JP2016186058A - Water-soluble polymer - Google Patents
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Abstract
Description
本発明は、凝集性能に優れるポリアミジン系の水溶性高分子に関するものである。 The present invention relates to a polyamidine-based water-soluble polymer having excellent aggregation performance.
アミジン型水溶性高分子は、その高いカチオン密度によって有機汚泥に対して効率的に吸着し、脱水性に優れた強固なフロックを形成することができ、腐敗が進行した難脱水性の汚泥に対する凝集剤として特に有効であることが知られている。 Amidine-type water-soluble polymers can be efficiently adsorbed to organic sludge by their high cation density, and can form strong flocs with excellent dewatering properties. It is known to be particularly effective as an agent.
従来、アミジン型水溶性高分子の製造は、ビニルホルムアミドとアクリロニトリルとの共重合体を酸性処理することによりホルムアミド基をアミノ基へ化学変性し、その後、加熱処理することにより隣接するニトリル基と分子内環化させて、高分子鎖にアミジン環を形成させていた。この方法は、アミノ基を効率的に形成させることができることから高アミジン化が容易であり、副生物も少なく優れた製造方法であると言える（例えば、特許文献１参照）。しかしながら、原料モノマーの一つであるビニルホルムアミドが極めて高価であることから、その製造コストを低減することは難しいとされてきた。 Conventionally, amidine-type water-soluble polymers have been produced by chemically modifying a formamide group into an amino group by acid treatment of a copolymer of vinylformamide and acrylonitrile, and then heat-treating the adjacent nitrile group and molecule. It was cyclized internally to form an amidine ring in the polymer chain. Since this method can efficiently form an amino group, it can be easily produced as a high amidine, and it can be said to be an excellent production method with few by-products (see, for example, Patent Document 1). However, since vinylformamide, which is one of the raw material monomers, is extremely expensive, it has been difficult to reduce its production cost.
一方、低コストのアミジン型水溶性高分子の製造方法として、特許文献２に記載の方法が提案されている。この方法は、安価なアクリルアミドとアクリロニトリルを原料としてベースとなるポリマーを重合し、これを次亜塩素酸ナトリウム等の酸化剤と苛性ソーダ等のアルカリを用いるホフマン反応によってアミド基をアミノ基へ変性した後、上記の方法と同様に酸性処理、加熱処理によってアミジン環を形成させる方法である。 On the other hand, a method described in Patent Document 2 has been proposed as a method for producing a low-cost amidine-type water-soluble polymer. This method involves polymerizing a base polymer using inexpensive acrylamide and acrylonitrile as raw materials, and then modifying the amide group to an amino group by a Hofmann reaction using an oxidizing agent such as sodium hypochlorite and an alkali such as caustic soda. In the same manner as described above, an amidine ring is formed by acid treatment and heat treatment.
しかしながら、特許文献２で提案された方法では、過酷な塩基性条件下で酸化剤を用いてホフマン反応によりアミド基からアミノ基へと変性しているため、酸化剤による分子切断が生じ、得られる水溶性高分子の分子量が低くなり、凝集性能が低下するといった問題や、塩基性条件下でホフマン反応した後に中和、酸性化してアミジン化しているため、多量のアルカリや酸が必要となる上、多量の塩が副生するという問題が生じる。 However, in the method proposed in Patent Document 2, since the amide group is denatured from the amide group to the amino group by the Hofmann reaction using an oxidizing agent under severe basic conditions, molecular cleavage by the oxidizing agent occurs and is obtained. Problems such as low molecular weight of water-soluble polymers and degradation of aggregation performance, and neutralization, acidification and amidineization after the Hoffman reaction under basic conditions require a large amount of alkali and acid. This causes a problem that a large amount of salt is produced as a by-product.
そのため、水溶性高分子の凝集性能が必ずしも十分ではないといった課題や生産性が悪いといった課題があった。 For this reason, there is a problem that the aggregation performance of the water-soluble polymer is not always sufficient and a problem that productivity is poor.
本発明者らは、上記課題を解決すべく鋭意検討した結果、特定のポリアミジン系の水溶性高分子が凝集性能に優れることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific polyamidine-based water-soluble polymer is excellent in aggregation performance, and have completed the present invention.
すなわち、本発明は、アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素化合物とを酸性条件下で加熱処理して得られる、下記式（１）で示される構造単位、下記式（２）で示される構造単位、下記式（３）で示される構造単位、下記式（４）で示される構造単位、および下記式（５）で示される構造単位を含み、且つ下記式（１）で示される構造単位が２０モル％以上であることを特徴とする水溶性高分子に関するものである。 That is, the present invention is a structural unit represented by the following formula (1), which is obtained by heat-treating a copolymer of acrylamide and acrylonitrile and a hypervalent iodine compound under acidic conditions: A structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5), and represented by the following formula (1): The present invention relates to a water-soluble polymer having a structural unit of 20 mol% or more.
