JPWO2019054301A1 - A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same. - Google Patents
A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same. Download PDFInfo
- Publication number
- JPWO2019054301A1 JPWO2019054301A1 JP2019542033A JP2019542033A JPWO2019054301A1 JP WO2019054301 A1 JPWO2019054301 A1 JP WO2019054301A1 JP 2019542033 A JP2019542033 A JP 2019542033A JP 2019542033 A JP2019542033 A JP 2019542033A JP WO2019054301 A1 JPWO2019054301 A1 JP WO2019054301A1
- Authority
- JP
- Japan
- Prior art keywords
- highly branched
- branched polymer
- sulfo group
- sulfuric acid
- containing highly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
Abstract
スルホ基含有高分岐ポリマーの硫酸溶液を水へ投入して、前記スルホ基含有高分岐ポリマーを再沈殿させる再沈殿処理工程、及び前記再沈殿処理工程で得た沈殿物を含む液と有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程を含むことを特徴とするスルホ基含有高分岐ポリマーの精製方法を提供する。A reprecipitation treatment step of adding a sulfuric acid solution of a sulfo group-containing highly branched polymer to water to reprecipitate the sulfo group-containing highly branched polymer, and a liquid containing a precipitate obtained in the reprecipitation treatment step and an organic solvent. Provided is a method for purifying a sulfo group-containing highly branched polymer, which comprises an aggregation step of mixing and stirring to aggregate the precipitate.
Description
本発明は、スルホ基含有高分岐ポリマーの精製方法及びその製造方法に関する。 The present invention relates to a method for purifying a highly branched polymer containing a sulfo group and a method for producing the same.
スルホ基を有する高分岐ポリマーはカーボンナノチューブ（ＣＮＴ）の分散剤として使用できるだけでなく、各種溶媒に溶解させて膜形成組成物として好適に用いることができる。 The highly branched polymer having a sulfo group can be used not only as a dispersant for carbon nanotubes (CNTs), but also can be suitably used as a film-forming composition by dissolving it in various solvents.
高分岐ポリマーとしては、トリアリールアミン構造を分岐点として含有する高分岐ポリマー等が例示されるが、このようなポリマーにスルホ基を導入する場合、一般的に、スルホ基が導入されたトリアリールアミン化合物、アルデヒド化合物及びケトン化合物等のポリマー原料を用いて製造する方法や、スルホ基を有しない高分岐ポリマーを合成した後、スルホ基を導入可能な試薬で処理する方法がある。通常は、製造の簡便さを考慮して、後者の方法を用いることが多い。後者の方法において、スルホ基を導入する方法としては、従来公知の方法から選択することができ、特に制限されるものではないが、過剰量の硫酸を用いてスルホン化する方法等を用いることができる。 Examples of the highly branched polymer include a highly branched polymer containing a triarylamine structure as a branching point. When a sulfo group is introduced into such a polymer, a triaryl having a sulfo group introduced is generally used. There are a method of producing using a polymer raw material such as an amine compound, an aldehyde compound and a ketone compound, and a method of synthesizing a highly branched polymer having no sulfo group and then treating with a reagent capable of introducing a sulfo group. Usually, the latter method is often used in consideration of manufacturing convenience. In the latter method, the method for introducing a sulfo group can be selected from conventionally known methods, and is not particularly limited, but a method of sulfonation with an excess amount of sulfuric acid or the like can be used. it can.
なお、本発明に関連する先行技術文献としては下記のものが挙げられる。 The following are examples of prior art documents related to the present invention.
スルホ基含有高分岐ポリマーの精製は、該ポリマーの硫酸溶液を貧溶媒へと滴下する再沈殿操作にて行われているが、再沈殿溶媒の貧溶媒として水が選定されると、再沈殿操作で生じるポリマー粒子の粒径が小さく、その後の沈殿物の濾過性が極めて悪いという問題がある。この濾過性の悪さのため、濾過の長時間化による生産効率低下、あるいは細かい粒子の目詰まりによる作業中断、またポリマーへの残留硫酸量の増加等の問題が生じている。 Purification of the sulfo group-containing highly branched polymer is performed by a reprecipitation operation in which a sulfuric acid solution of the polymer is dropped into a poor solvent, but when water is selected as the poor solvent for the reprecipitation solvent, a reprecipitation operation is performed. There is a problem that the particle size of the polymer particles produced in the above is small and the filterability of the subsequent precipitate is extremely poor. Due to this poor filterability, there are problems such as a decrease in production efficiency due to a long filtration time, work interruption due to clogging of fine particles, and an increase in the amount of residual sulfuric acid in the polymer.
この問題については、前記硫酸溶液のｐＨを等電点付近まで調整し、沈殿物の凝集を促す方法が考えられるが、硫酸中でスルホン化した場合には中和に多量のアルカリを必要とすること、膨大な中和熱の制御が必要であること等の理由により、生産性の高い製法とは言い難く、当該問題を解決し得る新たな方法の開発が望まれている。 To solve this problem, a method of adjusting the pH of the sulfuric acid solution to near the isoelectric point to promote the aggregation of the precipitate can be considered, but when sulfonated in sulfuric acid, a large amount of alkali is required for neutralization. It is hard to say that it is a highly productive manufacturing method because of the fact that it is necessary to control a huge amount of neutralization heat, and the development of a new method that can solve the problem is desired.
本発明は、このような事情に鑑みてなされたものであり、スルホ基含有高分岐ポリマーを短時間で効率的に精製し得、得られる精製物の残留硫酸量も低減し得るスルホ基含有高分岐ポリマーの精製方法、及びスルホ基含有高分岐ポリマーをより効率よく製造することができるスルホ基含有高分岐ポリマーの製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and the sulfo group-containing highly branched polymer can be efficiently purified in a short time, and the amount of residual sulfuric acid in the obtained purified product can be reduced. An object of the present invention is to provide a method for purifying a branched polymer and a method for producing a sulfo group-containing highly branched polymer capable of more efficiently producing a sulfo group-containing highly branched polymer.
本発明者は、前記目的を達成するために鋭意検討した結果、スルホ基含有高分岐ポリマーの硫酸溶液を水に投入して再沈殿処理を行った後、沈殿物を含む液に、更に有機溶媒を添加して撹拌することにより、沈殿物を凝集成長させ、良好な濾過性等の高い操作性が得られ、残留硫酸量の低さにおいても優れた精製効果が得られることを見出し、本発明を完成させた。 As a result of diligent studies to achieve the above object, the present inventor puts a sulfuric acid solution of a sulfo group-containing highly branched polymer into water to perform reprecipitation treatment, and then adds an organic solvent to the solution containing a precipitate. By adding and stirring the precipitate, the precipitate is coagulated and grown, high operability such as good filterability can be obtained, and an excellent purification effect can be obtained even when the amount of residual sulfuric acid is low. Was completed.
