WO2010143556A1 - フルオレン誘導体の非晶質形態およびその製造方法 - Google Patents
フルオレン誘導体の非晶質形態およびその製造方法 Download PDFInfo
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- WO2010143556A1 WO2010143556A1 PCT/JP2010/059245 JP2010059245W WO2010143556A1 WO 2010143556 A1 WO2010143556 A1 WO 2010143556A1 JP 2010059245 W JP2010059245 W JP 2010059245W WO 2010143556 A1 WO2010143556 A1 WO 2010143556A1
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- fluorene
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- hydroxyethoxy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
- C07C35/38—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings derived from the fluorene skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Definitions
- the present invention relates to an amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and a method for producing the same.
- fluorene derivatives such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene have been excellent in heat resistance and transparency, and have a high refractive index (for example, epoxy resins, polyesters, polyethers, Polycarbonate, etc.) is promising as a raw material for producing optical lenses, films, plastic optical fibers, optical disk bases, heat-resistant resins, engineering plastics, and the like.
- Amorphous solids also have transparency, uniformity, isotropic properties, excellent processability, etc., and can be used as photonics materials such as organic electroluminescence elements, recording elements, storage elements, electric field sensors, and optical sampling oscilloscopes. Promising.
- amorphous low-molecular-weight organic compounds have attracted attention in recent years because they are expected as high-resolution and low-roughness resist materials.
- low molecular weight organic compounds are generally known to be very easy to crystallize and difficult to become amorphous, and usually exist as crystals below the melting point.
- amorphous form may be observed in pharmaceuticals with a complicated structure, but the amorphous form is in a non-equilibrium state thermodynamically and is more unstable than the crystalline form, so that the transition occurs easily. Recrystallize. For this reason, finding amorphous low molecular weight organic compounds that easily form a stable glass state is extremely important from the viewpoint of creating new functional materials that are different from conventional amorphous polymers and polymer composite materials. It is.
- Non-Patent Document 1 As a method of producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, fluorenone and phenoxyethanol are subjected to dehydration condensation using sulfuric acid and thiols as catalysts (Patent Document 1), 9,9-bis ( A method of reacting 4-hydroxyphenyl) fluorene with ethylene carbonate (Non-Patent Document 1) is disclosed. In addition, we applied for a new manufacturing method different from the manufacturing method (Patent Document 2).
- the crystal form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is a polymorph having a melting point of 100 to 130 ° C. (hereinafter referred to as polymorph A).
- polymorph B there is a polymorph having a melting point of 150 ° C. to 180 ° C.
- Japanese Patent Publication Japanese Patent Laid-Open No. 7-165657 (published on June 27, 1995)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2007-23016 (published on Feb. 1, 2007)” Japanese Patent Gazette “Patent No. 4140975 (published on June 20, 2008)”
- the object of the present invention is 9,9-bis (4- (2-hydroxyethoxy) phenyl) which maintains a certain quality, is excellent as a polymer raw material, and is useful as a novel functional material such as an optical material and a photonics material. It is to provide a novel amorphous form of fluorene and to provide a method for producing the amorphous form.
- 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene has two types of crystalline substances, polymorph A and polymorph B. It has been found that there is an amorphous form other than the form, that is, an amorphous form. In addition, the present inventors have completed the present invention by finding a production method for selectively obtaining such an amorphous form.
- the present invention provides the following (1) to (6).
- Amorphous 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene means, in other words, an amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (Amorphous).
- the X-ray diffraction peak pattern contains a broad halo at 2 ⁇ of about 5 ° to 30 °; and
- the differential scanning calorimetry thermogram shows a crystalline 9,9-bis (4- An amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having the endothermic peaks at about 161 ° C. and about 119 ° C. of (2-hydroxyethoxy) phenyl) fluorene.
- a novel amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and a method for producing the same can be provided.
- the known polymorph A and polymorph B are powdery crystals
- the amorphous form obtained by the present invention is a glassy substance, and there is a risk of explosion due to dust and health hazard. This is advantageous for industrial handling in that the particle size can be freely changed by pulverization or the like according to equipment and applications.
- polymorph A and polymorph B which are crystalline are powdery, there is a problem that they are easily solidified by absorbing moisture, but the amorphous form obtained by the present invention is a glassy substance. Therefore, there is no such problem and the handleability is excellent.
- the amorphous form obtained by the present invention is a glassy substance that is stable and excellent in transparency without easily undergoing transition and recrystallization, it has new functions such as optical materials and photonics materials. It is also useful as a property material.