以下、本発明を詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明の水溶性高分子は、アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素化合物とを酸性条件下で加熱処理して得られる、下記式（１）で示される構造単位、下記式（２）で示される構造単位、下記式（３）で示される構造単位、下記式（４）で示される構造単位、および下記式（５）で示される構造単位を含み、且つ下記式（１）で示される構造単位が２０モル％以上であることを特徴とするものである。 The water-soluble polymer of the present invention is a structural unit represented by the following formula (1) obtained by heat-treating a copolymer of acrylamide and acrylonitrile and a hypervalent iodine compound under acidic conditions, 2), a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5), and the following formula (1) The structural unit is represented by 20 mol% or more.
本発明の水溶性高分子は、下記式（１）で示される構造単位、下記式（２）で示される構造単位、下記式（３）で示される構造単位、下記式（４）で示される構造単位、および下記式（５）で示される構造単位を含み、優れた凝集性能が得られることから、下記式（１）で示される構造単位を２０モル％以上含むものであり、２５モル％以上含むことが好ましい。 The water-soluble polymer of the present invention is represented by the structural unit represented by the following formula (1), the structural unit represented by the following formula (2), the structural unit represented by the following formula (3), and the following formula (4). Since the structural unit and the structural unit represented by the following formula (5) are included and excellent aggregation performance is obtained, the structural unit represented by the following formula (1) is contained in an amount of 20 mol% or more, and 25 mol%. It is preferable to include the above.
本発明の水溶性高分子の製造に用いるアクリルアミドとアクリロニトリルからなる共重合物は、アクリルアミドとアクリロニトリルからなる共重合物であれば如何なるものでも使用することができるが、凝集性能と生産性の観点より、アクリルアミドを４０モル％以上８０モル％未満含み、残部がアクリロニトリルである共重合物が好ましく、アクリルアミドを５０モル％以上７０モル％未満含み、残部がアクリロニトリルである共重合物がさらに好ましい。 Any copolymer consisting of acrylamide and acrylonitrile used for the production of the water-soluble polymer of the present invention can be used as long as it is a copolymer consisting of acrylamide and acrylonitrile, but from the viewpoint of aggregation performance and productivity. A copolymer containing 40 mol% or more and less than 80 mol% of acrylamide and the balance being acrylonitrile is preferred, and a copolymer containing acrylamide or less and less than 70 mol% and the remainder being acrylonitrile is more preferred.
アクリルアミドとアクリロニトリルとの共重合は、従来知られている溶液重合、乳化重合、懸濁重合、分散重合等の方法を用いることができる。その際、重合温度は、特に限定するものではないが、例えば、０〜７０℃の範囲から選択することができる。また、モノマー濃度は、特に限定するものではないが、例えば、１〜６０重量％の範囲から選択することができる。 For copolymerization of acrylamide and acrylonitrile, conventionally known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and dispersion polymerization can be used. In that case, although superposition | polymerization temperature is not specifically limited, For example, it can select from the range of 0-70 degreeC. The monomer concentration is not particularly limited, but can be selected from a range of 1 to 60% by weight, for example.
共重合反応を行うためのラジカル重合開始剤としては、油溶性開始剤、水溶性開始剤ともに使用することができるが、モノマーの親水性が比較的高いので、水溶性開始剤を使用する方がより好ましい。水溶性開始剤としては、アゾ系として２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物、２，２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素化物、４，４’−アゾビス（４−シアノ吉草酸）等を挙げることができる。また、過酸化物系としてはペルオクソ二硫酸アンモニウム、ペルオクソ二硫酸カリウム、過酸化水素等を挙げることができ、それぞれを単独または組み合わせて使用することができる。過酸化物系に対しては、より低温で重合を進めるため、亜硫酸ナトリウム、亜硫酸水素ナトリウム等の還元剤との組合せによるレドックス開始剤系の構築も適用できる。 As the radical polymerization initiator for carrying out the copolymerization reaction, both an oil-soluble initiator and a water-soluble initiator can be used. However, since the hydrophilicity of the monomer is relatively high, it is preferable to use a water-soluble initiator. More preferred. Examples of water-soluble initiators include 2,2′-azobis (2-amidinopropane) dichloride as an azo group, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of peroxides include ammonium peroxodisulfate, potassium peroxodisulfate, and hydrogen peroxide. These can be used alone or in combination. For peroxide systems, it is also possible to apply a redox initiator system in combination with a reducing agent such as sodium sulfite or sodium bisulfite in order to proceed the polymerization at a lower temperature.
得られた共重合物は、超原子価ヨウ素化合物とともに酸性条件下で加熱処理することにより、アミド基をアミノ基に変性し、生じたアミノ基は隣接するニトリル基と環化してアミジン環を形成することができる。 The resulting copolymer is heat-treated with a hypervalent iodine compound under acidic conditions to modify the amide group into an amino group, and the resulting amino group cyclizes with the adjacent nitrile group to form an amidine ring. can do.