すなわち、本発明は、
１． スルホ基含有高分岐ポリマーの硫酸溶液を水へ投入して、前記スルホ基含有高分岐ポリマーを再沈殿させる再沈殿処理工程、及び
前記再沈殿処理工程で得た沈殿物を含む液と有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程
を含むことを特徴とするスルホ基含有高分岐ポリマーの精製方法、
２． 前記硫酸溶液が、高分岐ポリマーを硫酸中でスルホン化した後の反応液である１のスルホ基含有高分岐ポリマーの精製方法、
３． 前記硫酸が、濃硫酸又は発煙硫酸である１又は２のスルホ基含有高分岐ポリマーの精製方法、
４． 前記有機溶媒が、水と混和する有機溶媒である１〜３のいずれかのスルホ基含有高分岐ポリマーの精製方法、
５． 前記有機溶媒が、テトラヒドロフラン、アセトニトリル、ジオキサン又はこれらの混合溶媒である４のスルホ基含有高分岐ポリマーの精製方法、
６． 前記スルホ基含有高分岐ポリマーが、トリアリールアミン構造を含有する高分岐ポリマーである１〜５のいずれかのスルホ基含有高分岐ポリマーの精製方法、
７． 前記スルホ基含有高分岐ポリマーが、トリアリールアミン化合物及びアルデヒド化合物から得られるノボラック型高分岐ポリマーである６のスルホ基含有高分岐ポリマーの精製方法、
８． 前記再沈殿処理工程において、硫酸の質量に対する水の質量比（水／硫酸）を０．９５〜１．２５とし、かつ、凝集工程において、硫酸の質量に対する有機溶媒の質量比（有機溶媒／硫酸）を０．９〜１．１とする１〜７のいずれかのスルホ基含有高分岐ポリマーの精製方法、
９． 前記凝集工程において、撹拌時間を２時間以上とする１〜８のいずれかのスルホ基含有高分岐ポリマーの精製方法、
１０． 前記凝集工程において、温度を２５〜１００℃とする１〜９のいずれかのスルホ基含有高分岐ポリマーの精製方法、
１１． トリアリールアミン化合物及びアルデヒド化合物を重合させて高分岐ポリマーを得る重合工程、
前記高分岐ポリマーを硫酸中でスルホン化して、スルホ基含有高分岐ポリマーの硫酸溶液を得るスルホン化工程、
前記スルホン化工程で得たスルホ基含有高分岐ポリマーの硫酸溶液を水へ投入して、前記スルホ基含有高分岐ポリマーを再沈殿させる再沈殿処理工程、及び
前記再沈殿処理工程で得た沈殿物を含む液と、水と混和する有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程
を含むことを特徴とするスルホ基含有高分岐ポリマーの製造方法、
１２． 前記有機溶媒が、テトラヒドロフラン、アセトニトリル、ジオキサン又はこれらの混合溶媒である１１のスルホ基含有高分岐ポリマーの製造方法
を提供する。That is, the present invention
1. 1. A reprecipitation treatment step of adding a sulfuric acid solution of a sulfo group-containing highly branched polymer to water to reprecipitate the sulfo group-containing highly branched polymer, and a liquid containing a precipitate obtained in the reprecipitation treatment step and an organic solvent. A method for purifying a sulfo group-containing highly branched polymer, which comprises an aggregation step of mixing and stirring to aggregate the precipitate.
2. A method for purifying a sulfo group-containing highly branched polymer according to which the sulfuric acid solution is a reaction solution after sulfonated the highly branched polymer in sulfuric acid.
3. 3. A method for purifying a highly branched polymer containing 1 or 2 sulfo groups, wherein the sulfuric acid is concentrated sulfuric acid or fuming sulfuric acid.
4. A method for purifying a sulfo group-containing highly branched polymer according to any one of 1 to 3, wherein the organic solvent is an organic solvent miscible with water.
5. A method for purifying a sulfo group-containing highly branched polymer of 4, wherein the organic solvent is tetrahydrofuran, acetonitrile, dioxane or a mixed solvent thereof.
6. The method for purifying a sulfo group-containing highly branched polymer according to any one of 1 to 5, wherein the sulfo group-containing highly branched polymer is a highly branched polymer containing a triarylamine structure.
7. 6. A method for purifying a sulfo group-containing highly branched polymer, wherein the sulfo group-containing highly branched polymer is a novolak-type highly branched polymer obtained from a triarylamine compound and an aldehyde compound.
8. In the reprecipitation treatment step, the mass ratio of water to the mass of sulfuric acid (water / sulfuric acid) was 0.95 to 1.25, and in the aggregation step, the mass ratio of the organic solvent to the mass of sulfuric acid (organic solvent / sulfuric acid). ) Is 0.9 to 1.1, and the method for purifying a highly branched polymer containing a sulfo group according to any one of 1 to 7.
9. The method for purifying a sulfo group-containing highly branched polymer according to any one of 1 to 8 in which the stirring time is 2 hours or more in the aggregation step.
10. The method for purifying a sulfo group-containing highly branched polymer according to any one of 1 to 9, wherein the temperature is 25 to 100 ° C. in the aggregation step.
11. Polymerization step of polymerizing a triarylamine compound and an aldehyde compound to obtain a highly branched polymer,
A sulfonate step of sulfonated the highly branched polymer in sulfuric acid to obtain a sulfuric acid solution of the sulfo group-containing highly branched polymer.
A reprecipitation treatment step in which a sulfuric acid solution of the sulfo group-containing highly branched polymer obtained in the sulfonated step is added to water to reprecipitate the sulfo group-containing highly branched polymer, and a precipitate obtained in the reprecipitation treatment step. A method for producing a sulfo group-containing highly branched polymer, which comprises a coagulation step of mixing a liquid containing the above-mentioned material and an organic solvent to be mixed with water and stirring the mixture to coagulate the precipitate.
12. Provided is a method for producing a sulfo group-containing highly branched polymer of 11 in which the organic solvent is tetrahydrofuran, acetonitrile, dioxane or a mixed solvent thereof.
本発明によれば、再沈殿処理後の沈殿物を含む液と有機溶媒とを混合して撹拌することで、ポリマー粒子が適度に凝集するため、沈殿物の濾過性等の操作性が良好になる。また、濾過性の大幅な改善により濾過時間が短縮するため、生産性向上に寄与することができ、更には、濾物への通液洗浄を容易に行うことができるため、ポリマー中の残存硫酸量を十分に低減させることができる。 According to the present invention, by mixing and stirring the liquid containing the precipitate after the reprecipitation treatment and the organic solvent, the polymer particles are appropriately aggregated, so that the operability such as the filterability of the precipitate is good. Become. In addition, since the filtration time is shortened due to the significant improvement in the filterability, it is possible to contribute to the improvement in productivity, and further, since the liquid-passing cleaning through the filter medium can be easily performed, the residual sulfuric acid in the polymer can be easily performed. The amount can be sufficiently reduced.
本発明のスルホ基含有高分岐ポリマーの精製方法は、重合反応後のスルホ基含有高分岐ポリマーの硫酸溶液を水へ投入し、前記スルホ基含有高分岐ポリマーを再沈殿させる再沈殿処理工程、及び前記再沈殿処理工程で得た沈殿物を含む液と有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程を含むものである。以下、各工程について詳細に説明する。 The method for purifying a sulfo group-containing highly branched polymer of the present invention includes a reprecipitation treatment step of adding a sulfuric acid solution of the sulfo group-containing highly branched polymer after the polymerization reaction to water to reprecipitate the sulfo group-containing highly branched polymer. This includes a coagulation step in which a solution containing a precipitate obtained in the reprecipitation treatment step and an organic solvent are mixed and stirred to agglomerate the precipitate. Hereinafter, each step will be described in detail.
（１）再沈殿処理工程
再沈殿処理工程は、スルホ基含有高分岐ポリマーの硫酸溶液を水へ投入して、前記スルホ基含有高分岐ポリマーを再沈殿させる工程である。なお、本発明において、前記スルホ基含有高分岐ポリマーの硫酸溶液は、スルホ基含有高分岐ポリマーを硫酸に溶かして調製した溶液でも、高分岐ポリマーを硫酸中でスルホン化した後の反応液でもよいが、作業効率等を考慮すると、スルホン化後の反応液が好ましい。以降の説明において、硫酸の質量は、スルホ基含有高分岐ポリマーを硫酸に溶かして調製した溶液を使用する場合は、スルホ基含有高分岐ポリマーを溶かす際に使用する硫酸の質量を意味し、高分岐ポリマーを硫酸中でスルホン化した後の反応液を使用する場合は、前記高分岐ポリマーをスルホン化する際に使用する硫酸の質量を意味するものとする。例えば、高分岐ポリマーのスルホン化において９５質量％濃度の硫酸を４０ｇ使用した場合、使用した硫酸の質量は３８ｇとなる。(1) Reprecipitation Treatment Step The reprecipitation treatment step is a step of adding a sulfuric acid solution of a sulfo group-containing highly branched polymer to water to reprecipitate the sulfo group-containing highly branched polymer. In the present invention, the sulfuric acid solution of the sulfo group-containing highly branched polymer may be a solution prepared by dissolving the sulfo group-containing highly branched polymer in sulfuric acid or a reaction solution after sulfonated the highly branched polymer in sulfuric acid. However, in consideration of work efficiency and the like, the reaction solution after sulfonate is preferable. In the following description, the mass of sulfuric acid means the mass of sulfuric acid used when dissolving the sulfo group-containing highly branched polymer when a solution prepared by dissolving the sulfo group-containing highly branched polymer in sulfuric acid is used, and is high. When the reaction solution after sulfonated the branched polymer in sulfuric acid is used, it means the mass of sulfuric acid used when sulfonated the highly branched polymer. For example, when 40 g of sulfuric acid having a concentration of 95% by mass is used in the sulfonation of a highly branched polymer, the mass of sulfuric acid used is 38 g.