- FIG. 1 shows a characteristic powder X-ray diffraction pattern of an amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 2 shows a characteristic differential scanning calorimetry (DSC) curve of the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 3 shows a characteristic powder X-ray diffraction pattern of polymorph B of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 4 shows a characteristic differential scanning calorimetry (DSC) curve of polymorph B of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 1 shows a characteristic powder X-ray diffraction pattern of an amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 2 shows a characteristic differential
- FIG. 5 shows the characteristic powder X-ray diffraction pattern of polymorph A of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- FIG. 6 shows a characteristic differential scanning calorimetry (DSC) curve of polymorph A of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
- an amorphous solid consists of a disordered molecular arrangement and does not possess a distinguishable crystal lattice. Also, the solubility of amorphous solids is usually higher than the crystalline form and does not have a constant melting point. Therefore, the absence of a clear peak in the powder X-ray diffraction pattern and the absence of the melting endothermic peak in the differential scanning calorimetry (DSC) curve indicate that it is an amorphous form.
- the amorphous form of the present invention has at least one of the following features (a) to (d).
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in the present invention does not have any sharp peaks characteristic of the crystalline form in powder X-ray diffraction, It has a powder X-ray diffraction pattern (halo pattern) showing a broad peak of typical amorphous at diffraction angles (2 ⁇ ) in the range of about 5 ° to about 60 °. More specifically, essentially the same powder X-ray diffraction pattern as in FIG. 1 is shown.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in the present invention has (I) a broad X-ray diffraction peak pattern at 2 ⁇ of about 5 ° to 30 °. And (II) endothermic peaks at about 161 ° C. and about 119 ° C. of the crystalline 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. Lack.
- crystalline 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene includes polymorph A and polymorph A as disclosed in Japanese Patent No. 4140975. Form B exists.
- Polymorph A has an endothermic peak in the differential scanning calorimetry temperature recording diagram of 100 to 130 ° C.
- polymorph B has an endothermic peak in the differential scanning calorimetry temperature recording diagram of 150 to 180 ° C. Therefore, the above (II) is not limited to those lacking the endothermic peaks at about 161 ° C. and about 119 ° C.
- the differential scanning calorimetry temperature recording diagram shows a crystalline 9,9-bis (4- ( This includes the case where 2-hydroxyethoxy) phenyl) fluorene lacks the 150-180 ° C. and 100-130 ° C. endothermic peaks.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in the present invention has a clear first-order transition such as the melting point of the crystal in differential scanning calorimetry (DSC). There is no melting endothermic peak associated with. More particularly, it shows essentially the same DSC curve as in FIG.
- the powder X-ray diffraction pattern of the present invention was measured using a Spectris X-ray diffractometer (X'PertPRO) equipped with a CuX ray source operating at 45 kV and 40 mA. During the measurement, the sample was rotated at 120 rpm and analyzed at an angle of 5 ° -70 ° ( ⁇ -2 ⁇ ) at 2.0 ° / min.
- X'PertPRO Spectris X-ray diffractometer
- the differential scanning calorimetry (DSC) curve of the present invention was measured using a differential scanning calorimeter (DSC220C) manufactured by Seiko Denshi Kogyo.
- the sample was precisely weighed in an aluminum pan and purged with nitrogen gas at a flow rate of 40 ml / min.
- the scanning temperature range was 40-260 ° C. and analyzed at a scanning rate of 10 ° C./min.
- the solid form of the present invention exhibits essentially the same powder X-ray diffraction pattern as depicted in the given figure, or essentially the same DSC curve as depicted in the given figure. Where indicated to indicate, the term “essentially identical” is intended to encompass such experimental differences.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention has a single or other crystalline or amorphous form content of the same compound. It refers to a solid form of less than wt%, preferably less than 10 wt%, more preferably less than 3 wt%, and most preferably less than 1 wt%.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention is amorphous 9,9-bis (4- (2-hydroxyethoxy) It may be composed only of (phenyl) fluorene, or may contain other crystalline forms or other amorphous forms in the above proportions.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention has at least one of the other crystalline form and the other amorphous form in the above proportion. May be included.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention is obtained by cooling a melt of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. It is obtained by solidifying. 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene does not crystallize upon cooling from the melt.
- molten liquid means a substance state that has been heated to a temperature higher than the melting point or the temperature at which it begins to deform when heated and changed into a liquid.