本発明の水溶性高分子に用いる超原子価ヨウ素化合物は、分子内に３配位、５配位、７配位または８配位の超原子価のヨウ素を含むものならば如何なるものでも使用することができ、例えば、［ビス（トリフルオロアセトキシ）ヨード］ベンゼン、［ビス（トリフルオロアセトキシ）ヨード］ペンタフルオロベンゼン、ビス（２，４，６−トリメチルピリジン）ヨードニウムヘキサフルオロホスファート、ヨードベンゼンジアセタート、デス−マーチンペルヨージナン等を挙げることができ、反応性や生産性の観点より、［ビス（トリフルオロアセトキシ）ヨード］ベンゼン、［ビス（トリフルオロアセトキシ）ヨード］ペンタフルオロベンゼン、ビス（２，４，６−トリメチルピリジン）ヨードニウムヘキサフルオロホスファートが好ましい。 Any hypervalent iodine compound used for the water-soluble polymer of the present invention may be used as long as it contains tri-coordinate, 5-coordinate, 7-coordinate or 8-coordinate hypervalent iodine in the molecule. For example, [bis (trifluoroacetoxy) iodo] benzene, [bis (trifluoroacetoxy) iodo] pentafluorobenzene, bis (2,4,6-trimethylpyridine) iodonium hexafluorophosphate, iodobenzenedia Cetate, Dess-Martin periodinane, and the like. From the viewpoint of reactivity and productivity, [bis (trifluoroacetoxy) iodo] benzene, [bis (trifluoroacetoxy) iodo] pentafluorobenzene, bis (2,4,6-trimethylpyridine) iodonium hexafluorophosphate is preferred .
本発明の水溶性高分子に用いる超原子価ヨウ素化合物の配合量は、特に限定されるものではないが、凝集性能に優れることから、共重合体中のアクリルアミド単位に対して０．４〜１．５重量部が好ましく、０．６〜１．２重量部がさらに好ましい。 The blending amount of the hypervalent iodine compound used in the water-soluble polymer of the present invention is not particularly limited, but is 0.4 to 1 with respect to the acrylamide unit in the copolymer because of excellent aggregation performance. 0.5 parts by weight is preferable, and 0.6 to 1.2 parts by weight is more preferable.
アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素化合物を反応させる際の条件は、如何なるものでも用いることができ、特に制限されるものではないが、例えば、重合して得られたアクリルアミドとアクリロニトリルからなる共重合物のポリマー懸濁液に超原子価ヨウ素化合物を加えて酸性下で加熱する方法や、重合して得られたアクリルアミドとアクリロニトリルからなる共重合物を単離した後、溶媒中に投入し、超原子価ヨウ素化合物を加えて酸性下で加熱する方法等が挙げられる。 Any conditions can be used for the reaction between the copolymer of acrylamide and acrylonitrile and the hypervalent iodine compound, and there is no particular limitation. For example, acrylamide and acrylonitrile obtained by polymerization are used. A method of adding a hypervalent iodine compound to a polymer suspension of a copolymer and heating under acidic conditions, or isolating a copolymer of acrylamide and acrylonitrile obtained by polymerization, and then in a solvent And a method of adding a hypervalent iodine compound and heating under acidic conditions.
アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素を反応させる際の温度は、特に限定されるものではないが、反応速度や熱安定性の観点より、２５〜１００℃が好ましく、４０〜９０℃がさらに好ましい。 The temperature at which the copolymer of acrylamide and acrylonitrile and the hypervalent iodine are reacted is not particularly limited, but is preferably 25 to 100 ° C from the viewpoint of reaction rate and thermal stability, and 40 to 90 More preferably.
アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素化合物とを反応させる際、酸性条件下であることが好ましく、使用する酸としては、塩酸、硫酸、リン酸、硝酸、ギ酸、酢酸、クエン酸等を挙げることができるが、塩酸が特に好ましい。 When reacting the copolymer of acrylamide and acrylonitrile with the hypervalent iodine compound, it is preferably under acidic conditions, and the acid used is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, citric acid. Hydrochloric acid is particularly preferable.
アクリルアミドとアクリロニトリルからなる共重合物と超原子価ヨウ素化合物とを反応させる際の溶媒は、一般に溶剤として使用されるものならば如何なるものでも使用することができ、特に限定されるものではないが、溶解性や経済性の観点より水が好ましい。 As the solvent for reacting the copolymer of acrylamide and acrylonitrile with the hypervalent iodine compound, any solvent can be used as long as it is generally used as a solvent, but it is not particularly limited. Water is preferable from the viewpoint of solubility and economy.
以下に実施例に基づき本発明をさらに詳しく説明する。尚、用いた試薬等は断りのない限り市販品を用いた。 Hereinafter, the present invention will be described in more detail based on examples. Commercially available products were used unless otherwise specified.
＜酸化剤（Ａ）＞
酸化剤（Ａ−１）：［ビス（トリフルオロアセトキシ）ヨード］ベンゼン（一般試薬）東京化成工業株式会社製。
<Oxidizing agent (A)>
Oxidizing agent (A-1): [Bis (trifluoroacetoxy) iodo] benzene (general reagent) manufactured by Tokyo Chemical Industry Co., Ltd.
酸化剤（Ａ−２）：［ビス（トリフルオロアセトキシ）ヨード］ペンタフルオロベンゼン（一般試薬）東京化成工業株式会社製。 Oxidizing agent (A-2): [Bis (trifluoroacetoxy) iodo] pentafluorobenzene (general reagent) manufactured by Tokyo Chemical Industry Co., Ltd.
