタノールに溶解した。しかし、イソプロピルアルコール、アセトン、ジメチルホルムアミドには溶解しなかった。また、この重合体のＩＲの結果を図２に、この重合体を塩酸塩にして測定したＧＰＣの結果を図３に示す。
Example 1 Preparation of Free N-Methyldiallylamine Polymer Aqueous Solution I
75.52 g (0.28 mol) of 2,2′-azobis- (2-amidinopropane) dihydrochloride as radical polymerization initiator was added in four portions, while N-methyldiallylamine hydrochloride as a monomer was added. 73.8.25 g (5.0 mol) was added in three portions for polymerization, followed by neutralization and desalting to produce the title polymer aqueous solution. This will be described in detail below.
(1) Production of N-methyldiallylamine hydrochloride aqueous polymer solution First, 2582.20 g of distilled water was charged into a 10 L four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, and heated to 70 ° C. Warm, add 344.51 g of N-methyldiallylamine hydrochloride aqueous solution with a concentration of 71.43 mass% and 16.13 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride as a radical polymerization initiator, and polymerize Started. After the start of polymerization, 16.13 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added to the reaction solution twice every 2 hours. Moreover, after the start of polymerization, a polymerization reaction was carried out for 24 hours while adding 344.51 g of a 71.43% by mass N-methyldiallylamine hydrochloride aqueous solution to the reaction solution twice every 2 hours. Next, 27.12 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added all at once to the reaction solution, polymerization was carried out for a total of 48 hours, and the weight of N-methyldiallylamine hydrochloride having a weight average molecular weight of 3300 was increased. A combined aqueous solution was obtained.
(2) Production of free N-methyldiallylamine polymer aqueous solution 241.50 g of a 25% strength by weight aqueous sodium hydroxide solution was added dropwise to the resulting aqueous N-methyldiallylamine hydrochloride polymer aqueous solution to partially neutralize it. At this point, the hydrochloride polymer is converted to a free polymer, and when a molar amount of aqueous sodium hydroxide solution is added to the polymer monomer, precipitation occurs, and a water-soluble free N-methyldiallylamine polymer aqueous solution is formed. I couldn't get it). Next, the obtained aqueous solution having a pH of 9.5 was charged into an ion exchange membrane electrodialyzer equipped with a stirrer, and 560.00 g of 25% by mass aqueous sodium hydroxide solution was continuously added dropwise to slightly neutralize and desalinate. The electrodialysis treatment was performed one by one. As a result, 3348.13 g (yield 81%) of a free N-methyldiallylamine polymer aqueous solution having a concentration of 13.43% by mass was obtained. In addition, the ash content of the obtained polymer was 0.16 mass% with respect to the dry polymer. This aqueous solution was in the state of an aqueous solution even after being left at room temperature for 7 days, and no insoluble gel-like substance was produced.
Next, a part of the obtained free N-methyldiallylamine polymer aqueous solution is taken and poured into acetone to form a white precipitate, which is further washed with acetone, filtered, and vacuum dried at 40 ° C. for 48 hours. This gave the polymer as a solid. It was investigated whether 0.1 g of a solid polymer was dissolved in 2 g of various solvents. As a result, this polymer was dissolved in water, methanol, and ethanol. However, it did not dissolve in isopropyl alcohol, acetone, or dimethylformamide. Further, FIG. 2 shows the IR result of this polymer, and FIG. 3 shows the GPC result obtained by measuring the polymer as a hydrochloride.
