JP4670009B2 - High molecular weight polydiphenylvinylphosphine oxide, process for producing the same, and metal extractant - Google Patents
High molecular weight polydiphenylvinylphosphine oxide, process for producing the same, and metal extractant Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims description 11
- 239000002184 metal Substances 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- -1 acetylene compound Chemical class 0.000 description 13
- CQCGPNRIAFVNBY-UHFFFAOYSA-N [ethenyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(C=C)C1=CC=CC=C1 CQCGPNRIAFVNBY-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- APMAMJBVOGNAKB-UHFFFAOYSA-N C(C(C)C)C(=C[PH2]=O)CC(C)C Chemical compound C(C(C)C)C(=C[PH2]=O)CC(C)C APMAMJBVOGNAKB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004794 vinyl magnesium halides Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、新規なホスフィンオキシド重合体、特に高分子量ポリジフェニルビニルホスフィンオキシド、その製造方法及びそれを用いた金属抽出剤に関するものである。 The present invention relates to a novel phosphine oxide polymer, particularly high molecular weight polydiphenylvinylphosphine oxide, a process for producing the same, and a metal extractant using the same.
これまで、ビニルジフェニルホスフィンオキシド単独を有機過酸化物触媒の存在下で重合させて、分子量６９２又は１３４８の重合体を製造する方法、ジフェニルビニルホスフィンオキシドとスチレン又はメチルメタクリレートとをアゾビスイソブチロニトリル触媒の存在下で共重合させる方法、ビス（４‐ニトロフェニル）４‐クロロ‐１，２‐ブテニルホスフィンオキシドとビニルクロリド又はジイソブチルビニルホスフィンオキシドとステアリルメタクリレートとをアゾイソブチロニトリル触媒の存在下で共重合させる方法や、このようにして得た重合体又は共重合体が接着剤及び難燃剤として有用であることは知られている（特許文献１参照）。 Up to now, a method for producing a polymer having a molecular weight of 692 or 1348 by polymerizing vinyl diphenylphosphine oxide alone in the presence of an organic peroxide catalyst, diphenylvinylphosphine oxide and styrene or methyl methacrylate are combined with azobisisobutyro Copolymerization in the presence of a nitrile catalyst, bis (4-nitrophenyl) 4-chloro-1,2-butenylphosphine oxide and vinyl chloride or diisobutylvinylphosphine oxide and stearyl methacrylate. It is known that a method of copolymerization in the presence, and the polymer or copolymer thus obtained are useful as an adhesive and a flame retardant (see Patent Document 1).
また、トルエン中、グリニャール化合物の存在下でジフェニルビニルホスフィンオキシドを重合させることにより、低分子量のジフェニルビニルホスフィンオキシドオリゴマーを得たことが報告されている（非特許文献１参照）。
しかしながら、分子量１０，０００以上の高分子量ポリジフェニルビニルホスフィンオキシドは知られていない。
It has also been reported that diphenylvinylphosphine oxide oligomers were obtained by polymerizing diphenylvinylphosphine oxide in toluene in the presence of a Grignard compound (see Non-Patent Document 1).
However, a high molecular weight polydiphenylvinylphosphine oxide having a molecular weight of 10,000 or more is not known.
他方、パラジウム触媒の存在下、アセチレン化合物に、第二級ホスフィンオキシドを反応させてアルケニルホスフィンオキシド化合物を製造する方法（特許文献２、３参照）、ロジウム触媒の存在下、アセチレン化合物に第二級ホスフィンオキシドを反応させてアルケニルホスフィンオキシド化合物を製造する方法（特許文献４参照）など、アルケニルホスフィンオキシド化合物又はその製造方法は知られているが、このようにして得られたアルケニルホスフィンオキシド化合物の重合体は知られていない。 On the other hand, a method for producing an alkenylphosphine oxide compound by reacting an acetylene compound with a secondary phosphine oxide in the presence of a palladium catalyst (see Patent Documents 2 and 3), and a secondary reaction with an acetylene compound in the presence of a rhodium catalyst. Alkenyl phosphine oxide compounds or their production methods are known, such as a method for producing alkenyl phosphine oxide compounds by reacting phosphine oxide (see Patent Document 4). Coalescence is not known.