酸化剤（Ａ−３）：ビス（２，４，６−トリメチルピリジン）ヨードニウムヘキサフルオロホスファート（一般試薬）東京化成工業株式会社製。 Oxidizing agent (A-3): bis (2,4,6-trimethylpyridine) iodonium hexafluorophosphate (general reagent) manufactured by Tokyo Chemical Industry Co., Ltd.
酸化剤（Ａ−４）：次亜臭素酸ナトリウム水溶液（一般試薬）濃度５％、キシダ化学株式会社製。 Oxidizing agent (A-4): Sodium hypobromite aqueous solution (general reagent) concentration 5%, manufactured by Kishida Chemical Co., Ltd.
＜構造単位比率＞
試料中の構造単位比率は、１３Ｃ−ＮＭＲのスペクトルから対応する各構造単位のピーク面積の比より含有量を算出した。
<Structural unit ratio>
The content of the structural unit ratio in the sample was calculated from the ratio of the peak area of each corresponding structural unit from the 13 C-NMR spectrum.
＜水溶液粘度＞
試料０．４ｇを精秤し、イオン交換水を加えて０．２重量％の水溶液２００ｇを調製した。この水溶液の２５℃でのＢ型粘度計５０ｒｐｍにおける粘度を測定した。
<Aqueous solution viscosity>
0.4 g of a sample was precisely weighed, and ion exchange water was added to prepare 200 g of a 0.2 wt% aqueous solution. The viscosity of the aqueous solution at 25 ° C. and B type viscometer at 50 rpm was measured.
＜カチオン度＞
２００ｍｌビーカーにイオン交換水９０ｍｌをとり、５００ｐｐｍの試料水溶液を加えた後、塩酸水溶液でｐＨを４．０とし、約１分間撹拌した。このようにして調製した測定試料に、トルイジンブルー指示薬を３〜５滴加え、Ｎ／４００ポリビニル硫酸カリウム試薬（Ｎ／４００ＰＶＳＫ）で滴定し、カチオン度を算出した。
<Cation degree>
In a 200 ml beaker, 90 ml of ion-exchanged water was added, 500 ppm of an aqueous sample solution was added, the pH was adjusted to 4.0 with an aqueous hydrochloric acid solution, and the mixture was stirred for about 1 minute. 3-5 drops of toluidine blue indicator was added to the measurement sample thus prepared, and titration was performed with N / 400 polyvinyl potassium sulfate reagent (N / 400 PVSK) to calculate the cation degree.
＜凝集試験＞
活性汚泥処理した工業排水（固形分０．２４％、ｐＨ８．１）１００ｇを２００ｍｌビーカーに計量し、０．２重量％の水溶性高分子水溶液１０ｇを添加した。長さ３ｃｍの回転子を入れ、マグネティックスターラーにより１０００ｒｐｍで１０秒間撹拌し、３０秒静置した後、直径７ｃｍの３００メッシュのろ布でろ過した。ろ布上に回収された凝集物の凝集状態を目視評価し、凝集性の指標とした。
<Aggregation test>
100 g of industrial sludge treated with activated sludge (solid content 0.24%, pH 8.1) was weighed into a 200 ml beaker, and 10 g of a 0.2 wt% aqueous water-soluble polymer solution was added. A rotor having a length of 3 cm was placed, stirred for 10 seconds at 1000 rpm with a magnetic stirrer, allowed to stand for 30 seconds, and then filtered through a 300-mesh filter cloth having a diameter of 7 cm. The aggregation state of the aggregate collected on the filter cloth was visually evaluated and used as an index of aggregation.
（判定基準）
○：大きな凝集塊が、ろ布上に数個分散。
(Criteria)
○: Several large aggregates are dispersed on the filter cloth.
×：懸濁粒子がろ布を通過し、ろ布上に凝集粒子をほとんど観察できない状態。 X: Suspended particles pass through the filter cloth, and almost no aggregated particles can be observed on the filter cloth.
実施例１
撹拌機と冷却管を備えた３００ｍｌの四つ口フラスコに、アクリルアミド３０．０５ｇ（４２３ｍｍｏｌ）とアクリロニトリル１４．９５ｇ（２８２ｍｍｏｌ）とイオン交換水１８０．０ｇを仕込み、窒素気流下で１時間撹拌し、２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物の２重量％水溶液４．５ｇをフラスコ内に注入し、４０℃で２４時間重合させた。その後、５５℃に昇温し、さらに６時間重合を継続し、ポリマー懸濁液を得た。得られたポリマー懸濁液の固形分濃度は１９．６重量％、転化率は９８％であった。
Example 1
A 300 ml four-necked flask equipped with a stirrer and a condenser is charged with 30.05 g (423 mmol) of acrylamide, 14.95 g (282 mmol) of acrylonitrile and 180.0 g of ion-exchanged water, and stirred for 1 hour under a nitrogen stream. 4.5 g of a 2 wt% aqueous solution of 2,2'-azobis (2-amidinopropane) dichloride was poured into the flask and polymerized at 40 ° C for 24 hours. Thereafter, the temperature was raised to 55 ° C., and the polymerization was further continued for 6 hours to obtain a polymer suspension. The obtained polymer suspension had a solid content concentration of 19.6% by weight and a conversion rate of 98%.