スルホ基含有高分岐ポリマーの硫酸溶液に使用できる硫酸としては、濃硫酸や発煙硫酸等を挙げることができるが、コストや取扱性の観点から、特に濃硫酸を好適に使用できる。前記硫酸の濃度も、特に限定されるものではないが、ポリマーを効率的に沈殿させることを考慮すると、９０質量％以上が好ましく、９５質量％以上がより好ましい。（以下、単に％と表記することもある。） Examples of sulfuric acid that can be used in the sulfuric acid solution of the sulfo group-containing highly branched polymer include concentrated sulfuric acid and fuming sulfuric acid, but from the viewpoint of cost and handleability, concentrated sulfuric acid can be particularly preferably used. The concentration of the sulfuric acid is also not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, in consideration of efficient precipitation of the polymer. (Hereinafter, it may be simply expressed as%.)
スルホ基含有高分岐ポリマーの硫酸溶液において、硫酸の使用量は、特に限定されるものではないが、スルホ基含有高分岐ポリマーを硫酸に溶かして調製した溶液を使用する場合は、スルホ基含有高分岐ポリマーに対して、また、高分岐ポリマーを硫酸中でスルホン化した後の反応液を使用する場合は、スルホン化前の原料ポリマーに対して、２〜５０質量倍が好ましく、１０〜３０質量倍がより好ましい。 The amount of sulfuric acid used in the sulfuric acid solution of the sulfo group-containing highly branched polymer is not particularly limited, but when a solution prepared by dissolving the sulfo group-containing highly branched polymer in sulfuric acid is used, the sulfo group content is high. When the reaction solution after sulfonated the highly branched polymer in sulfuric acid is used for the branched polymer, it is preferably 2 to 50 times by mass, preferably 10 to 30 mass by mass, compared to the raw material polymer before sulfonation. Double is more preferable.
再沈殿処理工程で使用する水の量は、特に制限はないが、スルホ基含有高分岐ポリマーを速やかに再沈殿させる観点から、硫酸の質量に対する水の質量比（水／硫酸）は、０．５〜２が好ましく、高分岐ポリマーの凝集を適切に制御して濾過性をより向上させる観点から、０．９５〜１．２５がより好ましく、１〜１．２１が最適である。 The amount of water used in the reprecipitation treatment step is not particularly limited, but from the viewpoint of rapidly reprecipitating the sulfo group-containing highly branched polymer, the mass ratio of water to the mass of sulfuric acid (water / sulfuric acid) is 0. 5 to 2 is preferable, 0.95 to 1.25 is more preferable, and 1 to 1.21 is optimal from the viewpoint of appropriately controlling the aggregation of the highly branched polymer to further improve the filterability.
再沈殿処理時の液の温度（内温）は、特に制限されるものではないが、凝集を促進させる観点から、２５〜１００℃の範囲に制御することが好ましく、３０〜６０℃がより好ましい。 The temperature (internal temperature) of the liquid during the reprecipitation treatment is not particularly limited, but is preferably controlled in the range of 25 to 100 ° C., more preferably 30 to 60 ° C. from the viewpoint of promoting aggregation. ..
（２）凝集工程
凝集工程は、前記再沈殿処理工程で得た沈殿物を含む液と有機溶媒とを混合し、撹拌して前記沈殿物を適度に凝集させる工程である。(2) Aggregation Step The aggregation step is a step of mixing a liquid containing a precipitate obtained in the reprecipitation treatment step with an organic solvent and stirring the mixture to appropriately agglomerate the precipitate.
前記有機溶媒は、目的のスルホ基含有高分岐ポリマーを凝集させることができる溶媒であれば特に限定されるものではないが、プロトン性の有機溶媒、非プロトン性の有機溶媒等が挙げられる。 The organic solvent is not particularly limited as long as it is a solvent capable of aggregating the target sulfo group-containing highly branched polymer, and examples thereof include a protic organic solvent and an aprotic organic solvent.
プロトン性の有機溶媒としては、例えば、メタノール、エタノール、２−プロパノール等のアルコール系溶媒が挙げられる。
非プロトン性の有機溶媒としては、例えば、アセトニトリル等のニトリル系溶媒、テトラヒドロフラン、ジオキサン等の環状エーテル系溶媒、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒、ジメチルスルホキシド等のスルホキシド系溶媒が挙げられる。Examples of the protic organic solvent include alcohol solvents such as methanol, ethanol and 2-propanol.
Examples of the aprotonic organic solvent include a nitrile solvent such as acetonitrile, a cyclic ether solvent such as tetrahydrofuran and dioxane, and an amide solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide and dimethylacetamide. , Dimethyl sulfoxide and other sulfoxide-based solvents.
本発明において、有機溶媒は、前記で例示したものの中でも水と任意の割合で混和するものが好ましく、高分岐ポリマーの凝集を適切に制御できる観点から、テトラヒドロフラン、アセトニトリル、ジオキサン又はこれらの混合溶媒が好ましく、テトラヒドロフラン、ジオキサン又はこれらの混合溶媒がより好ましく、テトラヒドロフランがより一層好ましい。 In the present invention, the organic solvent is preferably miscible with water at an arbitrary ratio among those exemplified above, and from the viewpoint of appropriately controlling the aggregation of the highly branched polymer, tetrahydrofuran, acetonitrile, dioxane or a mixed solvent thereof is used. Preferably, tetrahydrofuran, dioxane or a mixed solvent thereof is more preferable, and tetrahydrofuran is even more preferable.
また、有機溶媒の使用量は、特に制限されないが、硫酸の質量に対する有機溶媒の質量比（有機溶媒／硫酸）は、０．５〜１．５が好ましく、高分岐ポリマーの凝集を適切に制御して濾過性をより向上させる観点から、０．５〜１．１がより好ましく、０．９〜１．１が更に好ましく、０．９５〜１．０５が最も好ましい。 The amount of the organic solvent used is not particularly limited, but the mass ratio of the organic solvent to the mass of sulfuric acid (organic solvent / sulfuric acid) is preferably 0.5 to 1.5, and the aggregation of the highly branched polymer is appropriately controlled. From the viewpoint of further improving the filterability, 0.5 to 1.1 is more preferable, 0.9 to 1.1 is further preferable, and 0.95 to 1.05 is most preferable.
液の温度（内温）は、高分岐ポリマーの凝集を適切に制御して濾過性をより向上させる観点から、２５〜１００℃が好ましく、３０〜６０℃がより好ましい。 The temperature (internal temperature) of the liquid is preferably 25 to 100 ° C., more preferably 30 to 60 ° C., from the viewpoint of appropriately controlling the aggregation of the highly branched polymer to further improve the filterability.
撹拌時間は、粒径１μｍ未満の細かい粒子を凝集させる観点から、２時間以上とすることが好ましく、４時間以上がより好ましい。また、その上限は特に制限されないが、５０時間以下が好ましく、２５時間以下がより好ましい。 The stirring time is preferably 2 hours or more, and more preferably 4 hours or more, from the viewpoint of aggregating fine particles having a particle size of less than 1 μm. The upper limit thereof is not particularly limited, but is preferably 50 hours or less, and more preferably 25 hours or less.
硫酸、水及び有機溶媒の合計使用量は、スルホン化前の原料ポリマーに対し５〜２００質量倍が好ましく、２０〜１００質量倍がより好ましく、４０〜８０質量倍が更に好ましい。合計使用量が、前記の範囲から外れた場合、凝集が進行しない場合がある。 The total amount of sulfuric acid, water and organic solvent used is preferably 5 to 200 times by mass, more preferably 20 to 100 times by mass, and even more preferably 40 to 80 times by mass with respect to the raw material polymer before sulfonation. If the total amount used is out of the above range, aggregation may not proceed.
