JPH08196911A - Synthesizing method of phosphorus-based latent catalyst - Google Patents
Synthesizing method of phosphorus-based latent catalystInfo
- Publication number
- JPH08196911A JPH08196911A JP7012488A JP1248895A JPH08196911A JP H08196911 A JPH08196911 A JP H08196911A JP 7012488 A JP7012488 A JP 7012488A JP 1248895 A JP1248895 A JP 1248895A JP H08196911 A JPH08196911 A JP H08196911A
- Authority
- JP
- Japan
- Prior art keywords
- borate
- tetra
- substituted
- acid
- phosphonium
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 9
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 35
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 23
- 150000007524 organic acids Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- -1 phosphonium organic acid Chemical group 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000004593 Epoxy Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 125000005496 phosphonium group Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- YZMXTFHCEYRBGW-UHFFFAOYSA-N benzoic acid tetraphenylphosphanium borate Chemical compound B([O-])([O-])[O-].C(C1=CC=CC=C1)(=O)O.C(C1=CC=CC=C1)(=O)O.C(C1=CC=CC=C1)(=O)O.C(C1=CC=CC=C1)(=O)O.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 YZMXTFHCEYRBGW-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- RTWDNEGAXDZHLL-UHFFFAOYSA-J [O-]B([O-])[O-].[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound [O-]B([O-])[O-].[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.[O-]C(=O)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 RTWDNEGAXDZHLL-UHFFFAOYSA-J 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 1
- NBWCUDDSVCYILY-UHFFFAOYSA-M [O-]C(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.C(C=C1)=CC=C1[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [O-]C(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.OC(C1=CC=CC2=CC=CC=C12)=O.C(C=C1)=CC=C1[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 NBWCUDDSVCYILY-UHFFFAOYSA-M 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Epoxy Resins (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はエポキシ化合物等の硬化
触媒、特に潜伏性という性質を兼ね備えた硬化触媒、テ
トラ置換ホスホニウムテトラ有機酸ボレートの合成法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing a curing catalyst such as an epoxy compound, especially a curing catalyst having a latent property, and a tetra-substituted phosphonium tetraorganic acid borate.
【０００２】[0002]
【従来の技術】潜伏性触媒として特公昭５１−２４３９
９号公報に示されるようなテトラ置換ホスホニウムテト
ラ置換ボレートの合成法としては従来、次の式［Ｉ］で
示される反応、As a latent catalyst, Japanese Patent Publication No. 51-2439.
As a method for synthesizing a tetra-substituted phosphonium tetra-substituted borate as shown in Japanese Patent Laid-Open No. 9, a reaction represented by the following formula [I] is conventionally used:
【０００３】[0003]
【化４】 [Chemical 4]
【０００４】（式中のＸはハロゲンを示す。） 即ち、テトラ置換ホスホニウムハライドとテトラ置換ボ
レートのナトリウム塩を水または水と有機溶剤との混合
物中で反応させる方法が代表的に知られている。上記の
式［Ｉ］の反応において、出発原料であるテトラ置換ボ
レートのナトリウム塩は次の式［II］、［III］で示さ
れるように、(X in the formula represents halogen.) That is, a method is known in which a tetra-substituted phosphonium halide and a sodium salt of a tetra-substituted borate are reacted in water or a mixture of water and an organic solvent. . In the reaction of the above formula [I], the sodium salt of tetra-substituted borate, which is a starting material, is represented by the following formulas [II] and [III]:
【０００５】[0005]
【化５】 Embedded image
【０００６】[0006]
【化６】 [Chemical 6]
【０００７】２段階の反応により得られる。しかしなが
ら、この反応は式［II］中に示されるＲＭｇＸというグ
リニャール（Grignard）試薬を用いており、完全な無水
系でなければ進行しないことから、工業的に合成するに
は困難である。Obtained by a two-step reaction. However, this reaction uses a Grignard reagent of RMgX represented by the formula [II], and since it does not proceed unless it is a completely anhydrous system, it is difficult to synthesize industrially.