得られたポリマー懸濁液１５．０ｇ（固形分２．９４ｇ、アクリルアミド含有量６０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−１）をポリマー中のアクリルアミドに対して１．２当量部（１３．３ｇ）と７．２重量％の塩酸２２．７ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．８ｇ）を得た。 15.0 g of the obtained polymer suspension (solid content 2.94 g, acrylamide content 60 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser and diluted with 100 g of ion-exchanged water. . The polymer suspension was acidified by adding 1.2 equivalent parts (13.3 g) of oxidizing agent (A-1) to acrylamide in the polymer and 22.7 g of 7.2% by weight hydrochloric acid. Heat at 6 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.8 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が４５モル％、上記式（２）で示される構造単位が１０モル％、上記式（３）で示される構造単位が１７モル％、上記式（４）で示される構造単位が２６モル％、および上記式（５）で示される構造単位が２モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が高く、優れた凝集性能を示した。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 45 mol%, and the structural unit represented by the above formula (2) was 10 mol. %, The structural unit represented by the formula (3) is 17 mol%, the structural unit represented by the formula (4) is 26 mol%, and the structural unit represented by the formula (5) is 2 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had high aqueous solution viscosity and high cation degree, and showed excellent aggregation performance.
実施例１で得られたポリマー懸濁液１５．０ｇ（固形分２．９４ｇ、アクリルアミド含有量６０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−１）をポリマー中のアクリルアミドに対して０．６当量部（６．６３ｇ）と７．２重量％の塩酸２２．７ｇ）を加えて酸性化し、６０℃で４時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．６ｇ）を得た。
15.0 g of the polymer suspension obtained in Example 1 (solid content 2.94 g, acrylamide content 60 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser, and ion-exchanged water. Dilute with 100 g. To this polymer suspension, an oxidizing agent (A-1) was acidified by adding 0.6 equivalent part (6.63 g) and 7.2 wt% hydrochloric acid (22.7 g) with respect to acrylamide in the polymer, Heated at 60 ° C. for 4 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.6 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が３０モル％、上記式（２）で示される構造単位が２４モル％、上記式（３）で示される構造単位が２５モル％、上記式（４）で示される構造単位が２０モル％、および上記式（５）で示される構造単位が１モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が高く、優れた凝集性能を示した。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 30 mol%, and the structural unit represented by the above formula (2) was 24 mol. %, The structural unit represented by the formula (3) is 25 mol%, the structural unit represented by the formula (4) is 20 mol%, and the structural unit represented by the formula (5) is 1 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had high aqueous solution viscosity and high cation degree, and showed excellent aggregation performance.
実施例３
撹拌機と冷却管を備えた３００ｍｌの四つ口フラスコに、アクリルアミド３７．９２ｇ（５３３ｍｍｏｌ）とアクリロニトリル７．０８ｇ（１３３ｍｍｏｌ）とイオン交換水１８０．０ｇを仕込み、窒素気流下で１時間撹拌し、２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物の２重量％水溶液４．５ｇをフラスコ内に注入し、４０℃で２４時間重合させた。その後、５５℃に昇温し、さらに６時間重合を継続し、ポリマー懸濁液を得た。得られたポリマー懸濁液の固形分濃度は１９．０重量％、転化率は９５％であった。
Example 3
A 300 ml four-necked flask equipped with a stirrer and a condenser is charged with 37.92 g (533 mmol) of acrylamide, 7.08 g (133 mmol) of acrylonitrile and 180.0 g of ion-exchanged water, and stirred for 1 hour under a nitrogen stream. 4.5 g of a 2 wt% aqueous solution of 2,2'-azobis (2-amidinopropane) dichloride was poured into the flask and polymerized at 40 ° C for 24 hours. Thereafter, the temperature was raised to 55 ° C., and the polymerization was further continued for 6 hours to obtain a polymer suspension. The obtained polymer suspension had a solid content concentration of 19.0% by weight and a conversion rate of 95%.
得られたポリマー懸濁液１５．０ｇ（固形分２．８５ｇ、アクリルアミド含有量８０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−２）をポリマー中のアクリルアミドに対して１．４当量部（１８．１ｇ）と７．２重量％の塩酸２２．１ｇを加えて酸性化し、６０℃で８時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．８ｇ）を得た。 15.0 g of the obtained polymer suspension (solid content 2.85 g, acrylamide content 80 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser and diluted with 100 g of ion-exchanged water. . To this polymer suspension, 1.4 parts by weight (18.1 g) of the oxidizing agent (A-2) with respect to acrylamide in the polymer and 22.1 g of 7.2% by weight hydrochloric acid were added to acidify the suspension. Heated at 0 ° C. for 8 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.8 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が３２モル％、上記式（２）で示される構造単位が２０モル％、上記式（３）で示される構造単位が６モル％、上記式（４）で示される構造単位が３８モル％、および上記式（５）で示される構造単位が４モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が高く、優れた凝集性能を示した。 As a result of calculating the ratio of each repeating unit to the obtained polymer using 13 C-NMR, the structural unit represented by the above formula (1) was 32 mol%, and the structural unit represented by the above formula (2) was 20 mol. %, The structural unit represented by the formula (3) is 6 mol%, the structural unit represented by the formula (4) is 38 mol%, and the structural unit represented by the formula (5) is 4 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had high aqueous solution viscosity and high cation degree, and showed excellent aggregation performance.