加熱撹拌工程後は、沈殿物を瀘別し、濾物を必要に応じて水等で洗浄し、これを乾燥することで目的のポリマーを得ることができる。濾過設備は特に限定されるものではなく、公知の吸引濾過設備等を用いればよい。また、乾燥温度及び時間は、前記有機溶媒の種類やポリマーの耐熱性等によって異なるため一概に規定することはできないが、５０〜２００℃程度、好ましくは８０〜１５０℃程度で、１〜２００時間程度である。なお、乾燥時、−１０〜−１００ｋＰａ程度に減圧してもよい。 After the heating and stirring step, the precipitate is separated, the filter medium is washed with water or the like as necessary, and this is dried to obtain the desired polymer. The filtration equipment is not particularly limited, and a known suction filtration equipment or the like may be used. The drying temperature and time cannot be unconditionally defined because they differ depending on the type of the organic solvent, the heat resistance of the polymer, etc., but are about 50 to 200 ° C., preferably about 80 to 150 ° C. for 1 to 200 hours. Degree. When drying, the pressure may be reduced to about -10 to -100 kPa.
本発明の精製方法を実施することで、スルホ基含有高分岐ポリマーについては、残留硫酸を通常１，０００ｐｐｍ以下、場合によっては２００ｐｐｍ以下程度まで低減することができる。 By carrying out the purification method of the present invention, the residual sulfuric acid of the sulfo group-containing highly branched polymer can be reduced to about 1,000 ppm or less, and in some cases, about 200 ppm or less.
本発明の精製方法を適用できるスルホ基含有高分岐ポリマーは、その構造中にスルホ基を含有するものであれば特に制限はなく、例えば、トリアリールアミン構造を有する高分岐ポリマー（例えば、国際公開第２０１１／０６５３９５号等）、トリアジン環を含有する高分岐ポリマー（例えば、特開２０１４−０９８１０１号公報等）又はトリカルボニルベンゼン構造を有する高分岐ポリマー（例えば、特開２０１５−０９６６２５号公報等）等の高分岐ポリマーにスルホ基を導入したもの、特にポリマーの繰り返し単位の芳香環上にスルホ基を導入したものを挙げることができる。なお、これら高分岐ポリマーに対するスルホ基の導入は、例えば、過剰量の硫酸を用いてスルホン化する方法等により行うことができる（例えば、国際公開第２０１２／１６１３０７号等）。 The sulfo group-containing highly branched polymer to which the purification method of the present invention can be applied is not particularly limited as long as it contains a sulfo group in its structure, and is, for example, a highly branched polymer having a triarylamine structure (for example, international publication). No. 2011/065395, etc.), a highly branched polymer containing a triazine ring (for example, JP-A-2014-098101, etc.) or a highly branched polymer having a tricarbonylbenzene structure (for example, JP-A-2015-096625, etc.) Examples thereof include those in which a sulfo group is introduced into a highly branched polymer such as, and in particular, a polymer in which a sulfo group is introduced on the aromatic ring of a repeating unit of the polymer. The introduction of sulfo groups into these highly branched polymers can be carried out, for example, by a method of sulfonation with an excess amount of sulfuric acid (for example, International Publication No. 2012/161307, etc.).
本発明の精製方法は、これらの高分岐ポリマーの中でも、トリアリールアミン構造を有する高分岐ポリマー、より具体的には、トリアリールアミン化合物及びアルデヒド化合物を重合させることにより得られるノボラック型高分岐ポリマーにスルホ基を導入したもの、特にその繰り返し単位の芳香環上にスルホ基を導入したものにおいて好適に採用することができる。 Among these highly branched polymers, the purification method of the present invention is a novolak type highly branched polymer obtained by polymerizing a highly branched polymer having a triarylamine structure, more specifically, a triarylamine compound and an aldehyde compound. In particular, a polymer having a sulfo group introduced therein, particularly a polymer having a sulfo group introduced on the aromatic ring of the repeating unit, can be suitably adopted.
前記ノボラック型高分岐ポリマーは、上述した国際公開第２０１１／０６５３９５号に記載の方法によりトリアリールアミン化合物及びアルデヒド化合物を重合させることで得ることができるが、特に生成物のゲル化、高粘度化、壁固着物等の製造上の問題を回避する観点から、より好適な方法として以下の重合工程及びスルホン化工程を含む製造方法を採用することができる。 The novolak type highly branched polymer can be obtained by polymerizing a triarylamine compound and an aldehyde compound by the method described in International Publication No. 2011/065395 described above, and in particular, gelation and high viscosity of the product are obtained. From the viewpoint of avoiding problems in the production of wall-adhered substances and the like, a production method including the following polymerization step and sulfonate step can be adopted as a more preferable method.
［スルホ基含有高分岐ポリマーの合成］
（１）重合工程
重合工程は、トリアリールアミン化合物及びアルデヒド化合物を重合させてノボラック型高分岐ポリマーを得る工程である。[Synthesis of sulfo group-containing highly branched polymer]
(1) Polymerization Step The polymerization step is a step of polymerizing a triarylamine compound and an aldehyde compound to obtain a novolak type highly branched polymer.
前記トリアリールアミン化合物としては、下記式（Ａ）で表されるトリアリールアミン化合物が好ましい。
式（Ａ）中、Ａｒ1〜Ａｒ3は、それぞれ独立に、式（Ａ−１）〜（Ａ−５）のいずれかで表される２価の有機基であるが、特に、式（Ａ−１）で表される基が好ましい。In the formula (A), Ar 1 to Ar 3 are divalent organic groups represented by any of the formulas (A-1) to (A-5) independently, and in particular, the formula (A). The group represented by -1) is preferable.
式（Ａ−１）〜（Ａ−５）中、Ｒ1〜Ｒ34は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基である。In formulas (A-1) to (A-5), R 1 to R 34 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms. ..
ここで、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
炭素数１〜５のアルキル基としては、直鎖状又は分岐状のものが好ましく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基等が挙げられる。 The alkyl group having 1 to 5 carbon atoms is preferably linear or branched, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or an isobutyl group. , Tert-Butyl group, n-pentyl group and the like.
炭素数１〜５のアルコキシ基としては、直鎖状又は分岐状のものが好ましく、例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、イソブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペンチルオキシ基等が挙げられる。 The alkoxy group having 1 to 5 carbon atoms is preferably linear or branched, and for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, or an isobutoxy group. Groups, tert-butoxy group, n-pentyloxy group and the like can be mentioned.
好ましいトリアリールアミン化合物としては、トリフェニルアミン及びその誘導体等が挙げられる。 Preferred triarylamine compounds include triphenylamine and its derivatives.
前記アルデヒド化合物としては、特に限定されないが、下記式（Ｂ）で表されるものが好ましい。
式（Ｂ）中、Ｒは、それぞれ独立に、水素原子、炭素数１〜５のアルキル基、又は下記式（Ｂ−１）〜（Ｂ−４）のいずれかで表される１価の有機基である。
式（Ｂ−１）〜（Ｂ−４）中、Ｒ35〜Ｒ58は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のハロアルキル基、フェニル基、−ＯＲ59、−ＣＯＲ60、−ＮＲ61Ｒ62又は−ＣＯＯＲ63であり、Ｒ59〜Ｒ62は、それぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数１〜５のハロアルキル基又はフェニル基であり、Ｒ63は、炭素数１〜５のアルキル基、炭素数１〜５のハロアルキル基又はフェニル基である。Wherein (B-1) ~ (B -4), R 35 ~R 58 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, phenyl Group, -OR 59 , -COR 60 , -NR 61 R 62 or -COOR 63 , and R 59 to R 62 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and 1 to 5 carbon atoms, respectively. R 63 is an alkyl group having 1 to 5 carbon atoms and a haloalkyl group or phenyl group having 1 to 5 carbon atoms.