- the method for preparing the melt to be used is not particularly limited. For example, even if the 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene crystals are heated and melted as they are, Well, a melt obtained by dissolving 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene in a suitable solvent to form a solution and distilling off the solvent from this solution. Further, it may be a melt recovered by distillation under reduced pressure of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene at a temperature equal to or higher than the melting point.
- the crystalline form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene used is not particularly limited, and either polymorph A or polymorph B is used. Or a mixture thereof. These polymorphs do not recrystallize upon cooling from the melt. Also, recrystallization does not cause recrystallization.
- the heating temperature for preparing the melt is not particularly limited as long as it is equal to or higher than the temperature at which 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene melts, but usually 100 ° C. to 400 ° C.
- the temperature is preferably 150 to 350 ° C, more preferably 170 to 250 ° C. If the heating temperature is high, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene may be decomposed, which is not preferable.
- the temperature at which 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is distilled under reduced pressure is preferably 170 to 400 ° C, more preferably 200 to 350 ° C.
- the molten state may be cooled immediately after melting, it is preferably cooled after stirring for a certain time (for example, 30 minutes or more) in the molten state.
- the cooling temperature is not particularly limited as long as it is not higher than the temperature at which 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is solidified, but is preferably 150 ° C. or less, more preferably 100 ° C. or less. is there. Usually, it is cooled to room temperature (about 25 ° C.).
- the cooling rate is not particularly limited, and is amorphous when the melt is slowly cooled (for example, cooling rate 0.2 ° C./min) or rapidly cooled (for example, cooling rate 10 ° C./min). A solid in solid form can be obtained.
- the cooling rate is more preferably 0.5 to 10 ° C./min, and further preferably 2 to 10 ° C./min.
- the method for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene as a melt is not particularly limited, but preferably fluorenone and 2-phenoxyethanol are reacted in the presence of an acid catalyst. Can be obtained. More preferably, it can be obtained by reacting fluorenone with 2-phenoxyethanol in the presence of a heteropolyacid catalyst (for example, phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, phosphovanadmolybdic acid, etc.).
- Polymorph B can be obtained, for example, by the method described in Japanese Patent Publication No. 4140975.
- Example 1 Polymorph B of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was obtained by the method described in Example 2 of Japanese Patent Publication No. 4140975. The obtained polymorph B was charged into a glass flask, heated and melted at 230 ° C., and then heated at the same temperature for 1 hour. The melt was cooled to room temperature over about 4 hours to obtain a colorless and transparent glassy solid. The powder X-ray diffraction pattern and DSC curve of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained showed the characteristics shown in FIGS. 1 and 2, respectively, and were in an amorphous form.
- Example 2 Polymorph A of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was obtained by the method described in Comparative Example 1 of Japanese Patent Publication No. 4140975. The obtained polymorph A was charged into a Kugelrohr distillation apparatus and distilled at 300 ° C. under reduced pressure to recover a 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene melt. The melt was cooled to room temperature over about 10 hours to obtain a colorless and transparent glassy solid. The powder X-ray diffraction pattern and DSC curve of the 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained showed the same characteristics as in FIGS. 1 and 2 and were in an amorphous form.
- a novel amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and a method for producing the same can be provided.
- the known polymorph A and polymorph B are powdery crystals
- the amorphous form obtained by the present invention is a glassy substance, and there is a risk of explosion due to dust and health hazard. This is advantageous for industrial handling in that the particle size can be freely changed by pulverization or the like according to equipment and applications.
- the amorphous form obtained by the present invention is a glassy substance having excellent transparency, it is also useful as a novel functional material such as an optical material or a photonics material.
- the amorphous form of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene of the present invention is useful as a raw material for polymers, and can be used as a raw material for epoxy resins, polyesters, polyethers, and polycarbonates. Can do.