実施例４
撹拌機と冷却管を備えた３００ｍｌの四つ口フラスコに、アクリルアミド２１．２３ｇ（２９９ｍｍｏｌ）とアクリロニトリル２３．７７ｇ（４４８ｍｍｏｌ）とイオン交換水１８０．０ｇを仕込み、窒素気流下で１時間撹拌し、２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物の２重量％水溶液４．５ｇをフラスコ内に注入し、４０℃で２４時間重合させた。その後、５５℃に昇温し、さらに６時間重合を継続し、ポリマー懸濁液を得た。得られたポリマー懸濁液の固形分濃度は１９．２重量％、転化率は９６％であった。
Example 4
A 300 ml four-necked flask equipped with a stirrer and a condenser is charged with 21.23 g (299 mmol) of acrylamide, 23.77 g (448 mmol) of acrylonitrile and 180.0 g of ion-exchanged water, and stirred for 1 hour under a nitrogen stream. 4.5 g of a 2 wt% aqueous solution of 2,2'-azobis (2-amidinopropane) dichloride was poured into the flask and polymerized at 40 ° C for 24 hours. Thereafter, the temperature was raised to 55 ° C., and the polymerization was further continued for 6 hours to obtain a polymer suspension. The resulting polymer suspension had a solid content concentration of 19.2% by weight and a conversion rate of 96%.
得られたポリマー懸濁液１５．０ｇ（固形分２．８８ｇ、アクリルアミド含有量４０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−３）をポリマー中のアクリルアミドに対して１．２当量部（１５．５ｇ）と７．２重量％の塩酸２２．３ｇを加えて酸性化し、４０℃で１０時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．７ｇ）を得た。 15.0 g of the obtained polymer suspension (solid content 2.88 g, acrylamide content 40 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser and diluted with 100 g of ion-exchanged water. . The polymer suspension was acidified by adding 1.2 equivalent parts (15.5 g) of oxidizing agent (A-3) to acrylamide in the polymer and 22.3 g of 7.2% by weight hydrochloric acid. Heat at 10 ° C. for 10 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.7 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が２３モル％、上記式（２）で示される構造単位が５モル％、上記式（３）で示される構造単位が３７モル％、上記式（４）で示される構造単位が３４モル％、および上記式（５）で示される構造単位が１モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が高く、優れた凝集性能を示した。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 23 mol%, and the structural unit represented by the above formula (2) was 5 mol. %, The structural unit represented by the above formula (3) is 37 mol%, the structural unit represented by the above formula (4) is 34 mol%, and the structural unit represented by the above formula (5) is 1 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had high aqueous solution viscosity and high cation degree, and showed excellent aggregation performance.
比較例１
実施例１で得られたポリマー懸濁液１５．０ｇ（固形分２．９４ｇ、アクリルアミド含有量６０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−４）をポリマー中のアクリルアミドに対して１．５当量部（９６．５ｇ）と７．２重量％の塩酸２２．７ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより濃赤色のポリマー（３．０ｇ）を得た。
Comparative Example 1
15.0 g of the polymer suspension obtained in Example 1 (solid content 2.94 g, acrylamide content 60 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser, and ion-exchanged water. Dilute with 100 g. The polymer suspension was acidified by adding 1.5 equivalent parts (96.5 g) of oxidizing agent (A-4) to acrylamide in the polymer and 22.7 g of 7.2% by weight hydrochloric acid. Heat at 6 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain a deep red polymer (3.0 g).
得られたポリマーは水に不溶であり、１３Ｃ−ＮＭＲによる構造解析、水溶液粘度、カチオン度および凝集性能を評価することができなかった。 The obtained polymer was insoluble in water, and structural analysis by 13 C-NMR, aqueous solution viscosity, cation degree and aggregation performance could not be evaluated.
比較例２
撹拌機と冷却管を備えた３００ｍｌの四つ口フラスコに、アクリルアミド４１．５５ｇ（５８４ｍｍｏｌ）とアクリロニトリル３．４５ｇ（６５ｍｍｏｌ）とイオン交換水１８０．０ｇを仕込み、窒素気流下で１時間撹拌し、２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物の２重量％水溶液４．５ｇをフラスコ内に注入し、４０℃で２４時間重合させた。その後、５５℃に昇温し、さらに６時間重合を継続し、ポリマー懸濁液を得た。得られたポリマー懸濁液の固形分濃度は１７．０重量％、転化率は８５％であった。
Comparative Example 2
A 300 ml four-necked flask equipped with a stirrer and a condenser is charged with 41.55 g (584 mmol) of acrylamide, 3.45 g (65 mmol) of acrylonitrile and 180.0 g of ion-exchanged water, and stirred for 1 hour under a nitrogen stream. 4.5 g of a 2 wt% aqueous solution of 2,2'-azobis (2-amidinopropane) dichloride was poured into the flask and polymerized at 40 ° C for 24 hours. Thereafter, the temperature was raised to 55 ° C., and the polymerization was further continued for 6 hours to obtain a polymer suspension. The obtained polymer suspension had a solid content concentration of 17.0% by weight and a conversion rate of 85%.
得られたポリマー懸濁液１５．０ｇ（固形分２．５５ｇ、アクリルアミド含有量９０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−１）をポリマー中のアクリルアミドに対して１．２当量部（１７．１ｇ）と７．２重量％の塩酸１９．７ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．２ｇ）を得た。 15.0 g of the obtained polymer suspension (solid content: 2.55 g, acrylamide content: 90 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser and diluted with 100 g of ion-exchanged water. . The polymer suspension was acidified by adding 1.2 equivalent parts (17.1 g) of oxidizing agent (A-1) to acrylamide in the polymer and 19.7 g of 7.2 wt% hydrochloric acid, Heat at 6 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.2 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が１１モル％、上記式（２）で示される構造単位が１９モル％、上記式（３）で示される構造単位が６モル％、上記式（４）で示される構造単位が５４モル％、および上記式（５）で示される構造単位が１０モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が低く、凝集性能に劣った。 As a result of calculating the ratio of each repeating unit of the obtained polymer using 13 C-NMR, the structural unit represented by the above formula (1) was 11 mol%, and the structural unit represented by the above formula (2) was 19 mol. %, The structural unit represented by the formula (3) is 6 mol%, the structural unit represented by the formula (4) is 54 mol%, and the structural unit represented by the formula (5) is 10 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had low aqueous solution viscosity and cation degree and was inferior in agglomeration performance.
比較例３
撹拌機と冷却管を備えた３００ｍｌの四つ口フラスコに、アクリルアミド１６．４１ｇ（２３１ｍｍｏｌ）とアクリロニトリル２８．５９ｇ（５３９ｍｍｏｌ）とイオン交換水１８０．０ｇを仕込み、窒素気流下で１時間撹拌し、２，２’−アゾビス（２−アミジノプロパン）二塩化水素化物の２重量％水溶液４．５ｇをフラスコ内に注入し、４０℃で２４時間重合させた。その後、５５℃に昇温し、さらに６時間重合を継続し、ポリマー懸濁液を得た。得られたポリマー懸濁液の固形分濃度は１９．５重量％、転化率は９８％であった。
Comparative Example 3
A 300 ml four-necked flask equipped with a stirrer and a condenser is charged with 16.41 g (231 mmol) of acrylamide, 28.59 g (539 mmol) of acrylonitrile and 180.0 g of ion-exchanged water, and stirred for 1 hour under a nitrogen stream. 4.5 g of a 2 wt% aqueous solution of 2,2'-azobis (2-amidinopropane) dichloride was poured into the flask and polymerized at 40 ° C for 24 hours. Thereafter, the temperature was raised to 55 ° C., and the polymerization was further continued for 6 hours to obtain a polymer suspension. The obtained polymer suspension had a solid content concentration of 19.5% by weight and a conversion rate of 98%.
得られたポリマー懸濁液１５．０ｇ（固形分２．９２ｇ、アクリルアミド含有量３０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−２）をポリマー中のアクリルアミドに対して１．０当量部（１５．９ｇ）と７．２重量％の塩酸２２．６ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより黄土色のポリマー（２．４ｇ）を得た。 15.0 g of the obtained polymer suspension (solid content: 2.92 g, acrylamide content: 30 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser and diluted with 100 g of ion-exchanged water. . To this polymer suspension, an oxidizing agent (A-2) was acidified by adding 1.0 equivalent part (15.9 g) and 22.6 g of 7.2% by weight hydrochloric acid with respect to acrylamide in the polymer. Heat at 6 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain an ocher polymer (2.4 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が１４モル％、上記式（２）で示される構造単位が６モル％、上記式（３）で示される構造単位が６７モル％、上記式（４）で示される構造単位が１２モル％、および上記式（５）で示される構造単位が１モル％と解析された。水溶液粘度、カチオン度および凝集試験の評価結果を表１に示す。得られたポリマーは水溶液粘度およびカチオン度が低く、凝集性能に劣った。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 14 mol%, and the structural unit represented by the above formula (2) was 6 mol. %, The structural unit represented by the above formula (3) is 67 mol%, the structural unit represented by the above formula (4) is 12 mol%, and the structural unit represented by the above formula (5) is 1 mol%. It was. Table 1 shows the evaluation results of the aqueous solution viscosity, the cation degree, and the aggregation test. The obtained polymer had low aqueous solution viscosity and cation degree and was inferior in agglomeration performance.