炭素数１〜５のハロアルキル基としては、直鎖状又は分岐状のものが好ましく、例えば、ジフルオロメチル基、トリフルオロメチル基、ブロモジフルオロメチル基、２−クロロエチル基、２−ブロモエチル基、１,１−ジフルオロエチル基、２,２,２−トリフルオロエチル基、１,１,２,２−テトラフルオロエチル基、２−クロロ−１,１,２−トリフルオロエチル基、ペンタフルオロエチル基、３−ブロモプロピル基、２,２,３,３−テトラフルオロプロピル基、１,１,２,３,３,３−ヘキサフルオロプロピル基、１,１,１,３,３,３−ヘキサフルオロプロパン−２−イル基、３−ブロモ−２−メチルプロピル基、４−ブロモブチル基、パーフルオロペンチル基等が挙げられる。なお、ハロゲン原子及び炭素数１〜５のアルキル基としては、前述したものと同様のものが挙げられる。 The haloalkyl group having 1 to 5 carbon atoms is preferably linear or branched, and for example, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, 1, 1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-Bromopropyl group, 2,2,3,3-Tetrafluoropropyl group, 1,1,2,3,3,3-Hexafluoropropyl group, 1,1,1,1,3,3,3-Hexafluoro Propyl-2-yl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, perfluoropentyl group and the like can be mentioned. Examples of the halogen atom and the alkyl group having 1 to 5 carbon atoms are the same as those described above.
前記アルデヒド化合物としては、芳香族アルデヒド化合物が好ましい。具体的には、式（Ｂ）で表されるアルデヒド化合物において、Ｒが、式（Ｂ−１）〜（Ｂ−４）のいずれかで表される基であるものが好ましく、２−若しくは３−チエニル基、又は式（Ｂ−１）で表される基であるものが好ましく、２−若しくは３−チエニル基、又は式（Ｂ−１）で表される基のうちＲ37がフェニル基であるもの若しくはメトキシ基であるものがより好ましく、２−若しくは３−チエニル基、又は式（Ｂ−１）で表される基のうちＲ37がフェニル基であるものがより一層好ましい。As the aldehyde compound, an aromatic aldehyde compound is preferable. Specifically, among the aldehyde compounds represented by the formula (B), those in which R is a group represented by any of the formulas (B-1) to (B-4) are preferable, and 2- or 3 -A thienyl group or a group represented by the formula (B-1) is preferable, and among the groups represented by the 2- or 3-thienyl group or the formula (B-1), R 37 is a phenyl group. A certain group or a methoxy group is more preferable, and a group represented by 2- or 3-thienyl group or the group represented by the formula (B-1) in which R 37 is a phenyl group is even more preferable.
好ましいアルデヒド化合物としては、ベンズアルデヒド、４−メチルベンズアルデヒド、３−トリフルオロメチルベンズアルデヒド、４−トリフルオロメチルベンズアルデヒド、３−フェニルベンズアルデヒド、４−フェニルベンズアルデヒド、サリチルアルデヒド、アニスアルデヒド、４−アセトキシベンズアルデヒド、４−アセチルベンズアルデヒド、２−ホルミル安息香酸、３−ホルミル安息香酸、４−ホルミル安息香酸、２−ホルミル安息香酸メチル、３−ホルミル安息香酸メチル、４−ホルミル安息香酸メチル、４−アミノベンズアルデヒド、４−ジメチルアミノベンズアルデヒド、４−ジフェニルアミノベンズアルデヒド、１−ナフトアルデヒド、２−ナフトアルデヒド、２−チオフェンカルバルデヒド、３−チオフェンカルバルデヒド、９−アントラセンカルバルデヒド等の芳香族アルデヒド化合物が挙げられる。 Preferred aldehyde compounds include benzaldehyde, 4-methylbenzaldehyde, 3-trifluoromethylbenzaldehyde, 4-trifluoromethylbenzaldehyde, 3-phenylbenzaldehyde, 4-phenylbenzaldehyde, salicylaldehyde, anisaldehyde, 4-acetoxybenzaldehyde, 4- Acetylbenzaldehyde, 2-formyl benzoic acid, 3-formyl benzoic acid, 4-formyl benzoic acid, 2-formyl benzoate methyl, 3-formyl benzoate methyl, 4-formyl benzoate methyl, 4-aminobenzaldehyde, 4-dimethyl Examples thereof include aromatic aldehyde compounds such as aminobenzaldehyde, 4-diphenylaminobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2-thiophenecarbaldehyde, 3-thiofencarbaldehyde, and 9-anthracenecarbaldehyde.
式（Ａ）で表されるトリアリールアミン化合物と、式（Ｂ）で表されるアルデヒド化合物とを、酸触媒存在下で重合させることで、下記式（Ｃ）で表される繰り返し単位を含む高分岐ポリマーを合成することができる。 By polymerizing the triarylamine compound represented by the formula (A) and the aldehyde compound represented by the formula (B) in the presence of an acid catalyst, the repeating unit represented by the following formula (C) is contained. Highly branched polymers can be synthesized.
前記高分岐ポリマーとして好ましくは、下記式で表される繰り返し単位を有するものが挙げられるが、これらに限定されない。 The highly branched polymer preferably includes, but is not limited to, a polymer having a repeating unit represented by the following formula.
前記式（Ｂ）で表されるアルデヒド化合物の使用量は、式（Ａ）で表されるトリアリールアミン化合物１当量に対し、前記アルデヒド化合物０．１〜１．０当量が好ましく、０．７〜０．９５当量がより好ましい。 The amount of the aldehyde compound represented by the formula (B) to be used is preferably 0.1 to 1.0 equivalents, preferably 0.7, with respect to 1 equivalent of the triarylamine compound represented by the formula (A). ~ 0.95 equivalent is more preferred.
前記高分岐ポリマーの平均分子量は特に限定されないが、重量平均分子量（Ｍｗ）が１,０００〜２,０００,０００が好ましく、２,０００〜２００,０００がより好ましい。なお、本発明においてＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算測定値である。 The average molecular weight of the highly branched polymer is not particularly limited, but the weight average molecular weight (Mw) is preferably 1,000 to 2,000,000, more preferably 2,000 to 200,000. In the present invention, Mw is a polystyrene-equivalent measured value by gel permeation chromatography (GPC).
前記酸触媒としては、硫酸、リン酸、過塩素酸等の無機酸や、ｐ−トルエンスルホン酸、メタンスルホン酸、カンファースルホン酸等のスルホン酸、ギ酸、シュウ酸等のカルボン酸等の有機酸を用いることができるが、硫酸、スルホン酸が好ましい。酸触媒の使用量は、その種類によって適宜設定されるが、通常、トリアリールアミン化合物１当量に対し、０.０１〜０.５当量が好ましく、０.０２〜０.２当量がより好ましい。 Examples of the acid catalyst include inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid, sulfonic acids such as p-toluene sulfonic acid, methane sulfonic acid and camphor sulfonic acid, and organic acids such as carboxylic acid such as formic acid and oxalic acid. Can be used, but sulfuric acid and sulfonic acid are preferable. The amount of the acid catalyst used is appropriately set depending on the type thereof, but is usually preferably 0.01 to 0.5 equivalents, more preferably 0.02 to 0.2 equivalents, relative to 1 equivalent of the triarylamine compound.
前記トリアリールアミン化合物とアルデヒド化合物との縮合重合によって合成されるが、このとき脱水が起こるため、副生成物として水が生じる。本発明の製造方法においては、この副生した水を反応系内から除去しながら重合反応を行うことが好ましい。 It is synthesized by condensation polymerization of the triarylamine compound and an aldehyde compound, but dehydration occurs at this time, so that water is produced as a by-product. In the production method of the present invention, it is preferable to carry out the polymerization reaction while removing the by-produced water from the reaction system.
前記副生成物の水を除去する方法としては、特に限定されないが、共沸によって除去する方法が、大量製造の点から好ましい。共沸によって水を除去する方法としては、例えば、ディーンスターク装置を用いて副生する水を除去する方法が挙げられる。 The method for removing water as a by-product is not particularly limited, but a method for removing water by azeotrope is preferable from the viewpoint of mass production. Examples of the method of removing water by azeotrope include a method of removing by-produced water using a Dean-Stark apparatus.