実施例２ 遊離のＮ−メチルジアリルアミン重合体水溶液の製造II
２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩１０．２６ｇ（０．０４モル）とＮ−メチルジアリルアミン塩酸塩７３．８２ｇ（０．５モル）を連続的に添加して重合した後、中和・脱塩し標記の重合体水溶液を製造した。以下に詳述する。
（１）Ｎ−メチルジアリルアミン塩酸塩重合体水溶液の製造
撹拌機、ジムロート冷却管、温度計を装備した５００ｍＬの４つ口セパラブルフラスコ中に蒸留水３７５．５７ｇを仕込み、７０℃に加温し、濃度６９．４５質量％のＮ−メチルジアリルアミン塩酸塩水溶液１０６．３０ｇと２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩１０．２６ｇとを６時間かけて連続的に添加し重合を行った。その後、さらに反応を行い、合計４８時間重合反応を行ない、重量平均分子量２５００のＮ−メチルジアリルアミン塩酸塩重合体水溶液を得た。
（２）遊離のＮ−メチルジアリルアミン重合体水溶液の製造
得られたＮ−メチルジアリルアミン塩酸塩重合体水溶液に濃度２５質量％水酸化ナトリウム水溶液２８．４０ｇを滴下し、一部中和した。次いで、得られたｐＨ９．５の水溶液を、撹拌機を装備した電気透析機に仕込み、２５質量％水酸化ナトリウム水溶液５８．９３ｇを連続的に滴下しながら中和と脱塩を少しずつ行いながらイオン交換膜電気透析処理した。なお、この際、水溶液のｐＨは９〜１１に維持した。その結果、濃度１２．１１質量％の遊離のＮ−メチルジアリルアミン重合体水溶液３４９．９６ｇ（収率７６％）を得た。なお、得られた重合体の灰分は、乾燥重合体に対し０．１３質量％であった。
Example 2 Preparation of aqueous solution of free N-methyldiallylamine polymer II
Polymerization was carried out by continuously adding 10.26 g (0.04 mol) of 2,2′-azobis- (2-amidinopropane) dihydrochloride and 73.82 g (0.5 mol) of N-methyldiallylamine hydrochloride. Thereafter, neutralization and desalting were carried out to produce the aqueous polymer solution. This will be described in detail below.
(1) Production of N-methyldiallylamine hydrochloride aqueous polymer solution 375.57 g of distilled water was charged into a 500 mL four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, and heated to 70 ° C. And continuously adding 106.30 g of an N-methyldiallylamine hydrochloride aqueous solution having a concentration of 69.45% by mass and 10.26 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride over 6 hours. Went. Thereafter, the reaction was further carried out, and the polymerization reaction was carried out for a total of 48 hours to obtain an aqueous solution of N-methyldiallylamine hydrochloride polymer having a weight average molecular weight of 2500.
(2) Production of free aqueous N-methyldiallylamine polymer solution 28.40 g of a 25% strength by weight aqueous sodium hydroxide solution was added dropwise to the resulting N-methyldiallylamine hydrochloride polymer aqueous solution to partially neutralize it. Next, the obtained aqueous solution having a pH of 9.5 was charged into an electrodialyzer equipped with a stirrer, and while neutralizing and desalting little by little while continuously dropping 58.93 g of a 25% by mass aqueous sodium hydroxide solution. Ion exchange membrane electrodialysis treatment. At this time, the pH of the aqueous solution was maintained at 9-11. As a result, 349.96 g (yield 76%) of a free N-methyldiallylamine polymer aqueous solution having a concentration of 12.11% by mass was obtained. In addition, the ash content of the obtained polymer was 0.13 mass% with respect to the dry polymer.
実施例３ 遊離のＮ−メチルジアリルアミン重合体水溶液の製造III
ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩とＮ−メチルジアリルアミン塩酸塩とを、一括添加して重合した後、中和・脱塩して標記の重合体水溶液を製造した。以下、詳述する。
（１）Ｎ−メチルジアリルアミン塩酸塩重合体水溶液の製造
撹拌機、ジムロート冷却管、温度計を装備した５Ｌの４つ口セパラブルフラスコ中に濃度６８．６６質量％のＮ−メチルジアリルアミン塩酸塩水溶液４３０．０９ｇと蒸留水１９０８．１８ｇを仕込んだ。このモノマー溶液を８０℃に加温し、ラジカル重合開始剤として濃度１５．０２質量％の２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩水溶液７２３．１９ｇを一括で添加し、２４時間の重合を行った。この重合体の重量平均分子量は１３００であった。
（２）遊離のＮ−メチルジアリルアミン重合体水溶液の製造
得られたＮ−メチルジアリルアミン塩酸塩重合体水溶液に、濃度２５質量％の水酸化ナトリウム水溶液１１０．８７ｇを滴下し部分中和した。次いで、得られたｐＨ９．５の水溶液を、撹拌機を装備したイオン交換膜電気透析機に仕込み、２５質量％水酸化ナトリウム２２５．１０ｇを連続的に滴下しながら中和と脱塩を少しずつ行いながらイオン交換膜電気透析処理した。なお、その結果、濃度１１．９３質量％の遊離のＮ−メチルジアリルアミン重合体水溶液１５８４．４２ｇ（収率８５％）を得た。なお、得られた重合体の灰分は、乾燥重合体に対し０．１５質量％であった。
Example 3 Preparation of Free N-Methyldiallylamine Polymer Aqueous Solution III
As a radical polymerization initiator, 2,2′-azobis- (2-amidinopropane) dihydrochloride and N-methyldiallylamine hydrochloride are added together and polymerized, and then neutralized and desalted to give the title polymer. An aqueous solution was prepared. Details will be described below.
(1) Production of N-methyldiallylamine hydrochloride aqueous polymer solution N-methyldiallylamine hydrochloride aqueous solution having a concentration of 68.66% by mass in a 5 L four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer. 430.09 g and distilled water 1908.18 g were charged. This monomer solution was heated to 80 ° C., and 723.19 g of a 2,2′-azobis- (2-amidinopropane) dihydrochloride aqueous solution having a concentration of 15.02% by mass as a radical polymerization initiator was added all at once. Time polymerization was carried out. The weight average molecular weight of this polymer was 1300.
(2) Manufacture of free N-methyl diallylamine polymer aqueous solution 110.87 g of 25 mass% sodium hydroxide aqueous solution was dripped at the obtained N-methyl diallylamine hydrochloride polymer aqueous solution and partially neutralized. Next, the obtained aqueous solution of pH 9.5 was charged into an ion exchange membrane electrodialyzer equipped with a stirrer, and neutralization and desalting were carried out little by little while continuously dropping 225.10 g of 25% by mass sodium hydroxide. While performing, ion exchange membrane electrodialysis treatment was performed. As a result, 1584.42 g (yield 85%) of a free N-methyldiallylamine polymer aqueous solution having a concentration of 11.93% by mass was obtained. In addition, the ash content of the obtained polymer was 0.15 mass% with respect to the dry polymer.
実施例４ 遊離のＮ−メチルジアリルアミン重合体水溶液の製造IV
ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩とＮ−メチルジアリルアミン塩酸塩とを、一括添加して、次亜リン酸ナトリウムの存在下で重合した後、中和・脱塩し標記の重合体水溶液を製造した。以下に詳述する。
（１）Ｎ−メチルジアリルアミン塩酸塩重合体水溶液の製造
撹拌機、ジムロート冷却管、温度計を装備した１Ｌの４つ口セパラブルフラスコ中に濃度６９．４５質量％のＮ−メチルジアリルアミン塩酸塩水溶液４２５．２０ｇ、蒸留水３１３．０５ｇと次亜リン酸ナトリウム４．２４ｇを仕込んだ。そのモノマー溶液を７０℃に加温し、ラジカル重合開始剤として２，２‘−アゾビス−（２−アミジノプロパン）二塩酸塩１８．９８ｇを添加し、４８時間の重合を行った。この重合体の重量平均分子量は３１００であった。
（２）遊離のＮ−メチルジアリルアミン重合体水溶液の製造
得られたＮ−メチルジアリルアミン塩酸塩重合体水溶液に、濃度２５質量％水酸化ナトリウム水溶液１０８．２３ｇを滴下し部分中和した。次いで、得られたｐＨ９．５の水溶液を、撹拌機を装備したイオン交換膜電気透析機に仕込み、２５質量％水酸化ナトリウム水溶液２１９．７５ｇを連続的に滴下しながら中和と脱塩を少しずつ行いながらイオン交換膜電気透析処理した。その結果、濃度１１．８５質量％の遊離のＮ−メチルジアリルアミン重合体水溶液１５２０．０８ｇ（収率８１％）を得た。なお、得られた重合体の灰分は、乾燥重合体に対し０．２０質量％であった。
Example 4 Preparation of an aqueous solution of free N-methyldiallylamine polymer IV
2,2′-azobis- (2-amidinopropane) dihydrochloride and N-methyldiallylamine hydrochloride were added together as a radical polymerization initiator and polymerized in the presence of sodium hypophosphite. The title polymer aqueous solution was prepared by summing and desalting. This will be described in detail below.
(1) Production of N-methyldiallylamine hydrochloride aqueous polymer solution N-methyldiallylamine hydrochloride aqueous solution having a concentration of 69.45% by mass in a 1 L four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer. 425.20 g, distilled water 313.05 g and sodium hypophosphite 4.24 g were charged. The monomer solution was heated to 70 ° C., 18.98 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added as a radical polymerization initiator, and polymerization was performed for 48 hours. The weight average molecular weight of this polymer was 3100.
(2) Production of free aqueous N-methyldiallylamine polymer solution 108.23 g of a 25% strength by weight aqueous sodium hydroxide solution was dropped into the obtained N-methyldiallylamine hydrochloride polymer aqueous solution to partially neutralize it. Next, the obtained aqueous solution with a pH of 9.5 was charged into an ion exchange membrane electrodialyzer equipped with a stirrer, and a little neutralization and desalting were carried out while 219.75 g of a 25% by mass aqueous sodium hydroxide solution was continuously added dropwise. The ion exchange membrane electrodialysis treatment was carried out step by step. As a result, 1520.08 g (yield 81%) of a free N-methyldiallylamine polymer aqueous solution having a concentration of 11.85% by mass was obtained. The ash content of the obtained polymer was 0.20% by mass relative to the dry polymer.
実施例５ 遊離のジアリルアミン重合体水溶液の製造
ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩４．８４ｇ（０．０２モル）を、３回に分割して添加し、モノマーとしてジアリルアミン塩酸塩６６．８１ｇ（０．５モル）を３回に分割して添加し重合した後、中和・脱塩し標記の重合体水溶液を製造した。以下に詳述する。
（１）ジアリルアミン塩酸塩重合体水溶液の製造
撹拌機、ジムロート冷却管、温度計を装備した５００ｍＬの４つ口セパラブルフラスコ中に蒸留水２２９．６０ｇを仕込み、７０℃に加温し、濃度６７．０７質量％のジアリルアミン塩酸塩水溶液３３．２０ｇとラジカル重合開始剤の２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩１．６１ｇを添加し、重合を開始した。重合開始後、１．６１ｇの２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩を、２時間ごとに２回、反応液に添加した。また、重合開始後、濃度６７．０７質量％のジアリルアミン塩酸塩水溶液３３．２０ｇを２時間ごとに２回、反応液に添加しながら、２４時間重合反応を行った。その結果、重量平均分子量３３００のジアリルアミン塩酸塩重合体水溶液を得た。
（２）遊離のジアリルアミン重合体水溶液の製造
得られたジアリルアミン塩酸塩重合体水溶液に、濃度２５質量％水酸化ナトリウム水溶液２６．４０ｇを滴下し中和した。次いで、得られたｐＨ９．５の水溶液を、撹拌機を装備したイオン交換膜電気透析機に仕込み、２５質量％水酸化ナトリウム５３．６０ｇを連続的に滴下しながら中和と脱塩を少しずつ行いながらイオン交換膜電気透析処理した。その結果、濃度１４．９２質量％の遊離のジアリルアミン重合体水溶液２３１．８４ｇ（収率７２％）を得た。この水溶液は、５０℃で７日放置しておいても水溶液の状態であり、不溶性のゲル状物質は生成しなかった。
また、遊離のジアリルアミン重合体水溶液の一部をとり、４０℃で４８時間加熱真空乾燥を行なうことで重合体を固体として得た。この重合体のＩＲを図４に示す。また、この重合体を塩酸塩にして測定したＧＰＣの結果を図５に示す。なお、得られた重合体の灰分は、乾燥重合体に対し０．２２質量％であった。
Example 5 Production of free diallylamine polymer aqueous solution 4.84 g (0.02 mol) of 2,2′-azobis- (2-amidinopropane) dihydrochloride as a radical polymerization initiator was added in three portions. Then, 66.81 g (0.5 mol) of diallylamine hydrochloride as a monomer was added in three portions for polymerization, followed by neutralization and desalting to produce the title polymer aqueous solution. This will be described in detail below.
(1) Production of diallylamine hydrochloride polymer aqueous solution 229.60 g of distilled water was charged into a 500 mL four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, heated to 70 ° C., and a concentration of 67 Polymerization was initiated by adding 33.20 g of a 0.07 mass% diallylamine hydrochloride aqueous solution and 1.61 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride as a radical polymerization initiator. After the start of polymerization, 1.61 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added to the reaction solution twice every 2 hours. Further, after the start of polymerization, a polymerization reaction was carried out for 24 hours while adding 33.20 g of a diallylamine hydrochloride aqueous solution having a concentration of 67.07% by mass to the reaction solution twice every 2 hours. As a result, a diallylamine hydrochloride polymer aqueous solution having a weight average molecular weight of 3300 was obtained.
(2) Production of free diallylamine polymer aqueous solution 26.40 g of 25% by weight sodium hydroxide aqueous solution was added dropwise to the obtained diallylamine hydrochloride polymer aqueous solution to neutralize it. Next, the obtained aqueous solution of pH 9.5 was charged into an ion exchange membrane electrodialyzer equipped with a stirrer, and neutralization and desalting were carried out little by little while dropping 53.60 g of 25% by mass sodium hydroxide continuously. While performing, ion exchange membrane electrodialysis treatment was performed. As a result, 231.84 g (yield 72%) of a free diallylamine polymer aqueous solution having a concentration of 14.92% by mass was obtained. This aqueous solution was in the form of an aqueous solution even after being left at 50 ° C. for 7 days, and no insoluble gel-like substance was produced.
A part of the free diallylamine polymer aqueous solution was taken and vacuum-dried by heating at 40 ° C. for 48 hours to obtain a polymer as a solid. The IR of this polymer is shown in FIG. Further, FIG. 5 shows the results of GPC measured using this polymer as a hydrochloride. In addition, the ash content of the obtained polymer was 0.22 mass% with respect to the dry polymer.
比較例１ 重量平均分子量１５０００の遊離のＮ−メチルジアリルアミン重合体水溶液の製造の試み
撹拌機、ジムロート冷却管、温度計を装備した５００ｍＬの４つ口セパラブルフラスコ中に濃度５５．０１質量％のＮ−メチルジアリルアミン塩酸塩水溶液３２４．９３ｇと蒸留水３７．４３ｇを仕込んだ。そのモノマー水溶液を６０℃に加温し、ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩２１．２４ｇを添加し、４８時間の重合を行い、Ｎ−メチルジアリルアミン塩酸塩重合体を水溶液として収率９４％で得た。この重合体の重量平均分子量は１５０００であった。この水溶液に２５質量％水酸化ナトリウム水溶液を加えたところ、沈殿が発生し、イオン交換膜電気透析等の処理をすることはできなかった。
Comparative Example 1 Trial of Production of Free N-Methyldiallylamine Polymer Aqueous Solution with Weight Average Molecular Weight of 15000 In a 500 mL four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer, a concentration of 55.01% by mass An N-methyldiallylamine hydrochloride aqueous solution (324.93 g) and distilled water (37.43 g) were charged. The monomer aqueous solution was heated to 60 ° C., and 21.24 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added as a radical polymerization initiator, followed by polymerization for 48 hours, and N-methyldiallylamine. The hydrochloride polymer was obtained in 94% yield as an aqueous solution. The weight average molecular weight of this polymer was 15000. When a 25% by mass aqueous sodium hydroxide solution was added to this aqueous solution, precipitation occurred and treatment such as ion exchange membrane electrodialysis could not be performed.
比較例２ 重量平均分子量６００００の遊離のジアリルアミン重合体水溶液の製造の試み
攪拌機、ジムロート冷却管、温度計を装備した５００ｍＬの４つ口セパラブルフラスコ中に濃度６５．５０質量％のジアリルアミン塩酸塩水溶液４２２．２８ｇと蒸留水６０．７１ｇを仕込んだ。そのモノマー溶液を６５℃加温し、ラジカル重合開始剤として２，２’−アゾビス−（２−アミジノプロパン）二塩酸塩３４．６１ｇを添加し、２４時間の重合を行い、ジアリルアミン塩酸塩重合体を水溶液として収率９５％で得た。この重合体の重量平均分子量は６００００であった。
この水溶液に２５質量％水酸化ナトリウム水溶液を加えたところ、最初は、溶液状態であったが、数分後に水不溶性のゲル状の沈殿が発生し、イオン交換膜電気透析等の処理をすることはできなかった。
Comparative Example 2 Attempt to produce a free diallylamine polymer aqueous solution having a weight average molecular weight of 60,000 A diallylamine hydrochloride aqueous solution having a concentration of 65.50% by mass in a 500 mL four-necked separable flask equipped with a stirrer, a Dimroth condenser, and a thermometer 422.28 g and distilled water 60.71 g were charged. The monomer solution was heated at 65 ° C., 34.61 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride was added as a radical polymerization initiator, polymerized for 24 hours, and diallylamine hydrochloride polymer. Was obtained in 95% yield as an aqueous solution. The weight average molecular weight of this polymer was 60000.
When 25% by weight sodium hydroxide aqueous solution was added to this aqueous solution, it was initially in a solution state, but after several minutes, a water-insoluble gel-like precipitate was generated, and treatment such as ion exchange membrane electrodialysis was performed. I couldn't.
本発明の方法によれば、従来得られにくかった遊離のアリルアミン類重合体水溶液を、工程中全て水溶液の状態で工業的に効率よく製造することができる。得られた遊離のアリルアミン類重合体水溶液は、ノンハロゲンであるので、ファインケミカル分野などに好適に用いられる。 According to the method of the present invention, it is possible to industrially efficiently produce a free allylamine polymer aqueous solution, which has been difficult to obtain conventionally, in the state of an aqueous solution in the whole process. Since the obtained free allylamine polymer aqueous solution is non-halogen, it is suitably used in the field of fine chemicals.
１ 原液槽
２ 濃縮液槽
３ 希釈室
４ 濃縮室
５ 電極室
６ 電極板
７ 原液経路
８ 濃縮液経路
９ 電槽
Ｐ１，Ｐ２ ポンプ
Ａ 陰イオン交換膜
Ｃ 陽イオン交換膜
1 stock solution tank 2
Claims (8)
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体であり、かつ遊離のアリルアミン類重合体が、一般式（II）
で表される繰り返し単位を有するジアリルアミン類重合体である請求項１に記載の方法。 Acid addition salt polymers of allylamines are represented by the general formula (I)
A diallylamine acid addition salt polymer having a repeating unit represented by general formula (II) and having a weight average molecular weight of 400 to 4500
The method according to claim 1, which is a diallylamine polymer having a repeating unit represented by the formula:
で表されるジアリルアミン類の酸付加塩を、濃度５〜３５質量％の状態で重合し、一般式（Ｉ）
で表される繰り返し単位を有する、重量平均分子量が４００〜４５００のジアリルアミン類の酸付加塩重合体を製造し、次いでその水溶液を中和しながら脱塩処理することを特徴とする、一般式（II）
で表される繰り返し単位を有する遊離のジアリルアミン類重合体水溶液の製造方法。 In an aqueous medium, in the presence of a radical polymerization initiator, the general formula (III)
The acid addition salt of diallylamines represented by the general formula (I) is polymerized in a concentration of 5 to 35% by mass.
A diallylamine acid addition salt polymer having a weight average molecular weight of 400 to 4500 and having a repeating unit represented by the following general formula ( II)
The manufacturing method of the free diallylamine polymer aqueous solution which has a repeating unit represented by these.
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