比較例４
実施例１で得られたポリマー懸濁液１５．０ｇ（固形分２．９４ｇ、アクリルアミド含有量６０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、７．２重量％の塩酸７．５ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより白色のポリマー（２．４ｇ）を得た。
Comparative Example 4
15.0 g of the polymer suspension obtained in Example 1 (solid content 2.94 g, acrylamide content 60 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser, and ion-exchanged water. Dilute with 100 g. The polymer suspension was acidified by adding 7.5 g of 7.2% by weight hydrochloric acid and heated at 60 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain a white polymer (2.4 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が０モル％、上記式（２）で示される構造単位が６０モル％、上記式（３）で示される構造単位が４０モル％、上記式（４）で示される構造単位が０モル％、および上記式（５）で示される構造単位が０モル％と解析された。得られたポリマーは水に不溶であり、水溶液粘度、カチオン度および凝集性能を評価することができなかった。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 0 mol%, and the structural unit represented by the above formula (2) was 60 mol. %, The structural unit represented by the formula (3) is 40 mol%, the structural unit represented by the formula (4) is 0 mol%, and the structural unit represented by the formula (5) is 0 mol%. It was. The obtained polymer was insoluble in water, and the aqueous solution viscosity, cation degree and aggregation performance could not be evaluated.
比較例５
実施例１で得られたポリマー懸濁液１５．０ｇ（固形分２．９４ｇ、アクリルアミド含有量６０モル％）を撹拌機と冷却管を備えた２００ｍｌの四つ口フラスコに計り取り、イオン交換水１００ｇで希釈した。このポリマー懸濁液に、酸化剤（Ａ−１）をポリマー中のアクリルアミドに対して０．３当量部（２８．９ｇ）と７．２重量％の塩酸２２．７ｇを加えて酸性化し、６０℃で６時間加熱した。その後、８５℃に昇温し、さらに４時間加熱した。反応終了後、反応溶液にアセトンを加えてポリマーを沈殿させ、真空乾燥することにより濃赤色のポリマー（２．８ｇ）を得た。
Comparative Example 5
15.0 g of the polymer suspension obtained in Example 1 (solid content 2.94 g, acrylamide content 60 mol%) was weighed into a 200 ml four-necked flask equipped with a stirrer and a condenser, and ion-exchanged water. Dilute with 100 g. The polymer suspension was acidified by adding 0.3 equivalent part (28.9 g) of oxidizing agent (A-1) to acrylamide in the polymer and 22.7 g of 7.2% by weight hydrochloric acid. Heat at 6 ° C. for 6 hours. Thereafter, the temperature was raised to 85 ° C. and further heated for 4 hours. After completion of the reaction, acetone was added to the reaction solution to precipitate the polymer, followed by vacuum drying to obtain a deep red polymer (2.8 g).
得られたポリマーを１３Ｃ−ＮＭＲを用いて各繰り返し単位の比率を算出した結果、上記式（１）で示される構造単位が４モル％、上記式（２）で示される構造単位が５２モル％、上記式（３）で示される構造単位が３６モル％、上記式（４）で示される構造単位が７モル％、および上記式（５）で示される構造単位が１モル％と解析された。得られたポリマーは水に不溶であり、水溶液粘度、カチオン度および凝集性能を評価することができなかった。 As a result of calculating the ratio of each repeating unit using 13 C-NMR for the obtained polymer, the structural unit represented by the above formula (1) was 4 mol%, and the structural unit represented by the above formula (2) was 52 mol. %, The structural unit represented by the formula (3) is 36 mol%, the structural unit represented by the formula (4) is 7 mol%, and the structural unit represented by the formula (5) is 1 mol%. It was. The obtained polymer was insoluble in water, and the aqueous solution viscosity, cation degree and aggregation performance could not be evaluated.
本発明の水溶性高分子は、水溶液粘度およびカチオン度が高く、剛直なアミジン骨格を主鎖中に有して凝集性能に優れるため、各種産業排水や汚泥処理および下水汚泥処理に用いる高分子凝集剤として有用である。 The water-soluble polymer of the present invention has high aqueous solution viscosity and cation degree, and has a rigid amidine skeleton in the main chain and excellent coagulation performance. Useful as an agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019026827A (en) * | 2017-07-27 | 2019-02-21 | 株式会社豊田中央研究所 | Carbon material precursor, carbon material precursor composition containing the same, and manufacturing method of carbon material using the same |
| CN111087507A (en) * | 2019-12-18 | 2020-05-01 | 常州大学 | Free radical polymerization of acrylamide initiated by redox of high valence iodide reagent |
| US11001660B2 (en) | 2017-07-27 | 2021-05-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019026827A (en) * | 2017-07-27 | 2019-02-21 | 株式会社豊田中央研究所 | Carbon material precursor, carbon material precursor composition containing the same, and manufacturing method of carbon material using the same |
| US11001660B2 (en) | 2017-07-27 | 2021-05-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using the same |
| CN111087507A (en) * | 2019-12-18 | 2020-05-01 | 常州大学 | Free radical polymerization of acrylamide initiated by redox of high valence iodide reagent |
| CN111087507B (en) * | 2019-12-18 | 2021-07-27 | 常州大学 | Free radical polymerization of acrylamide initiated by redox of high valence iodide reagent |
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