このとき、有機溶媒としては、水と共沸可能であって、水よりも比重が小さく、かつ水と混和しないものが好ましい。なお、本発明において「水と混和しない」とは、溶解する水分量が５.０質量％未満の有機溶媒を指す。このような有機溶媒としては、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン等の芳香族炭化水素類、ヘプタン、ヘキサン、シクロヘキサン等の脂肪族炭化水素類、ジエチルエーテル、シクロペンチルメチルエーテル等のエーテル類、２−メチルテトラヒドロフラン、４−メチルテトラヒドロピラン、メチルイソブチルケトン等のケトン類等が挙げられる。これらのうち、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン又はこれらの混合物が好ましい。前記有機溶媒の使用量は、トリアリールアミン化合物及びアルデヒド化合物の合計に対し、質量比で１〜５０となる量が好ましく、２〜１０となる量がより好ましい。 At this time, the organic solvent is preferably one that is azeotropic with water, has a lower specific gravity than water, and is immiscible with water. In the present invention, "immiscible with water" refers to an organic solvent having a dissolved water content of less than 5.0% by mass. Examples of such an organic solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene, aliphatic hydrocarbons such as heptane, hexane and cyclohexane, diethyl ether and cyclopentyl methyl ether. Examples thereof include ethers, ketones such as 2-methyl tetrahydrofuran, 4-methyltetrahydropyran, and methylisobutylketone. Of these, toluene, o-xylene, m-xylene, p-xylene or a mixture thereof is preferable. The amount of the organic solvent used is preferably 1 to 50 in terms of mass ratio with respect to the total of the triarylamine compound and the aldehyde compound, and more preferably 2 to 10.
重合反応時の温度は、用いる原料や溶媒に応じて適宜設定すればよいが、通常４０〜２００℃である。また、前述したようにディーンスターク装置を用いて共沸によって水の除去を行う場合、還流温度で反応させるが、このとき十分に還流させるため、外温を内温（還流温度）よりも１℃以上高く設定することが好ましく、内温よりも１０℃以上高く設定することがより好ましい。外温の上限は、特に限定されないが、通常、内温＋２０℃程度である。 The temperature at the time of the polymerization reaction may be appropriately set depending on the raw material and solvent used, but is usually 40 to 200 ° C. Further, as described above, when water is removed by azeotrope using a Dean-Stark apparatus, the reaction is carried out at the reflux temperature, but in order to sufficiently reflux the water at this time, the outside temperature is 1 ° C. higher than the internal temperature (reflux temperature). It is preferable to set it higher than that, and it is more preferable to set it higher than the internal temperature by 10 ° C. or more. The upper limit of the external temperature is not particularly limited, but is usually about + 20 ° C.
反応時間は、反応温度によって適宜選択されるが、通常１〜３０時間程度である。 The reaction time is appropriately selected depending on the reaction temperature, but is usually about 1 to 30 hours.
得られた高分岐ポリマーは、反応液をそのままで、又は精製して固体状としてから次のスルホン化工程に供される。 The obtained highly branched polymer is subjected to the next sulfonation step as it is or after being purified into a solid state.
（２）スルホン化工程
スルホン化工程は、前記重合工程で得た高分岐ポリマーにスルホ基を導入する工程であるが、スルホ基を導入する方法としては、特に制限はなく、例えば、過剰量の硫酸を用いてスルホン化する方法等を用いることができる（例えば、国際公開第２０１２／１６１３０７号等）。(2) Sulfonization Step The sulfonation step is a step of introducing a sulfo group into the highly branched polymer obtained in the polymerization step, but the method of introducing the sulfo group is not particularly limited, and for example, an excess amount is used. A method of sulfonation with sulfuric acid or the like can be used (for example, International Publication No. 2012/161307, etc.).
前記硫酸としては、濃硫酸、発煙硫酸等を使用することができ、コストや取扱性の観点から、濃硫酸を好適に採用し得る。なお、前記硫酸の濃度は、９０質量％以上が好ましく、９５質量％以上がより好ましい。 As the sulfuric acid, concentrated sulfuric acid, fuming sulfuric acid and the like can be used, and concentrated sulfuric acid can be preferably used from the viewpoint of cost and handleability. The concentration of the sulfuric acid is preferably 90% by mass or more, more preferably 95% by mass or more.
スルホン化に用いる硫酸の量としては特に制限はないが、高分岐ポリマー１質量部に対して１００質量部以下が好ましく、後処理時に水へ投入する際の発熱制御等の操作を考慮すると５０質量部以下がより好ましく、３０質量部以下が更に好ましい。下限は特に制限されないが、２質量部以上が好ましく、１０質量部以上がより好ましい。 The amount of sulfuric acid used for sulfonation is not particularly limited, but is preferably 100 parts by mass or less with respect to 1 part by mass of the highly branched polymer, and 50 mass by mass in consideration of operations such as heat generation control when adding to water during post-treatment. It is more preferably parts or less, and even more preferably 30 parts by mass or less. The lower limit is not particularly limited, but is preferably 2 parts by mass or more, and more preferably 10 parts by mass or more.
スルホン化の際の反応温度は、用いる原料や溶媒に応じて適宜設定すればよいが、通常２０〜１００℃であり、好ましくは３０〜６０℃である。 The reaction temperature at the time of sulfonation may be appropriately set depending on the raw material and solvent used, but is usually 20 to 100 ° C, preferably 30 to 60 ° C.
反応時間は、反応温度によって適宜選択されるが、通常１〜２４時間程度であり、１時間以上あれば特に制限はされない。 The reaction time is appropriately selected depending on the reaction temperature, but is usually about 1 to 24 hours, and is not particularly limited as long as it is 1 hour or more.
前記スルホ基含有高分岐ポリマーとして好ましくは、スルホ基がポリマーの繰り返し単位の芳香環上に導入されたものが好ましく、より好ましい具体例として、下記式で表される繰り返し単位を有するものが挙げられるが、これに限定されない。 The sulfo group-containing highly branched polymer is preferably one in which a sulfo group is introduced on the aromatic ring of the repeating unit of the polymer, and more preferable specific examples include those having a repeating unit represented by the following formula. However, it is not limited to this.
スルホン化後、前記スルホ基含有高分岐ポリマーは、硫酸溶液として得られ、反応液をそのままで、又は溶媒等を除去して固体状としてから前述の再沈殿工程へと供される。 After sulfonation, the sulfo group-containing highly branched polymer is obtained as a sulfuric acid solution, and the reaction solution is used as it is or after removing a solvent or the like to form a solid, and then subjected to the above-mentioned reprecipitation step.
以下、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、実施例で用いた各測定装置等は以下のとおりである。
（１）数平均分子量Ｍｎ，質量平均分子量Ｍｗ
ＧＰＣ（ゲル浸透クロマトグラフィ）
装置：（株）島津製作所製 ＳＣＬ−１０Ａｖｐシリーズ
カラム：Ｓｈｏｄｅｘ ＫＦ−８０５＋ＫＦ−８０４＋ＫＦ−８０３
カラム温度：４０℃
溶媒：テトラヒドロフラン
検出器：ＵＶ（２７１ｎｍ）
検量線：標準ポリスチレン
（２）残留硫酸量
イオンクロマトグラフ法
装置（燃焼）：（株）三菱アナリテック製 ＩＧＦ−１００
装置（イオンクロマトグラフ）：日本ダイオネクス（株）製 ＩＣＳ−１５００
試料１ｍｇに５ｍＭ−ＮａＯＨを１０ｍＬ加え、よく振とうし、液液抽出を行った。水相をイオンクロマトグラフで測定し、水相側に抽出された硫酸分を測定し、定量を行った。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring devices and the like used in the examples are as follows.
(1) Number average molecular weight Mn, mass average molecular weight Mw
GPC (Gel Permeation Chromatography)
Equipment: SCL-10Avp series manufactured by Shimadzu Corporation Column: Shodex KF-805 + KF-804 + KF-803
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (271 nm)
Calibration curve: Standard polystyrene (2) Residual sulfuric acid ion chromatograph method Equipment (combustion): IGF-100 manufactured by Mitsubishi Analytech Co., Ltd.