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Abstract
Description
(1)非晶質である9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン。非晶質である9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンとは、言い換えれば、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態(非晶質体)である。
(2)粉末X線回折において、シャープなピークを有さず、5°~60°の範囲内の回折角にハローパターンを有する、(1)に記載の9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態。
(3)以下の特徴:
(I)X線回折ピークパターンが、約5°~30°の2θにおけるブロードなハローを含むこと;および
(II)示差走査熱量測定温度記録図が、結晶状の9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの約161℃および約119℃の吸熱ピークを欠いていること
を有する9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態。
(4)9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの溶融液を、冷却固化させることを特徴とする9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態の製造方法。
(5)9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの溶融液が蒸留回収により得られたものである、前記(4)に記載の製造方法。
(6)溶融温度が100℃~400℃である、前記(4)または(5)に記載の製造方法。
日本国特許公報特許第4140975号明細書の実施例2に記載の方法により9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの多形体Bを得た。得られた多形体Bをガラス製フラスコに仕込み、230℃で加熱溶融した後、同温度で1時間加熱した。この溶融液を約4時間かけて室温まで冷却して無色透明のガラス状固体を得た。得られた9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの粉末X線回折パターンおよびDSC曲線はそれぞれ図1および図2の特徴を示し、非晶質形態であった。
日本国特許公報特許第4140975号明細書の比較例1に記載の方法により9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの多形体Aを得た。得られた多形体Aをクーゲルロール蒸留装置に仕込み、300℃で減圧蒸留して9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの溶融液を回収した。この溶融液を約10時間かけて室温まで冷却して無色透明のガラス状固体を得た。得られた9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの粉末X線回折パターンおよびDSC曲線は図1および図2と同様の特徴を示し非晶質形態であった。
日本国特許公報特許第4140975号明細書の実施例2に記載された方法により9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの多形体Bを白色結晶として得た。得られた多形体Bの粉末X線回折パターンおよびDSC曲線を図3および図4に示す。
日本国特許公報特許第4140975号明細書の比較例1に記載の方法により9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの多形体Aを白色結晶として得た。得られた多形体Aの粉末X線回折パターンおよびDSC曲線を図5および図6に示す。
Claims (6)
- 9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態。
- 粉末X線回折において、シャープなピークを有さず、5°~60°の範囲内の回折角にハローパターンを有することを特徴とする、請求項1に記載の9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態。
- 以下の特徴:
(I)X線回折ピークパターンが、約5°~30°の2θにおけるブロードなハローを含むこと;および
(II)示差走査熱量測定温度記録図が、結晶状の9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの約161℃および約119℃の吸熱ピークを欠いていること
を有する9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態。 - 9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの溶融液を、冷却固化させることを特徴とする、請求項1~3のいずれか1項に記載の9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの非晶質形態の製造方法。
- 9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの溶融液が蒸留回収により得られたものである、請求項4に記載の非晶質形態の製造方法。
- 溶融液の溶融温度が100℃~400℃である、請求項4または5に記載の非晶質形態の製造方法。
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EP10786087.6A EP2441746B1 (en) | 2009-06-11 | 2010-06-01 | Noncrystalline form of fluorene derivative and process for preparation thereof |
CN201080025677.0A CN102803192B (zh) | 2009-06-11 | 2010-06-01 | 芴衍生物的非晶质形态体及其制造方法 |
JP2010529173A JP4673936B2 (ja) | 2009-06-11 | 2010-06-01 | フルオレン誘導体の非晶質およびその製造方法 |
US13/376,516 US8436214B2 (en) | 2009-06-11 | 2010-06-01 | Noncrystalline form of fluorene derivative and process for preparation thereof |
KR1020117029799A KR101726889B1 (ko) | 2009-06-11 | 2010-06-01 | 플루오렌 유도체의 비결정질 형태 및 그의 제조방법 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013133106A1 (ja) * | 2012-03-09 | 2013-09-12 | 本州化学工業株式会社 | 9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレンの製造方法、その結晶体、及びその結晶体の製造方法 |
CN103317746A (zh) * | 2012-03-19 | 2013-09-25 | 宿迁市永星化工有限公司 | 高堆积密度bpef的制备工艺 |
WO2013183173A1 (ja) * | 2012-06-05 | 2013-12-12 | 帝人化成株式会社 | 9,9‐ビス(4‐(2‐ヒドロキシエトキシ)フェニル)フルオレン粉状体 |
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- 2010-06-01 EP EP10786087.6A patent/EP2441746B1/en active Active
- 2010-06-01 CN CN201080025677.0A patent/CN102803192B/zh active Active
- 2010-06-01 KR KR1020117029799A patent/KR101726889B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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US8436214B2 (en) | 2013-05-07 |
CN102803192B (zh) | 2015-05-20 |
EP2441746B1 (en) | 2017-04-05 |
EP2441746A1 (en) | 2012-04-18 |
CN102803192A (zh) | 2012-11-28 |
KR101726889B1 (ko) | 2017-04-13 |
EP2441746A4 (en) | 2012-12-12 |
JPWO2010143556A1 (ja) | 2012-11-22 |
TW201100369A (en) | 2011-01-01 |
TWI447104B (zh) | 2014-08-01 |
US20120095270A1 (en) | 2012-04-19 |
JP4673936B2 (ja) | 2011-04-20 |
KR20120032480A (ko) | 2012-04-05 |
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