【０００８】[0008]
【発明が解決しようとする課題】本発明は前項で述べた
ような合成法を経由せず、高収率で、エポキシ化合物等
の硬化触媒として有用な潜伏性触媒、テトラ置換ホスホ
ニウムテトラ有機酸ボレート（Ｃ）の合成法を提供する
ことにある。DISCLOSURE OF THE INVENTION The present invention does not go through the synthetic method described in the preceding paragraph, and is a latent catalyst useful as a curing catalyst for epoxy compounds and the like, in a high yield, and a tetrasubstituted phosphonium tetraorganic acid borate. It is to provide a synthetic method of (C).
【０００９】[0009]
【課題を解決するための手段】そこで本発明者らは、上
記課題を解決すべく鋭意検討した結果、本発明を完成す
るに至った。即ち本発明は、一般式（１）で示されるテ
トラ置換ホスホニウムテトラ置換ボレート（Ａ）、The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention is a tetra-substituted phosphonium tetra-substituted borate (A) represented by the general formula (1),
【００１０】[0010]
【化１】 Embedded image
【００１１】（式中のＲ1、Ｒ2、Ｒ3及びＲ4は各々１価の
芳香環を含む有機基または１価の脂肪族残基よりなる群
より選ばれた置換基を表し、それぞれ同じであっても異
なっていても良い。また、式中のＲ5、Ｒ6、Ｒ7及びＲ8は
炭化水素基（アルキル基、フェニル基、置換フェニル基
等）を表し、それぞれ同じであっても異なっていても良
い。）と、一般式（２）で示される、分子外に放出しう
るプロトンを少なくとも１個以上分子内に有するｎ（ｎ
≧１）価の有機酸（Ｂ）、(In the formula, R 1 , R 2 , R 3 and R 4 each represent a substituent selected from the group consisting of a monovalent aromatic ring-containing organic group or a monovalent aliphatic residue; R 5 , R 6 , R 7 and R 8 in the formula represent a hydrocarbon group (alkyl group, phenyl group, substituted phenyl group, etc.) and are the same. Or at least one proton which can be released to the outside of the molecule, represented by the general formula (2).
≧ 1) valent organic acid (B),
【００１２】[0012]
【化２】 Embedded image
【００１３】とを熱反応させることにより生成する、テ
トラ置換ホスホニウムテトラ置換ボレート（Ａ）のボロ
ン側のすべての置換基Ｒ5、Ｒ6、Ｒ7及びＲ8が有機酸
（Ｂ）のプロトンが分子外に１個放出されてなる根によ
る基に置換された一般式（３）で示される潜伏性触媒、
テトラ置換ホスホニウムテトラ有機酸ボレート（Ｃ）All the substituents R 5 , R 6 , R 7 and R 8 on the boron side of the tetra-substituted phosphonium tetra-substituted borate (A), which are produced by the thermal reaction of and, are the protons of the organic acid (B). A latent catalyst represented by the general formula (3), in which one radical is released outside the molecule and is substituted by a radical.
Tetra-substituted phosphonium tetra-organic acid borate (C)
【００１４】[0014]
【化３】 Embedded image
【００１５】（式中のＲ1、Ｒ2、Ｒ3及びＲ4は前記と同義
である。）の合成法に関するものである。The present invention relates to a method for synthesizing (wherein R 1 , R 2 , R 3 and R 4 are as defined above).
【００１６】[0016]
【作用】本発明はテトラ置換ホスホニウムテトラ置換ボ
レート（Ａ）と有機酸（Ｂ）との熱反応により潜伏性触
媒、テトラ置換ホスホニウムテトラ有機酸ボレート
（Ｃ）を合成するものであり、テトラ置換ホスホニウム
テトラ置換ボレート（Ａ）１モルに対し、有機酸（Ｂ）
４モルの反応を例にとり、以下に概略を示す。The present invention is to synthesize a latent catalyst, a tetra-substituted phosphonium tetra-organic acid borate (C), by a thermal reaction between a tetra-substituted phosphonium tetra-substituted borate (A) and an organic acid (B). Organic acid (B) to 1 mol of tetra-substituted borate (A)
An outline is shown below by taking a reaction of 4 mol as an example.