Equipment (ion chromatograph): ICS-1500 manufactured by Nippon Dionex Corporation
10 mL of 5 mM-NaOH was added to 1 mg of the sample, shaken well, and liquid-liquid extraction was performed. The aqueous phase was measured by an ion chromatograph, and the sulfuric acid content extracted on the aqueous phase side was measured and quantified.
［合成例１］原料ポリマーの合成
（１）下記スキームに示される反応に従って、ポリマーＰＴＰＡを合成した。
ディーンスターク装置を接続した２００ｍＬフラスコに、トリフェニルアミン（Zhenjiang Haitong Chemical Industry社製）１０ｇ、４−フェニルベンズアルデヒド（Beijing Odyssey Chemicals社製）６.５ｇ（０.８７ｅｑ.）、ｐ−トルエンスルホン酸（関東化学（株）製）０.３８８ｇ（０.０５ｅｑ.）、及びトルエン６０ｇを仕込み、還流状態（内温１１０〜１１５℃）となるよう昇温した。反応系内が常に還流状態となるように外温を還流温度（内温１１０〜１１５℃）＋２０℃に維持し、副生する水を共沸によって反応系内から除去しながら、３時間反応させた。３時間経過後、ＧＰＣにてポリマーのＭｗが３５,０００〜４５,０００付近に到達したことを確認し、４−フェニルベンズアルデヒドが全て消失し、重合が停止していることを確認した。得られたポリマーのトルエン溶液にトリエチルアミン（東京化成工業（株）製）０.２５ｇ（０.０６ｅｑ.）を加え、クエンチした。クエンチ後のポリマー溶液を貧溶媒であるアセトン３０ｇ及び水２７０ｇの混合溶媒へと投入し、再沈殿させた。沈殿物を濾別し、アセトンにて濾物通液洗浄を繰り返した後、乾燥機にて１００℃で乾燥し、目的のポリマーＰＴＰＡを得た。 In a 200 mL flask connected to the Dean-Stark apparatus, 10 g of triphenylamine (manufactured by Zhenjiang Haitong Chemical Industry), 6.5 g (0.87 eq.) Of 4-phenylbenzaldehyde (manufactured by Beijing Odyssey Chemicals), and p-toluenesulfonic acid (manufactured by Beijing Odyssey Chemicals). 0.388 g (0.05eq.) (Manufactured by Kanto Chemical Co., Ltd.) and 60 g of toluene were charged, and the temperature was raised so as to be in a reflux state (internal temperature 110 to 115 ° C.). The outside temperature is maintained at the reflux temperature (internal temperature 110-115 ° C) + 20 ° C. so that the inside of the reaction system is always in a reflux state, and the reaction is carried out for 3 hours while removing by-product water from the reaction system by azeotrope. It was. After 3 hours, it was confirmed by GPC that the Mw of the polymer reached the vicinity of 35,000 to 45,000, and it was confirmed that all 4-phenylbenzaldehyde disappeared and the polymerization was stopped. To a toluene solution of the obtained polymer, 0.25 g (0.06 eq.) Of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and quenched. The polymer solution after quenching was poured into a mixed solvent of 30 g of acetone and 270 g of water, which are poor solvents, and reprecipitated. The precipitate was separated by filtration, and the filtrate was washed with acetone repeatedly, and then dried in a dryer at 100 ° C. to obtain the desired polymer PTPA.
［実施例１］
５０ｍＬフラスコに９５％濃硫酸（純正化学（株）製）４０ｇを仕込み、内温を３５〜４５℃に調整した後、合成例１で得た原料ポリマーＰＴＰＡ２ｇを投入した。その後、内温３５〜４５℃にて３時間攪拌した後、室温付近まで冷却し、スルホン化されたＰＴＰＡ（以下、ＰＴＰＡ−Ｓ）の硫酸溶液を得た。別途用意した２００ｍＬフラスコに水４４ｇを仕込んだ後、得られたＰＴＰＡ−Ｓの硫酸溶液を、内温３０℃以下を維持しながら滴下し、再沈殿操作を行った。その後、テトラヒドロフラン（関東化学（株）製）４０ｇを加え、内温を４５〜５０℃に調整し、１０時間撹拌して沈殿物を凝集させた。得られた沈殿物を桐山ロート（Φ６０ｍｍ、濾紙Ｎｏ．５Ｂ）にて減圧濾別したところ、濾過時間１６秒で完了した。続く濾物通液洗浄においても、濾過性は悪化することなく、目的のポリマーＰＴＰＡ−Ｓを得ることができ、乾燥後に得られたＰＴＰＡ−Ｓ中の残留硫酸量は２００ｐｐｍ未満であった。[Example 1]
40 g of 95% concentrated sulfuric acid (manufactured by Junsei Chemical Co., Ltd.) was charged in a 50 mL flask, the internal temperature was adjusted to 35 to 45 ° C., and then 2 g of the raw material polymer PTPA obtained in Synthesis Example 1 was added. Then, after stirring at an internal temperature of 35 to 45 ° C. for 3 hours, the mixture was cooled to around room temperature to obtain a sulfuric acid solution of sulfonated PTPA (hereinafter, PTPA-S). After 44 g of water was charged into a separately prepared 200 mL flask, the obtained sulfuric acid solution of PTPA-S was added dropwise while maintaining an internal temperature of 30 ° C. or lower, and a reprecipitation operation was performed. Then, 40 g of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) was added, the internal temperature was adjusted to 45 to 50 ° C., and the mixture was stirred for 10 hours to aggregate the precipitate. The obtained precipitate was filtered under reduced pressure using a Kiriyama funnel (Φ60 mm, filter paper No. 5B), and the filtration time was 16 seconds. In the subsequent washing with a filter medium, the target polymer PTPA-S could be obtained without deteriorating the filterability, and the amount of residual sulfuric acid in the PTPA-S obtained after drying was less than 200 ppm.
［比較例１］
５０ｍＬフラスコに９５％濃硫酸４０ｇ（純正化学（株）製）を仕込み、内温を３５〜４５℃に調整した後、合成例１で得た原料ポリマーＰＴＰＡ２ｇを投入した。その後、内温３５〜４５℃にて３時間攪拌した後、室温付近まで冷却し、ＰＴＰＡ−Ｓの硫酸溶液を得た。別途用意した２００ｍＬフラスコに水８６ｇを仕込んだ後、得られたＰＴＰＡ−Ｓの硫酸溶液を、内温３０℃以下を維持しながら滴下し、再沈殿操作を行った。その後、５０℃にて１５時間攪拌し、得られた沈殿物を桐山ロート（Φ６０ｍｍ、濾紙Ｎｏ．５Ｂ）にて減圧濾別したところ、濾過時間９３秒を要した。続く濾物通液洗浄においては、経時的に濾過時間は長くなり、最終的に目詰まりして濾過操作を完了することができなかった。[Comparative Example 1]
40 g of 95% concentrated sulfuric acid (manufactured by Junsei Chemical Co., Ltd.) was charged in a 50 mL flask, the internal temperature was adjusted to 35 to 45 ° C., and then 2 g of the raw material polymer PTPA obtained in Synthesis Example 1 was added. Then, after stirring at an internal temperature of 35 to 45 ° C. for 3 hours, the mixture was cooled to near room temperature to obtain a sulfuric acid solution of PTPA-S. After charging 86 g of water into a separately prepared 200 mL flask, the obtained sulfuric acid solution of PTPA-S was added dropwise while maintaining an internal temperature of 30 ° C. or lower, and a reprecipitation operation was performed. Then, the mixture was stirred at 50 ° C. for 15 hours, and the obtained precipitate was filtered under reduced pressure with a Kiriyama funnel (Φ60 mm, filter paper No. 5B). As a result, a filtration time of 93 seconds was required. In the subsequent washing of the filter medium, the filtration time became longer with time, and finally the filtration operation could not be completed due to clogging.
Claims (12)
前記再沈殿処理工程で得た沈殿物を含む液と有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程
を含むことを特徴とするスルホ基含有高分岐ポリマーの精製方法。A reprecipitation treatment step of adding a sulfuric acid solution of a sulfo group-containing highly branched polymer to water to reprecipitate the sulfo group-containing highly branched polymer, and a liquid containing a precipitate obtained in the reprecipitation treatment step and an organic solvent. A method for purifying a sulfo group-containing highly branched polymer, which comprises an aggregation step of mixing and stirring to aggregate the precipitate.