本発明は、特に金属抽出剤として有用な、分子量１０，０００以上をもつ高分子量ポリジフェニルビニルホスフィンオキシド及びその製造方法を提供することを目的としてなされたものである。 An object of the present invention is to provide a high molecular weight polydiphenylvinylphosphine oxide having a molecular weight of 10,000 or more, which is particularly useful as a metal extractant, and a method for producing the same.
本発明者らは、これまで得られなかった高分子量ポリジフェニルビニルホスフィンオキシドを製造するために鋭意研究を重ねた結果、極性溶媒中、グリニャール化合物又は有機リチウム化合物を触媒としてジフェニルビニルホスフィンオキシドを重合させると、分子量１０，０００以上の高分子量ポリジフェニルビニルホスフィンオキシドが生成すること、及びこの高分子量重合体は、金属特にランタノイド金属の抽出剤として優れた機能を有することを見出し、この知見に基づいて本発明をなすに至った。 As a result of intensive research to produce a high molecular weight polydiphenylvinylphosphine oxide that has not been obtained so far, the present inventors polymerized diphenylvinylphosphine oxide in a polar solvent using a Grignard compound or an organolithium compound as a catalyst. In this way, it is found that a high molecular weight polydiphenylvinylphosphine oxide having a molecular weight of 10,000 or more is formed, and that this high molecular weight polymer has an excellent function as an extractant for metals, particularly lanthanoid metals. The present invention has been made.
すなわち、本発明は、一般式
で表わされる構成単位からなり、重量平均分子量が１０，０００〜１，０００，０００である高分子量ポリジフェニルビニルホスフィンオキシドからなる金属抽出剤を提供するものである。
That is, the present invention has the general formula
And a metal extractant comprising a high molecular weight polydiphenylvinylphosphine oxide having a weight average molecular weight of 10,000 to 1,000,000 .
本発明の高分子量ポリジフェニルビニルホスフィンオキシドは、分子量１０，０００以上という高分子量を有する点で、従来のポリジフェニルビニルホスフィンオキシドと明らかに異なっている。
本発明のポリジフェニルビニルホスフィンオキシドの分子量の上限については、特に制限はないが、通常の条件で重合させた場合には、１，０００，０００程度が上限になる。したがって、好ましい分子量は１０，０００〜１，０００，０００の範囲である。
The high molecular weight polydiphenylvinylphosphine oxide of the present invention is clearly different from conventional polydiphenylvinylphosphine oxide in that it has a high molecular weight of 10,000 or more.
The upper limit of the molecular weight of the polydiphenylvinylphosphine oxide of the present invention is not particularly limited, but when polymerized under normal conditions, the upper limit is about 1,000,000. Accordingly, the preferred molecular weight is in the range of 10,000 to 1,000,000.
このような高分子量ポリジフェニルビニルホスフィンオキシドは、一般式
そして、このような求核的付加反応は、極性溶媒中で進行するので、上記の重合反応は、極性溶媒中で行うことが必要であり、非極性溶媒例えばトルエン中では、所望の高分子量ポリジフェニルビニルホスフィンオキシドは全く得られない。 Since such a nucleophilic addition reaction proceeds in a polar solvent, it is necessary to carry out the above polymerization reaction in a polar solvent. In a nonpolar solvent such as toluene, the desired high molecular weight polymer is used. No diphenylvinylphosphine oxide is obtained.
上記の触媒として用いるグリニャール化合物としては、例えば、メチルマグネシウムハライド、ｎ‐ブチルマグネシウムハライド、ｔ‐ブチルマグネシウムハライド、ビニルマグネシウムハライド、アリルマグネシウムハライド、ベンジルマグネシウムハライド、フェニルマグネシウムハライドなどがある。ここでハライドとはクロリド、ブロミド及びヨージドを意味する。
また、有機リチウム化合物としては、例えばメチルリチウム、ｎ‐ブチルリチウム、ｔ‐ブチルリチウム、フェニルリチウムなどがある。
これらの触媒は、単量体のジフェニルビニルホスフィンオキシドに基づき０．１〜５０モル％、好ましくは１〜５モル％の範囲で用いられる。
Examples of the Grignard compound used as the catalyst include methyl magnesium halide, n-butyl magnesium halide, t-butyl magnesium halide, vinyl magnesium halide, allyl magnesium halide, benzyl magnesium halide, and phenyl magnesium halide. Here, halide means chloride, bromide and iodide.
Examples of the organic lithium compound include methyl lithium, n-butyl lithium, t-butyl lithium, and phenyl lithium.
These catalysts are used in the range of 0.1 to 50 mol%, preferably 1 to 5 mol%, based on the monomeric diphenylvinylphosphine oxide.
次に反応溶媒として用いられる極性溶媒には、例えばジエチルエーテル、酢酸エチル、酢酸ブチルなどが含まれるが、特に好ましいのは、テトラヒドロフラン、テトラヒドロピラン、ジオキサンなどである。 Next, polar solvents used as a reaction solvent include, for example, diethyl ether, ethyl acetate, butyl acetate, and the like, and tetrahydrofuran, tetrahydropyran, dioxane and the like are particularly preferable.
ジフェニルビニルホスフィンオキシドの重合反応は、通常０℃ないし１５０℃、好ましくは室温ないし５０℃の温度で行われる。
また、この重合反応は、大気中で行われるが、所望に応じ不活性雰囲気例えば窒素雰囲気中で行うこともできる。
重合は、通常３０分ないし２４時間で終了する。終了後、反応混合物から溶媒を留去し、水、希酸水溶液で洗浄したのち、真空乾燥すれば、所望の高分子量ポリジフェニルビニルホスフィンオキシドが難燃性、耐熱性の白色粉末として９５％以上の収率で得られる。
The polymerization reaction of diphenylvinylphosphine oxide is usually performed at a temperature of 0 ° C. to 150 ° C., preferably room temperature to 50 ° C.
The polymerization reaction is performed in the air, but can be performed in an inert atmosphere such as a nitrogen atmosphere as desired.
The polymerization is usually completed in 30 minutes to 24 hours. After completion of the reaction, the solvent is distilled off from the reaction mixture, washed with water and dilute aqueous acid solution, and then vacuum-dried, so that the desired high molecular weight polydiphenylvinylphosphine oxide is 95% or more as a flame-retardant, heat-resistant white powder. The yield is obtained.
本発明によれば、難燃性、耐熱性を有し、特に金属抽出剤として好適な高分子量ポリジフェニルビニルホスフィンオキシドを効率よく得ることができる。 According to the present invention, it is possible to efficiently obtain a high molecular weight polydiphenylvinylphosphine oxide having flame retardancy and heat resistance, and particularly suitable as a metal extractant.
次に実施例により本発明を実施するための最良の形態を説明するが、本発明はこれにより何ら限定されるものではない。 Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited thereto.
なお、実施例における分子量及び難燃性は以下の方法により測定した。
（１）分子量；
カラムとして、Ｔｏｓｏｈ社製、商品名「ＧＭＨＨＲ−Ｈ＊２」を、溶媒としてヘキサフルオロイソプロパノールを用い、ポリメチルメタクリレートをスタンダードとしたゲルパーミエーションクロマトグラフィにより測定した。
（２）難燃性；
試料をＵＬ−９４テストを行い、着火しない場合は難燃性ありとし、着火した場合は難燃性なしとした。
In addition, the molecular weight and flame retardance in an Example were measured with the following method.
(1) molecular weight;
The column was measured by gel permeation chromatography using Tosoh's trade name “GMHHR-H * 2”, hexafluoroisopropanol as a solvent, and polymethyl methacrylate as a standard.
(2) Flame retardancy;
The sample was subjected to a UL-94 test. When it did not ignite, it was regarded as flame retardant, and when ignited, it was regarded as not flame retardant.
製造例１
テトラヒドロフラン（ＴＨＦ）１０ｍｌにジフェニルビニルホスフィンオキシド１ｍｍｏｌと触媒として５ｍｏｌ％のｔ‐ブチルマグネシウムクロリドを加え、 大気中３０℃で２０時間かきまぜながら重合反応させた。反応終了後、溶媒を留去し、残渣を先ず０．１Ｍ−塩酸２ｍｌで、次に純水２ｍｌずつで３回洗浄したのち、真空乾燥することにより、重量平均分子量（Ｍｗ）２４，０００、分子量分布（Ｍｗ／Ｍｎ）２．１の高分子量ポリジフェニルビニルホスフィンオキシドを９７．５％の収率で得た。
このものについて、ＴＧＡを測定したところ、窒素雰囲気中では４２９℃、空気中では４１０℃で５質量％減が認められた。
Production Example 1
To 1 ml of tetrahydrofuran (THF), 1 mmol of diphenylvinylphosphine oxide and 5 mol% of t-butylmagnesium chloride as a catalyst were added, and a polymerization reaction was carried out while stirring in the atmosphere at 30 ° C. for 20 hours. After completion of the reaction, the solvent was distilled off, and the residue was washed 3 times with 2 ml of 0.1 M hydrochloric acid and then with 2 ml of pure water, and then vacuum-dried to obtain a weight average molecular weight (Mw) of 24,000, A high molecular weight polydiphenylvinylphosphine oxide having a molecular weight distribution (Mw / Mn) of 2.1 was obtained in a yield of 97.5%.
When TGA was measured for this product, a 5 mass% reduction was observed at 429 ° C. in a nitrogen atmosphere and 410 ° C. in air.
製造例２〜１０
表１に示す触媒、溶媒、反応条件を用い、製造例１と同様に操作して、表１に示す分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）をもつ高分子量ポリジフェニルビニルホスフィンオキシドを表１に示す収率で製造した。
Production Examples 2 to 10
A high molecular weight polydiphenylvinylphosphine oxide having the molecular weight (Mw) and the molecular weight distribution (Mw / Mn) shown in Table 1 was obtained by operating in the same manner as in Production Example 1 using the catalyst, solvent and reaction conditions shown in Table 1. 1 was produced with the yield shown.
比較例
製造例１で用いた溶媒のテトラヒドロフランを同量のトルエンで代えた以外は、製造例１と全く同様に操作してジフェニルビニルホスフィンオキシドの重合を行ったところ、反応は全く進行せず、重合体は全く得られなかった。
Comparative example
Was used in place of tetrahydrofuran solvent used in Production Example 1 with the same amount of toluene, was by operating in exactly the same manner as in Production Example 1 to perform polymerization of diphenyl vinyl phosphine oxide, at all does not proceed the reaction, the polymer Was not obtained at all.
実施例１
Ｌａ（ＩＩＩ）イオンを１０-4Ｍの濃度で含む１．０Ｍ ＨＮＯ3溶液に対し、製造例１で得た高分子量ポリジフェニルビニルホスフィンオキシドを金属イオンの５倍過剰量で加えて振りまぜたのち、高分子量ポリジフェニルビニルホスフィンオキシドをろ去した。このような処理の前後における液中のＬａ（ＩＩＩ）濃度原子吸光スペクトルにより測定したところ、処理後においてＬａ（ＩＩＩ）の４９％が抽出されていた。
同様にＥｕ（ＩＩＩ）についての抽出率を試験したところ、その抽出率は３５％であった。
Example 1
The 1.0M HNO 3 solution containing La (III) ions at a concentration of 10 −4 M was shaken by adding the high molecular weight polydiphenylvinylphosphine oxide obtained in Production Example 1 in a 5-fold excess of metal ions. Thereafter, the high molecular weight polydiphenylvinylphosphine oxide was filtered off. When measured by an atomic absorption spectrum of La (III) concentration in the liquid before and after such treatment, 49% of La (III) was extracted after the treatment.
Similarly, when the extraction rate for Eu (III) was tested, the extraction rate was 35%.
本発明の高分子量ポリジフェニルビニルホスフィンオキシドは、金属特にランタノイド系金属の抽出剤として有用である。
The high molecular weight polydiphenylvinylphosphine oxide of the present invention is useful as an extractant for metals, particularly lanthanoid metals.
Claims (2)
で表わされる構成単位からなり、重量平均分子量が１０，０００〜１，０００，０００である高分子量ポリジフェニルビニルホスフィンオキシドからなる金属抽出剤。 General formula
A metal extractant comprising a high molecular weight polydiphenylvinylphosphine oxide having a weight average molecular weight of 10,000 to 1,000,000 .
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| JP4736039B2 (en) * | 2005-11-25 | 2011-07-27 | 独立行政法人産業技術総合研究所 | Phosphorus-containing polymer having cycloalkylidenyl group and process for producing the same |
| JP2010120978A (en) * | 2008-11-17 | 2010-06-03 | Mitsubishi Engineering Plastics Corp | Flame-retardant thermoplastic resin composition and electric or electronic component obtained by molding the same |
| JP5339516B2 (en) * | 2009-02-09 | 2013-11-13 | 独立行政法人産業技術総合研究所 | Extractant made of phosphorus-containing polymer |
| JP5709094B2 (en) * | 2009-02-28 | 2015-04-30 | 独立行政法人産業技術総合研究所 | Alkenyl phosphorus compound, alkenyl phosphorus compound polymer, and alkenyl phosphorus compound copolymer |
| US9127109B2 (en) | 2012-05-01 | 2015-09-08 | Bridgestone Corporation | Preparation of functional polymers phosphorus-containing organometal initiators |
| JP6334514B2 (en) * | 2012-05-01 | 2018-05-30 | 株式会社ブリヂストン | Polydienes and diene copolymers having organophosphine functional groups |
| US9499651B2 (en) | 2013-03-13 | 2016-11-22 | Bridgestone Corporation | Copolymers of conjugated dienes and vinyl organophosphines prepared by anionic polymerization |
| US11505694B2 (en) * | 2018-03-08 | 2022-11-22 | Tdk Corporation | Resin composition, resin cured product and resin substrate |
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| JPS56103191A (en) * | 1979-12-28 | 1981-08-18 | Poudres & Explosifs Ste Nale | Synthesization of tertiary phosphine oxide |
| JPS5896605A (en) * | 1981-12-03 | 1983-06-08 | Takeo Saegusa | Manufacture of crosslinked polymer having polyphosphine oxide in the side chain |
| JPH10513171A (en) * | 1995-02-01 | 1998-12-15 | コミツサリア タ レネルジー アトミーク | Calixarene derivatives, their production and their use in the extraction of actinides and lanthanoids |
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| JPS4985185A (en) * | 1972-07-17 | 1974-08-15 | ||
| JPS56103191A (en) * | 1979-12-28 | 1981-08-18 | Poudres & Explosifs Ste Nale | Synthesization of tertiary phosphine oxide |
| JPS5896605A (en) * | 1981-12-03 | 1983-06-08 | Takeo Saegusa | Manufacture of crosslinked polymer having polyphosphine oxide in the side chain |
| JPH10513171A (en) * | 1995-02-01 | 1998-12-15 | コミツサリア タ レネルジー アトミーク | Calixarene derivatives, their production and their use in the extraction of actinides and lanthanoids |
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