【００１７】[0017]
【化７】 [Chemical 7]
【００１８】この反応では、テトラ置換ホスホニウムテ
トラ置換ボレート（Ａ）は有機酸（Ｂ）の存在下、熱が
加わることにより、テトラ置換ホスホニウムテトラ置換
ボレート（Ａ）のボロン側置換基であるＲ5、Ｒ6、Ｒ7
及びＲ8の炭化水素基は有機酸（Ｂ）のプロトンが分子
外に１個放出されてなる根による基に置換され、潜伏性
触媒、テトラ置換ホスホニウムテトラ有機酸ボレート
（Ｃ）を生成する。脱離したＲ5、Ｒ6、Ｒ7及びＲ8の炭
化水素基はそれぞれ有機酸（Ｂ）からのプロトンを受け
取り、Ｒ5Ｈ、Ｒ6Ｈ、Ｒ7Ｈ及びＲ8Ｈという副生成物と
なる。In this reaction, the tetra-substituted phosphonium tetra-substituted borate (A) is heated in the presence of the organic acid (B) to generate R 5 which is a boron side substituent of the tetra-substituted phosphonium tetra-substituted borate (A). , R 6 , R 7
The hydrocarbon group of R 8 and R 8 is substituted with a group formed by a root formed by releasing one proton of the organic acid (B) out of the molecule to form a latent catalyst, a tetra-substituted phosphonium tetraorganic acid borate (C). The eliminated hydrocarbon groups of R 5 , R 6 , R 7 and R 8 each receive a proton from the organic acid (B), and R 5 H, R 6 H, R 7 H and R 8 H are by-products. Becomes
【００１９】上記の反応では、市販されているテトラ置
換ホスホニウムテトラ置換ボレート（Ａ）を用い１段階
で反応させるため、非常に高収率で目的とする潜伏性触
媒、テトラ置換ホスホニウムテトラ有機酸ボレート
（Ｃ）を得ることができる。置換基Ｒ1、Ｒ2、Ｒ3及び
Ｒ4はそれぞれ同じであっても異なっていても良く、更
に特定の置換基の位置など何ら限定されるものではな
い。In the above reaction, a commercially available tetra-substituted phosphonium tetra-substituted borate (A) is used for the reaction in one step. Therefore, the desired latent catalyst, tetra-substituted phosphonium tetra-organic acid borate is obtained in a very high yield. (C) can be obtained. The substituents R 1 , R 2 , R 3 and R 4 may be the same or different, and the position of a specific substituent is not limited at all.
【００２０】ここで分子外に放出しうるプロトンを少な
くとも１個以上分子内に有するｎ（ｎ≧１）価の有機酸
（Ｂ）の具体的な例としては、酢酸、トリフルオロ酢酸
等の脂肪族カルボン酸、安息香酸、ナフトエ酸及びそれ
らの芳香核に官能基を有するものやフタル酸、トリメリ
ット酸、ピロメリット酸、２，６−ナフタレンジカルボ
ン酸等の多官能芳香族カルボン酸、ステアリルアルコー
ルなどの脂肪族アルコール、フェノールやナフトール、
フェノールやナフトールの芳香核に官能基を有するも
の、イソシアヌル酸、１，２，３−ベンゾトリアゾール
等が例示できる。Specific examples of the n (n ≧ 1) -valent organic acid (B) having at least one proton that can be released to the outside of the molecule, such as acetic acid and trifluoroacetic acid, are fats. Group carboxylic acid, benzoic acid, naphthoic acid and those having a functional group in their aromatic nucleus, polyfunctional aromatic carboxylic acid such as phthalic acid, trimellitic acid, pyromellitic acid, 2,6-naphthalenedicarboxylic acid, stearyl alcohol Aliphatic alcohols, such as phenol and naphthol,
Examples thereof include those having a functional group in the aromatic nucleus of phenol and naphthol, isocyanuric acid, 1,2,3-benzotriazole, and the like.
【００２１】また、一般式（１）で示されるテトラ置換
ホスホニウムテトラ置換ボレート（Ａ）及び一般式
（３）で示される潜伏性触媒、テトラ置換ホスホニウム
テトラ有機酸ボレート（Ｃ）の置換基Ｒ1、Ｒ2、Ｒ3及
びＲ4の例として、フェニル、トリル、エチルフェニ
ル、メトキシフェニル、ナフチル、ベンジル基等の芳香
環を含む基やエチル、ブチル基等のアルキル基が例示で
きる。Further, the tetra-substituted phosphonium tetra-substituted borate (A) represented by the general formula (1), the latent catalyst represented by the general formula (3), and the substituent R 1 of the tetra-substituted phosphonium tetra-organic acid borate (C). , R 2 , R 3 and R 4 include groups containing an aromatic ring such as phenyl, tolyl, ethylphenyl, methoxyphenyl, naphthyl and benzyl groups, and alkyl groups such as ethyl and butyl groups.
【００２２】本発明における合成法は、テトラ置換ホス
ホニウムテトラ置換ボレート（Ａ）に対し、相当する有
機酸（Ｂ）を窒素雰囲気下、１〜１２時間、好ましくは
４〜６時間、加熱することにより潜伏性触媒、テトラ置
換ホスホニウムテトラ有機酸ボレート（Ｃ）を合成する
方法であるが、１モルのテトラ置換ホスホニウムテトラ
置換ボレート（Ａ）に対する有機酸（Ｂ）のモル数は４
以上が好ましく、４未満だと未反応のテトラ置換ホスホ
ニウムテトラ置換ボレート（Ａ）が残り、このテトラ置
換ホスホニウムテトラ置換ボレート（Ａ）は常温では
Ｎ，Ｎ−ジメチルホルムアミドやＮ−メチル−２−ピロ
リドン等の強極性溶媒にしか溶解しないので除去が困難
である。In the synthesis method of the present invention, the tetra-substituted phosphonium tetra-substituted borate (A) is heated with a corresponding organic acid (B) in a nitrogen atmosphere for 1 to 12 hours, preferably 4 to 6 hours. This is a method for synthesizing a latent catalyst, tetra-substituted phosphonium tetra-organic acid borate (C), but the number of moles of organic acid (B) is 1 mol of tetra-substituted phosphonium tetra-substituted borate (A).
The above is preferable, and when it is less than 4, unreacted tetra-substituted phosphonium tetra-substituted borate (A) remains, and this tetra-substituted phosphonium tetra-substituted borate (A) is N, N-dimethylformamide or N-methyl-2-pyrrolidone at room temperature. It is difficult to remove because it dissolves only in a strong polar solvent such as.
【００２３】反応は有機酸（Ｂ）の融点以上、速やかに
反応させるため好ましくは２００℃以上且つ有機酸
（Ｂ）の融点以上の温度で行い、副生成物であるＲ
5Ｈ、Ｒ6Ｈ、Ｒ7Ｈ及びＲ8Ｈは系外に除去しながら実施
する。反応は無溶剤系で実施するが、場合によっては沸
点が２００℃以上の溶剤を用いても何ら差し支えない。The reaction is carried out at a temperature not lower than the melting point of the organic acid (B) and preferably not lower than 200 ° C. and not lower than the melting point of the organic acid (B) in order to react rapidly.
5 H, R 6 H, R 7 H and R 8 H is carried while removing out of the system. The reaction is carried out in a solvent-free system, but in some cases, a solvent having a boiling point of 200 ° C. or higher may be used.
【００２４】以上の条件で反応が終了した後は、常法の
手段により生成物を分離、洗浄及び乾燥することにより
潜伏性触媒、テトラ置換ホスホニウムテトラ有機酸ボレ
ート（Ｃ）を回収する。After the reaction is completed under the above conditions, the latent catalyst and the tetra-substituted phosphonium tetraorganic acid borate (C) are recovered by separating, washing and drying the product by a conventional method.
【００２５】[0025]
【実施例】次に、実施例を挙げて本発明を更に具体的に
説明するが、本発明はこれら実施例に限定されない。EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
【００２６】［実施例１］市販のテトラフェニルホスホ
ニウムテトラフェニルボレート（北興化学工業（株）製
ＴＰＰ−Ｋ）６５．８ｇ（０．１０モル）、安息香酸４
８．８ｇ（０．４０モル）を温度計、共沸分液漏斗、冷
却管及び撹拌機を付けたフラスコに仕込み、窒素雰囲気
下、２３０℃で４時間反応した。その際、副生成物であ
るベンゼンを系外に除去した。反応終了後冷却し、トル
エンで洗浄乾燥し、白色結晶の潜伏性触媒、テトラフェ
ニルホスホニウムテトラ安息香酸ボレートを得た。この
融点は２１１℃、収量は１０１ｇ（収率９８％）であっ
た。分析結果は下記構造（ａ）に相当する化合物と一致
する。Example 1 Commercially available tetraphenylphosphonium tetraphenylborate (TPP-K manufactured by Hokuko Kagaku Kogyo KK) 65.8 g (0.10 mol), benzoic acid 4
8.8 g (0.40 mol) was charged into a flask equipped with a thermometer, an azeotropic separatory funnel, a condenser and a stirrer, and reacted under a nitrogen atmosphere at 230 ° C. for 4 hours. At that time, benzene as a by-product was removed to the outside of the system. After completion of the reaction, the mixture was cooled, washed with toluene and dried to obtain a latent catalyst of tetraphenylphosphonium tetrabenzoate borate as white crystals. The melting point was 211 ° C., and the yield was 101 g (98% yield). The analysis result is consistent with the compound corresponding to the following structure (a).
【００２７】[0027]
【化８】 Embedded image
【００２８】［実施例２］市販のテトラフェニルホスホ
ニウムテトラフェニルボレート（北興化学工業（株）製
ＴＰＰ−Ｋ）３２．９ｇ（０．０５モル）、１−ナフト
エ酸３４．４ｇ（０．２０モル）を温度計、共沸分液漏
斗、冷却管及び撹拌機を付けたフラスコに仕込み、窒素
雰囲気下、２６０℃で５時間反応した。その際、副生成
物であるベンゼンを系外に除去した。反応終了後冷却
し、メタノールで洗浄乾燥し、白色結晶の潜伏性触媒、
テトラフェニルホスホニウムテトラ（１−ナフトエ酸）
ボレートを得た。この融点は２３９℃、収量は４８ｇ
（収率９３％）であった。分析結果は下記構造（ｂ）に
相当する化合物と一致する。Example 2 Commercially available tetraphenylphosphonium tetraphenylborate (TPP-K manufactured by Hokuko Chemical Co., Ltd.) 32.9 g (0.05 mol), 1-naphthoic acid 34.4 g (0.20 mol) Was charged into a flask equipped with a thermometer, an azeotropic separatory funnel, a condenser and a stirrer, and reacted at 260 ° C. for 5 hours under a nitrogen atmosphere. At that time, benzene as a by-product was removed to the outside of the system. After completion of the reaction, the mixture is cooled, washed with methanol and dried, and a latent catalyst of white crystals,
Tetraphenylphosphonium tetra (1-naphthoic acid)
Got borate. This melting point is 239 ° C, and the yield is 48g.
(Yield 93%). The analysis result is consistent with the compound corresponding to the following structure (b).
【００２９】[0029]
【化９】 [Chemical 9]
【００３０】［実施例３］市販のテトラフェニルホスホ
ニウムテトラフェニルボレート（北興化学工業（株）製
ＴＰＰ−Ｋ）６５．８ｇ（０．１０モル）、１−ナフト
ール１１５．２ｇ（０．４０モル）を温度計、共沸分液
漏斗、冷却管及び撹拌機を付けたフラスコに仕込み、窒
素雰囲気下、２４０℃で６時間反応した。その際、副生
成物であるベンゼンを系外に除去した。反応終了後冷却
し、再沈・洗浄乾燥し、白色結晶の潜伏性触媒、テトラ
フェニルホスホニウムテトラ（１−ナフトール）ボレー
トを得た。この融点は２０６℃、収量は１４１ｇ（収率
９４％）であった。分析結果は下記構造（ｃ）に相当す
る化合物と一致する。Example 3 Commercially available tetraphenylphosphonium tetraphenylborate (TPP-K manufactured by Hokuko Kagaku Kogyo KK) 65.8 g (0.10 mol), 1-naphthol 115.2 g (0.40 mol) Was charged into a flask equipped with a thermometer, an azeotropic separatory funnel, a condenser and a stirrer, and reacted at 240 ° C. for 6 hours under a nitrogen atmosphere. At that time, benzene as a by-product was removed to the outside of the system. After the completion of the reaction, the mixture was cooled, reprecipitated, washed and dried to obtain a white crystal latent catalyst, tetraphenylphosphonium tetra (1-naphthol) borate. The melting point was 206 ° C., and the yield was 141 g (94% yield). The analysis result is consistent with the compound corresponding to the following structure (c).
【００３１】[0031]
【化１０】 [Chemical 10]
【００３２】また分析結果の例として、実施例１のテト
ラフェニルホスホニウムテトラ安息香酸ボレートの分析
結果を図１、表１及び図２に示す。As an example of the analysis result, the analysis result of tetraphenylphosphonium tetrabenzoic acid borate of Example 1 is shown in FIG. 1, Table 1 and FIG.
【００３３】図１は昇温速度１０℃／分での示差熱分析
（ＤＳＣ）の結果であり、テトラフェニルホスホニウム
テトラ安息香酸ボレートが２１１℃で鋭い吸熱を示し、
これにより化合物が単一のものであるといえる。表１は
元素分析の結果であり、構造式（ａ）の理論値との良い
一致を示している。FIG. 1 shows the results of differential thermal analysis (DSC) at a heating rate of 10 ° C./min. Tetraphenylphosphonium tetrabenzoic acid borate showed a sharp endotherm at 211 ° C.
From this, it can be said that the compound is single. Table 1 shows the results of elemental analysis and shows good agreement with the theoretical value of the structural formula (a).
【００３４】[0034]
【表１】 [Table 1]
【００３５】図２は質量分析のFast Atom Bonbardment
法により正イオンと負イオンを検出した結果である。正
イオンモードではテトラフェニルホスホニウム部に相当
する質量数３３９のピークが、また負イオンモードでは
テトラ安息香酸ボレート部に相当する質量数４９５のピ
ークが検出された。以上のことから、テトラフェニルホ
スホニウムテトラ安息香酸ボレートが構造式（ａ）に示
されうる構造であることがわかった。FIG. 2 shows Fast Atom Bonbardment of mass spectrometry.
This is the result of detecting positive ions and negative ions by the method. A peak with a mass number of 339 corresponding to the tetraphenylphosphonium portion was detected in the positive ion mode, and a peak with a mass number of 495 corresponding to the tetrabenzoic acid borate portion was detected in the negative ion mode. From the above, it was found that tetraphenylphosphonium tetrabenzoic acid borate has a structure that can be represented by the structural formula (a).
【００３６】[0036]
【発明の効果】実施例１〜３から明らかなように、本発
明の合成法によれば目的の潜伏性触媒、テトラ置換ホス
ホニウムテトラ有機酸ボレートを工業的に有利で且つ効
率よく得ることが可能である。As is apparent from Examples 1 to 3, according to the synthesis method of the present invention, the target latent catalyst, tetra-substituted phosphonium tetraorganic acid borate, can be industrially advantageously and efficiently obtained. Is.
【図１】図１は、実施例１のテトラフェニルホスホニウ
ムテトラ安息香酸ボレートの昇温速度１０℃／分での示
差熱分析（ＤＳＣ）の結果を示す。FIG. 1 shows the results of differential thermal analysis (DSC) of tetraphenylphosphonium tetrabenzoic acid borate of Example 1 at a heating rate of 10 ° C./min.
【図２】図２は、実施例１のテトラフェニルホスホニウ
ムテトラ安息香酸ボレートについて、質量分析のFast A
tom Bonbardment法により正イオンと負イオンを検出し
た結果を示す。2 is a mass spectrometry analysis of Fast A of tetraphenylphosphonium tetrabenzoate borate of Example 1. FIG.
The results of detecting positive and negative ions by the tom Bonbardment method are shown.
Claims (6)
ホニウムテトラ置換ボレート（Ａ）、 【化１】 （式中のＲ1、Ｒ2、Ｒ3及びＲ4は各々１価の芳香環を含む
有機基または１価の脂肪族残基よりなる群より選ばれた
置換基を表し、それぞれ同じであっても異なっていても
良い。また、式中のＲ5、Ｒ6、Ｒ7及びＲ8は炭化水素基
（アルキル基、フェニル基、置換フェニル基等）を表
し、それぞれ同じであっても異なっていても良い。）
と、一般式（２）で示される、分子外に放出しうるプロ
トンを少なくとも１個以上分子内に有するｎ（ｎ≧１）
価の有機酸（Ｂ）、 【化２】 とを熱反応させることにより生成する、テトラ置換ホス
ホニウムテトラ置換ボレート（Ａ）のボロン側のすべて
の置換基Ｒ5、Ｒ6、Ｒ7及びＲ8が、有機酸（Ｂ）のプロト
ンが分子外に１個放出されてなる根による基に置換され
た一般式（３）で示される潜伏性触媒、テトラ置換ホス
ホニウムテトラ有機酸ボレート（Ｃ） 【化３】 （式中のＲ1、Ｒ2、Ｒ3及びＲ4は前記と同義である。）の
合成法。1. A tetra-substituted phosphonium tetra-substituted borate (A) represented by the general formula (1): (In the formula, R 1 , R 2 , R 3 and R 4 each represents a monovalent aromatic ring-containing organic group or a substituent selected from the group consisting of monovalent aliphatic residues, and they are the same. R 5 , R 6 , R 7 and R 8 in the formula represent a hydrocarbon group (alkyl group, phenyl group, substituted phenyl group, etc.) and may be the same or different. It may be.)
And n (n ≧ 1) having at least one proton that can be released to the outside of the molecule represented by the general formula (2)
Valent organic acid (B), All the substituents R 5 , R 6 , R 7 and R 8 on the boron side of the tetra-substituted phosphonium tetra-substituted borate (A), which are generated by the thermal reaction of the A latent catalyst represented by the general formula (3), which is substituted with a root group by releasing one of them, a tetra-substituted phosphonium tetraorganoic acid borate (C) (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above).
置換ボレート（Ａ）がテトラ置換ホスホニウムテトラフ
ェニルボレートである請求項１記載の潜伏性触媒、テト
ラ置換ホスホニウムテトラ有機酸ボレート（Ｃ）の合成
法。2. A process for synthesizing a latent catalyst, a tetra-substituted phosphonium tetraorganic acid borate (C) according to claim 1, wherein the tetra-substituted phosphonium tetra-substituted borate (A) is a tetra-substituted phosphonium tetraphenyl borate.
ボキシル基を少なくとも１個有するカルボン酸である請
求項１記載の潜伏性触媒、テトラ置換ホスホニウムテト
ラ有機酸ボレート（Ｃ）の合成法。3. The latent catalyst according to claim 1, wherein the organic acid (B) of claim 1 is a carboxylic acid having at least one carboxyl group in one molecule, and the tetrasubstituted phosphonium tetraorganic acid borate (C) is used. Synthetic method.
ボキシル基を少なくとも１個有する芳香族カルボン酸で
ある請求項１記載の潜伏性触媒、テトラ置換ホスホニウ
ムテトラ有機酸ボレート（Ｃ）の合成法。4. The latent catalyst according to claim 1, wherein the organic acid (B) according to claim 1 is an aromatic carboxylic acid having at least one carboxyl group in one molecule, and the tetrasubstituted phosphonium tetraorganic acid borate (C). ) Synthetic method.
ロキシル基を少なくとも１個有するアルコールである請
求項１記載の潜伏性触媒、テトラ置換ホスホニウムテト
ラ有機酸ボレート（Ｃ）の合成法。5. The synthesis of the latent catalyst tetra-substituted phosphonium tetraorganic acid borate (C) according to claim 1, wherein the organic acid (B) of claim 1 is an alcohol having at least one hydroxyl group in one molecule. Law.
ロキシル基を少なくとも１個有するフェノール類である
請求項１記載の潜伏性触媒、テトラ置換ホスホニウムテ
トラ有機酸ボレート（Ｃ）の合成法。6. The latent catalyst, tetra-substituted phosphonium tetraorganoic acid borate (C) according to claim 1, wherein the organic acid (B) of claim 1 is a phenol having at least one hydroxyl group in one molecule. Synthetic method.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01248895A JP3254619B2 (en) | 1995-01-30 | 1995-01-30 | Synthetic method of phosphorus-based latent catalyst |
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| Publication Number | Publication Date |
|---|---|
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| JP2002138091A (en) * | 2000-10-30 | 2002-05-14 | Sumitomo Bakelite Co Ltd | Method for synthesizing tetrax (acyloxy) borate (1-) and substistuted onium tetrax (acyloxy) borate (1-) |
| JP2002167390A (en) * | 2000-11-30 | 2002-06-11 | Sumitomo Bakelite Co Ltd | Synthesizing method of tetrakis(acyloxy)borate(1-) and substituted onium tetrakis(acyloxy)borate(1-) |
| JP2010189357A (en) * | 2009-02-20 | 2010-09-02 | Air Water Inc | Method for producing onium tetrakis(acyloxy)borate |
| JP5888230B2 (en) * | 2010-03-10 | 2016-03-16 | 味の素株式会社 | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3254619B2 (en) | 2002-02-12 |
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