前記高分岐ポリマーを硫酸中でスルホン化して、スルホ基含有高分岐ポリマーの硫酸溶液を得るスルホン化工程、
前記スルホン化工程で得たスルホ基含有高分岐ポリマーの硫酸溶液を水へ投入して、前記スルホ基含有高分岐ポリマーを再沈殿させる再沈殿処理工程、及び
前記再沈殿処理工程で得た沈殿物を含む液と、水と混和する有機溶媒とを混合し、撹拌して前記沈殿物を凝集させる凝集工程
を含むことを特徴とするスルホ基含有高分岐ポリマーの製造方法。Polymerization step of polymerizing a triarylamine compound and an aldehyde compound to obtain a highly branched polymer,
A sulfonate step of sulfonated the highly branched polymer in sulfuric acid to obtain a sulfuric acid solution of the sulfo group-containing highly branched polymer.
A reprecipitation treatment step of adding a sulfuric acid solution of the sulfo group-containing highly branched polymer obtained in the sulfonated step to water to reprecipitate the sulfo group-containing highly branched polymer, and a precipitate obtained in the reprecipitation treatment step. A method for producing a sulfo group-containing highly branched polymer, which comprises a coagulation step of mixing a liquid containing the above-mentioned substance and an organic solvent to be mixed with water and stirring the mixture to coagulate the precipitate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017177930 | 2017-09-15 | ||
| JP2017177930 | 2017-09-15 | ||
| PCT/JP2018/033252 WO2019054301A1 (en) | 2017-09-15 | 2018-09-07 | Method for purifying sulfo group-containing hyperbranched polymer and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2019054301A1 true JPWO2019054301A1 (en) | 2020-10-15 |
| JP7099466B2 JP7099466B2 (en) | 2022-07-12 |
Family
ID=65722677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019542033A Active JP7099466B2 (en) | 2017-09-15 | 2018-09-07 | A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same. |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7099466B2 (en) |
| CN (1) | CN111094372B (en) |
| TW (1) | TWI783039B (en) |
| WO (1) | WO2019054301A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012161306A1 (en) * | 2011-05-25 | 2012-11-29 | 日産化学工業株式会社 | Conductive composition, and conductive complex |
| WO2012161307A1 (en) * | 2011-05-25 | 2012-11-29 | 日産化学工業株式会社 | Highly branched polymer and diepsersant for carbon nanotubes |
| JP2012245441A (en) * | 2011-05-25 | 2012-12-13 | Nissan Chem Ind Ltd | Carbon nanotube dispersant |
| JP2013006756A (en) * | 2011-05-25 | 2013-01-10 | Nissan Chem Ind Ltd | Method for improving conductivity of carbon nanotube dispersion material |
| WO2014042080A1 (en) * | 2012-09-14 | 2014-03-20 | 日産化学工業株式会社 | Composite current collector for energy storage device electrode, and electrode |
| WO2016117524A1 (en) * | 2015-01-23 | 2016-07-28 | 日産化学工業株式会社 | Method for purifying triazine-ring-containing polymer |
| WO2016117531A1 (en) * | 2015-01-23 | 2016-07-28 | 日産化学工業株式会社 | Method for purifying triazine-ring-containing polymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016035823A1 (en) * | 2014-09-02 | 2017-06-15 | 国立大学法人九州大学 | Low resistance clad material and electro-optic polymer optical waveguide |
-
2018
- 2018-09-07 JP JP2019542033A patent/JP7099466B2/en active Active
- 2018-09-07 CN CN201880059465.0A patent/CN111094372B/en active Active
- 2018-09-07 WO PCT/JP2018/033252 patent/WO2019054301A1/en active Application Filing
- 2018-09-14 TW TW107132364A patent/TWI783039B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012161306A1 (en) * | 2011-05-25 | 2012-11-29 | 日産化学工業株式会社 | Conductive composition, and conductive complex |
| WO2012161307A1 (en) * | 2011-05-25 | 2012-11-29 | 日産化学工業株式会社 | Highly branched polymer and diepsersant for carbon nanotubes |
| JP2012245441A (en) * | 2011-05-25 | 2012-12-13 | Nissan Chem Ind Ltd | Carbon nanotube dispersant |
| JP2013006756A (en) * | 2011-05-25 | 2013-01-10 | Nissan Chem Ind Ltd | Method for improving conductivity of carbon nanotube dispersion material |
| WO2014042080A1 (en) * | 2012-09-14 | 2014-03-20 | 日産化学工業株式会社 | Composite current collector for energy storage device electrode, and electrode |
| WO2016117524A1 (en) * | 2015-01-23 | 2016-07-28 | 日産化学工業株式会社 | Method for purifying triazine-ring-containing polymer |
| WO2016117531A1 (en) * | 2015-01-23 | 2016-07-28 | 日産化学工業株式会社 | Method for purifying triazine-ring-containing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111094372A (en) | 2020-05-01 |
| CN111094372B (en) | 2022-10-21 |
| WO2019054301A1 (en) | 2019-03-21 |
| JP7099466B2 (en) | 2022-07-12 |
| TW202017961A (en) | 2020-05-16 |
| TWI783039B (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6192653B2 (en) | Method for producing trioxane from an aqueous formaldehyde source | |
| CN106432568B (en) | The preparation method of Yi Zhong Duo oxazolinyl chain extenders | |
| Wei et al. | Diels–Alder reaction in water for the straightforward preparation of thermoresponsive hydrogels | |
| CN111517989B (en) | Self-catalytic curing-based resin containing alkyl phthalonitrile and preparation method thereof | |
| Doganci et al. | Synthesis of AB 3‐type miktoarm star polymers with steroid core via a combination of “Click” chemistry and ring opening polymerization techniques | |
| CN104844772A (en) | Soluble elemental sulfur and alicyclic olefin copolymer and preparation method thereof | |
| JP7099466B2 (en) | A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same. | |
| CN106518926B (en) | A kind of preparation method of the water-soluble benzoxazine compound containing DOPO | |
| Cheng et al. | A facile method for the preparation of thermally remendable cross‐linked polyphosphazenes | |
| Gacal et al. | The synthesis of poly (ethylene glycol)(PEG) containing polymers via step‐growth click coupling reaction for CO2 separation | |
| Dou et al. | A simple and efficient synthetic method for poly (ethylene terephthalate): phenylalkyl pyrrolidinium ionic liquid as polycondensation medium | |
| JP2006225461A (en) | Polythiophene | |
| JP5394779B2 (en) | Modified natural rubber and method for producing modified natural rubber latex, modified natural rubber, modified natural rubber latex and tire using modified natural rubber | |
| Ding et al. | Catalytic Polymerizations of Hydrophobic, Substituted, Acetylene Monomers in an Aqueous Medium by Using a Monomer/Hydroxypropyl‐β‐cyclodextrin Inclusion Complex | |
| JP7131558B2 (en) | Method for producing novolak-type polymer | |
| JP4431790B2 (en) | Resorcinol novolac derivatives | |
| CN106046363A (en) | Tetramethoxyfluorene-structure-containing high-solubility polyaryl amides and preparation method thereof | |
| Shibata et al. | Intermolecular interaction of supramolecular organic–inorganic hybrid composites of sulfonated polystyrene and oligomeric silsesquioxane possessing pyridyl groups | |
| JP2002322293A (en) | Filmy material and method for producing the same | |
| CN105085919B (en) | Hydrocarbon system polymeric electrolyte synthetic method and the polymer solvent for it | |
| Jikei et al. | Synthesis and properties of hyperbranched poly (ether sulfone) s prepared by self‐polycondensation of novel AB2 monomer | |
| CN110003078B (en) | Preparation method of 1, 3-bis (furfuryl imide methyl) benzene as rubber anti-vulcanization reversion agent | |
| KR20170012974A (en) | Novel method for preparation of polybenzimidazole under mild condition | |
| KR20160140707A (en) | Alkylene oxide polymer production method | |
| CN103819316B (en) | Curable polyfluorene and the application as heat-stable material thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210825 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220531 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220613 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7099466 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |