JP6905293B2 - Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene and its production method - Google Patents
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene and its production method Download PDFInfo
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- HBTONAMIPDVQRI-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-phenylphenyl]fluoren-9-yl]-2-phenylphenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 HBTONAMIPDVQRI-UHFFFAOYSA-N 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000002411 thermogravimetry Methods 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 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 2
- 230000008025 crystallization Effects 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003921 particle size analysis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの特性及びその製造方法に関し、化学工業の技術分野に属する。 The present invention belongs to the technical field of the chemical industry with respect to the characteristics of pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene and the method for producing the same.
近年、原料樹脂として、９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの人気が高まっている。９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを原料として製造された樹脂は、耐熱性、透明性、高屈折率、優れた成形流動性などの利点を有する。例えば、エポキシ樹脂、ポリエステル樹脂、ポリカーボネート樹脂などは、カメラ、携帯電話のレンズ、車載カメラ、ドローンレンズなどの光学材料として使用されている。 In recent years, 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene has become increasingly popular as a raw material resin. Resins produced from 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene have advantages such as heat resistance, transparency, high refractive index, and excellent molding fluidity. .. For example, epoxy resin, polyester resin, polycarbonate resin and the like are used as optical materials for cameras, mobile phone lenses, in-vehicle cameras, drone lenses and the like.
９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンは、主に粉末状の形状であり、流動性が悪いため、産業的使用に不利である。例えば、ホッパー、材料貯蔵室などから排出されることが困難であり、「ブリッジ」を生成しやすく、輸送性が低いため、管路での流動が妨げられ、粉末が壁に付着して、完全に排出されない恐れがあるなどの欠点を有する。 9,9-Bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene is mainly in the form of powder and has poor fluidity, which is disadvantageous for industrial use. For example, it is difficult to drain from hoppers, material storage chambers, etc., it is easy to form "bridges", and it has low transportability, which hinders the flow in the pipeline, and the powder adheres to the wall, completely. It has drawbacks such as the possibility that it will not be discharged.
従って、産業的使用に有利であり、流動性及び輸送性が良好なペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを開発することが求められる。 Therefore, it is required to develop pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene which is advantageous for industrial use and has good fluidity and transportability.
本発明は、上記問題に対して、流動性及び輸送性が良好で、工業的生産に有利であるペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを提供することを目的とする。 In response to the above problems, the present invention provides pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene, which has good fluidity and transportability and is advantageous for industrial production. The purpose is to provide.
上記目的を実現するために、本発明の技術案は、以下のとおりである。 In order to realize the above object, the technical proposal of the present invention is as follows.
ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンであって、粒子径分布が１００ミクロン〜２０００ミクロンであり、粒子径が１８０ミクロン以上の部分が少なくとも、全体の９０％以上である。 Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene having a particle size distribution of 100 to 2000 microns and at least a portion having a particle size of 180 microns or more. It is more than 90% of the total.
ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの安息角が２５〜３９°である。 The angle of repose of pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene is 25 to 39 °.
さらに、前記ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンＴＧＡの熱重量分析により、乾燥減量が１％以下である。 Further, by thermogravimetric analysis of the pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene TGA, the weight loss by drying is 1% or less.
前記ペレット状９，９−ビス［３−フェニル−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であって、
９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン溶液を、芳香族炭化水素溶媒で結晶化して、結晶中の残留溶媒の量が１０％〜３０％となるように遠心分離するステップ１と、
ステップ１で結晶化して得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン結晶体を、穴径１ｍｍ〜２ｍｍの造粒機により造粒するステップ２と、
ステップ２で得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを、真空オーブンで乾燥させ、ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを得るステップ３と、を含む。
The method for producing pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
A 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene solution is crystallized with an aromatic hydrocarbon solvent so that the amount of residual solvent in the crystal is 10% to 30%. Step 1 of centrifugation and
In step 2, the 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene crystal obtained by crystallizing in step 1 is granulated by a granulator having a hole diameter of 1 mm to 2 mm. ,
The 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in step 2 is dried in a vacuum oven and pelletized 9,9-bis [3-phenyl-4- (3-phenyl-4-). 2-Hydroxyethoxy) Phenyl] Includes step 3 to obtain fluorene.
さらに、前記芳香族炭化水素溶媒は、ベンゼン、トルエン、キシレン、及びメシチレンを含む。トルエンが好ましい。 Furthermore, the aromatic hydrocarbon solvent contains benzene, toluene, xylene, and mesitylene. Toluene is preferred.
さらに、前記真空オーブンの真空度が１３３〜４０００Ｐａ、乾燥温度が６０〜１２０℃、乾燥時間が１８〜４０時間である。 Further, the degree of vacuum of the vacuum oven is 133 to 4000 Pa, the drying temperature is 60 to 120 ° C., and the drying time is 18 to 40 hours.
さらに、前記造粒機は、振動造粒機である。 Further, the granulator is a vibration granulator.
従来技術に対して、本発明は、以下の有益な効果を有する。 The present invention has the following beneficial effects on the prior art.
本発明のペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンは、流動性が大幅に改善され、排出及び輸送が容易になり、壁に付着せずに完全に排出させることができ、工業的生産により適する。 The pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene of the present invention has greatly improved fluidity, facilitates discharge and transportation, and does not adhere to the wall. It can be completely discharged and is more suitable for industrial production.
以下の実施例にて具体的に説明する。ただし、本特許は、以下の実施例に限定されるものではない。 This will be specifically described in the following examples. However, this patent is not limited to the following examples.
（実施例１）
撹拌器、冷却管、滴下装置を内蔵した３０００Ｌの反応釜を用意した。反応釜に７５０キログラムのトルエン、１５０キログラムの９−フルオレノン、５４０キログラムのオルトフェニルフェノキシエタノール、１０キログラムの３−メルカプトプロピオン酸を加えた。６０分間内で、２８０キログラムの９５％硫酸を滴下した。反応温度を５０℃に維持して、５時間反応させた。
(Example 1)
A 3000 L reaction kettle containing a stirrer, a cooling pipe, and a dropping device was prepared. To the reaction vessel, 750 kg of toluene, 150 kg of 9-fluorenone, 540 kg of orthophenylphenoxyethanol, and 10 kg of 3-mercaptopropionic acid were added. Within 60 minutes, 280 kilograms of 95% sulfuric acid was added dropwise. The reaction temperature was maintained at 50 ° C. and the reaction was carried out for 5 hours.
反応終了後、反応液に１５００Ｌのトルエン、５００Ｌの水を加え、ｐＨが７になるまで複数回水洗し、次に−５℃に冷却して、遠心分離機で遠心分離した。湿った結晶体（約２０％トルエン含有）を、ふるいのメッシュが１〜２ミリメートルの振動造粒機で造粒し、次に、真空オーブンで乾燥させた。１３００Ｐａの真空条件、６０〜１２０℃で２６時間乾燥させ、安息角が３２．３°であり、粒子径分布が表１に示される通りであり、ＴＧＡ乾燥減量が０．２３％であるペレット状製品を得た（粒子径分析方法：ふるい分け法、粒度標準ふるい、標準ＧＢ／ＴＴ２１０．３−２００４参照）。 After completion of the reaction, 1500 L of toluene and 500 L of water were added to the reaction solution, washed with water multiple times until the pH reached 7, then cooled to −5 ° C. and centrifuged by a centrifuge. Wet crystals (containing about 20% toluene) were granulated on a vibrating granulator with a sieve mesh of 1-2 mm and then dried in a vacuum oven. Pellet-like with a vacuum condition of 1300 Pa, dried at 60-120 ° C. for 26 hours, an angle of repose of 32.3 °, a particle size distribution as shown in Table 1, and a TGA drying weight loss of 0.23%. A product was obtained (see particle size analysis method: sieving method, particle size standard sieving, standard GB / TT210.3-2004).
表１
（実施例２）
撹拌器、冷却管、滴下装置を内蔵した３０００Ｌの反応釜を用意した。反応釜に７５０キログラムのキシレン、１５０キログラムの９−フルオレノン、５４０キログラムのオルトフェニルフェノキシエタノール、１０キログラムの３−メルカプトプロピオン酸を加えた。６０分間内で、２８０キログラムの９５％硫酸を滴下した。反応温度を５０℃に維持して、５時間反応させた。
(Example 2)
A 3000 L reaction kettle containing a stirrer, a cooling pipe, and a dropping device was prepared. To the reaction vessel, 750 kg of xylene, 150 kg of 9-fluorenone, 540 kg of orthophenylphenoxyethanol, and 10 kg of 3-mercaptopropionic acid were added. Within 60 minutes, 280 kilograms of 95% sulfuric acid was added dropwise. The reaction temperature was maintained at 50 ° C. and the reaction was carried out for 5 hours.
反応終了後、反応液に１５００Ｌのキシレン、５００Ｌの水を加え、ｐＨが７になるまで複数回水洗し、次に−５℃に冷却して、遠心分離機で遠心分離した。湿った結晶体（約２０％キシレン含有）を、ふるいのメッシュが１〜２ミリメートルの振動造粒機で造粒し、次に、真空オーブンで乾燥させた。１３００Ｐａの真空条件、６０〜１２０℃で３２時間乾燥させ、安息角が３４．８°であり、粒子径分布が表２に示されるとおりであり、ＴＧＡ乾燥減量が０．２１％であるペレット状製品を得た（粒子径分析方法：ふるい分け法、粒度標準ふるい、標準ＧＢ／ＴＴ２１０．３−２００４参照）。 After completion of the reaction, 1500 L of xylene and 500 L of water were added to the reaction solution, washed with water several times until the pH reached 7, then cooled to −5 ° C. and centrifuged by a centrifuge. Wet crystals (containing about 20% xylene) were granulated on a vibrating granulator with a sieve mesh of 1-2 mm and then dried in a vacuum oven. Pellet-like with a vacuum condition of 1300 Pa, dried at 60-120 ° C. for 32 hours, an angle of repose of 34.8 °, a particle size distribution as shown in Table 2, and a TGA drying weight loss of 0.21%. A product was obtained (see particle size analysis method: sieving method, particle size standard sieving, standard GB / TT210.3-2004).
表２
（比較例１）
撹拌器、冷却管、滴下装置を内蔵した３０００Ｌの反応釜を用意した。反応釜に７５０キログラムのトルエン、１５０キログラムの９−フルオレノン、５４０キログラムのオルトフェニルフェノキシエタノール、１０キログラムの３−メルカプトプロピオン酸を加えた。６０分間内で、２８０キログラムの９５％硫酸を滴下した。反応温度を５０℃に維持して、５時間反応させた。
(Comparative Example 1)
A 3000 L reaction kettle containing a stirrer, a cooling pipe, and a dropping device was prepared. To the reaction vessel, 750 kg of toluene, 150 kg of 9-fluorenone, 540 kg of orthophenylphenoxyethanol, and 10 kg of 3-mercaptopropionic acid were added. Within 60 minutes, 280 kilograms of 95% sulfuric acid was added dropwise. The reaction temperature was maintained at 50 ° C. and the reaction was carried out for 5 hours.
反応終了後、反応液に１５００Ｌのトルエン、５００Ｌの水を加え、ｐＨが７になるまで複数回水洗し、次に−５℃に冷却して、結晶を遠心分離機で取り出した。湿った結晶体（約２０％トルエン含有）を、造粒機で処理せずに真空オーブンに入れて乾燥させた。１３００Ｐａの真空条件、６０〜８０℃で１０時間乾燥させ、ペレット状ではなく粉末状の製品を得た。その安息角が４１度であり、粒子径分布が表３に示されるとおりであり、乾燥減量が２．５％であった（粒子径分析方法：マルバーンゼータサイザー２０００、標準ＧＢ／Ｔ１９０７７−２０１６参照）。 After completion of the reaction, 1500 L of toluene and 500 L of water were added to the reaction solution, washed with water multiple times until the pH reached 7, then cooled to −5 ° C., and the crystals were taken out by a centrifuge. Wet crystals (containing about 20% toluene) were placed in a vacuum oven to dry without treatment with a granulator. The product was dried at 60 to 80 ° C. for 10 hours under a vacuum condition of 1300 Pa to obtain a powdery product instead of pellets. The angle of repose was 41 degrees, the particle size distribution was as shown in Table 3, and the dry weight loss was 2.5% (see particle size analysis method: Malvern Zetasizer 2000, standard GB / T 19077-2016). ).
表３
（比較例２）
撹拌器、冷却管、滴下装置を内蔵した３０００Ｌの反応釜を用意した。反応釜に７５０キログラムのトルエン、１５０キログラムの９−フルオレノン、５４０キログラムのオルトフェニルフェノキシエタノール、１０キログラムの３−メルカプトプロピオン酸を加えた。６０分間内で、２８０キログラムの９５％硫酸を滴下した。反応温度を５０℃に維持して、５時間反応させた。
(Comparative Example 2)
A 3000 L reaction kettle containing a stirrer, a cooling pipe, and a dropping device was prepared. To the reaction vessel, 750 kg of toluene, 150 kg of 9-fluorenone, 540 kg of orthophenylphenoxyethanol, and 10 kg of 3-mercaptopropionic acid were added. Within 60 minutes, 280 kilograms of 95% sulfuric acid was added dropwise. The reaction temperature was maintained at 50 ° C. and the reaction was carried out for 5 hours.
反応終了後、反応液に１５００Ｌのトルエンを加え１時間撹拌し、次に５００Ｌの水を加え、ｐＨが７になるまで複数回水洗し、１０００Ｌのメタノールを加えて７０℃まで昇温して２時間撹拌し、次に−５℃に冷却して、結晶を遠心分離機で取り出した。湿った結晶体（約２５％残留溶媒含有）を、真空オーブンに入れて乾燥させた。１３００Ｐａの真空条件、６０〜７０℃で１０時間乾燥させ、粉末状の製品を得た。その安息角が４５度であり、粒子径分布が表４に示されるとおりであり、乾燥減量が０．６％であった（粒子径分析方法：マルバーンゼータサイザー２０００、標準ＧＢ／Ｔ１９０７７−２０１６参照）。 After completion of the reaction, 1500 L of toluene was added to the reaction solution, and the mixture was stirred for 1 hour, then 500 L of water was added, washed with water multiple times until the pH reached 7, and 1000 L of methanol was added to raise the temperature to 70 ° C. 2 The mixture was stirred for hours, then cooled to −5 ° C. and the crystals were centrifuged. Wet crystals (containing about 25% residual solvent) were placed in a vacuum oven and dried. A powdered product was obtained by drying at 60 to 70 ° C. for 10 hours under a vacuum condition of 1300 Pa. The angle of repose was 45 degrees, the particle size distribution was as shown in Table 4, and the dry weight loss was 0.6% (see particle size analysis method: Malvern Zetasizer 2000, standard GB / T 19077-2016). ).
表４
本発明の重要な特性は、以下の通りである。 The important properties of the present invention are as follows.
１）本特許で得られるペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンは、安息角が２５〜３９°である。 1) The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in this patent has an angle of repose of 25 to 39 °.
安息角が５０°である場合、流動性が不十分である。ホッパー、材料貯蔵室などから排出されるのは困難である（中間の粉末のみが下方に排出され、キャビティ／「ブリッジ」を形成する）。従って、ホッパーや材料貯蔵室で製品を移動するとき、振動器などで改善する必要がある。また、輸送性が悪く、管路の詰まりを引き起こす恐れがあり、粉末が壁に付着して、完全に排出されない可能性がある。 If the angle of repose is 50 °, the fluidity is inadequate. It is difficult to drain from hoppers, material storage chambers, etc. (only intermediate powders are drained downwards to form cavities / "bridges"). Therefore, when moving the product in the hopper or the material storage room, it is necessary to improve it with a vibrator or the like. In addition, the transportability is poor, which may cause clogging of the pipeline, and the powder may adhere to the wall and not be completely discharged.
安息角が２５〜３９°である場合、製品の流動性及び輸送性が良好で、生産効率も高い。 When the angle of repose is 25 to 39 °, the fluidity and transportability of the product are good, and the production efficiency is also high.
安息角が安息角測定器で測定され、測定方法がＧＢ／Ｔ１６９１３．５−１９９７である。 The angle of repose is measured by an angle of repose measuring device, and the measuring method is GB / T16913.5-1997.
２）本特許で得られるペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンは、粒子径分布が１００ミクロン〜２０００ミクロンであり、粒子径が１８０ミクロン以上の部分が少なくとも、全体の９０％以上である。 2) The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in this patent has a particle size distribution of 100 microns to 2000 microns and a particle size of 180 microns or more. Part is at least 90% or more of the whole.
３）本特許で得られるペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンについて、ＴＧＡ−Ｑ５０熱重量分析計を使用して３００℃の熱重量分析を行ったところ、乾燥減量が１％以下である。 3) The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in this patent was subjected to thermogravimetric analysis at 300 ° C. using a TGA-Q50 thermogravimetric analyzer. As a result, the dry weight loss was 1% or less.
［付記］
［付記１］
ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンであって、粒子径分布が１００ミクロン〜２０００ミクロンであり、粒子径が１８０ミクロン以上の部分が少なくとも全体の９０％以上である、
ことを特徴とするペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン。
[Additional Notes]
[Appendix 1]
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene having a particle size distribution of 100 to 2000 microns and at least the entire portion having a particle size of 180 microns or more. 90% or more of
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
［付記２］
前記ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンＴＧＡの熱重量分析により、乾燥減量が１％以下である、
ことを特徴とする付記１に記載のペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン。
[Appendix 2]
According to the thermogravimetric analysis of the pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene TGA, the weight loss on drying is 1% or less.
The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to Appendix 1, wherein the fluorene is characterized by the above.
［付記３］
ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンであって、ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの安息角が２５〜３９°である、
ことを特徴とするペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン。
[Appendix 3]
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene and pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene The angle of repose is 25-39 °,
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
［付記４］
前記ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンＴＧＡの熱重量分析により、乾燥減量が１％以下である、
ことを特徴とする付記３に記載のペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン。
[Appendix 4]
According to the thermogravimetric analysis of the pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene TGA, the weight loss on drying is 1% or less.
The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to Appendix 3, wherein the fluorene is characterized by the above.
［付記５］
付記１〜４の何れか１つに記載のペレット状９，９−ビス［３−フェニル−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であって、
９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン溶液を、芳香族炭化水素溶媒で結晶化して、結晶中の残留溶媒の量が１０％〜３０％となるように遠心分離するステップ１と、
ステップ１で結晶化して得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン結晶体を、穴径１ｍｍ〜２ｍｍの造粒機により造粒するステップ２と、
ステップ２で得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを、真空オーブンで乾燥させ、ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを得るステップ３と、を含む、
ことを特徴とするペレット状９，９−ビス［３−フェニル−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。
[Appendix 5]
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to any one of Supplementary notes 1 to 4.
A 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene solution is crystallized with an aromatic hydrocarbon solvent so that the amount of residual solvent in the crystal is 10% to 30%. Step 1 of centrifugation and
In step 2, the 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene crystal obtained by crystallizing in step 1 is granulated by a granulator having a hole diameter of 1 mm to 2 mm. ,
The 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in step 2 is dried in a vacuum oven and pelletized 9,9-bis [3-phenyl-4- (3-phenyl-4- (". 2-Hydroxyethoxy) phenyl] fluorene, including step 3 and.
A method for producing pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
［付記６］
前記芳香族炭化水素溶媒は、ベンゼン、トルエン、キシレン、及びメシチレンを含み、トルエンが好ましい、
ことを特徴とする付記５に記載のペレット状９，９−ビス［３−フェニル−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。
[Appendix 6]
The aromatic hydrocarbon solvent contains benzene, toluene, xylene, and mesitylene, preferably toluene.
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to Appendix 5, wherein the fluorene is produced.
［付記７］
前記真空オーブンの真空度が１３３〜４０００Ｐａ、乾燥温度が６０〜１２０℃、乾燥時間が１８〜４０時間である、
ことを特徴とする付記５に記載のペレット状９，９−ビス［３−フェニル−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。
[Appendix 7]
The degree of vacuum of the vacuum oven is 133 to 4000 Pa, the drying temperature is 60 to 120 ° C., and the drying time is 18 to 40 hours.
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to Appendix 5, wherein the fluorene is produced.
［付記８］
前記造粒機は、振動造粒機である、
ことを特徴とする付記５に記載のペレット状９，９−ビス［３−フェニル−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。
[Appendix 8]
The granulator is a vibration granulator,
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to Appendix 5, wherein the fluorene is produced.
Claims (5)
前記ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの安息角が２５〜３９°であり、
ＴＧＡの熱重量分析により、乾燥減量が１％以下である、
ことを特徴とするペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン。 Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene having a particle size distribution of 100 to 2000 microns and at least the entire portion having a particle size of 180 microns or more. der 90% or more of is,
The pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene has an angle of repose of 25 to 39 °.
The TGA thermogravimetric analysis, loss on drying Ru der than 1%,
Pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン溶液を、芳香族炭化水素溶媒で結晶化して、結晶中の残留溶媒の量が１０％〜３０％となるように遠心分離するステップ１と、
ステップ１で結晶化して得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレン結晶体を、穴径１ｍｍ〜２ｍｍの造粒機により造粒するステップ２と、
ステップ２で得られた９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを、真空オーブンで乾燥させ、ペレット状９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンを得るステップ３と、を含み、
前記ステップ１の結晶化で使用される前記芳香族炭化水素溶媒は１種類であり、９，９−ビス［３−フェニル−４−（２−ヒドロキシエトキシ）フェニル］フルオレンの合成では、結晶化と同じ１種類の溶媒を使用し、
前記真空オーブンの真空度が１３３〜４０００Ｐａ、乾燥温度が６０〜１２０℃、乾燥時間が１８〜４０時間である、
ことを特徴とするペレット状９，９−ビス［３−フェニル−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。 The method for producing pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to claim 1.
A 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene solution is crystallized with an aromatic hydrocarbon solvent so that the amount of residual solvent in the crystal is 10% to 30%. Step 1 of centrifugation and
In step 2, the 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene crystal obtained by crystallizing in step 1 is granulated by a granulator having a hole diameter of 1 mm to 2 mm. ,
The 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene obtained in step 2 is dried in a vacuum oven and pelletized 9,9-bis [3-phenyl-4- (3-phenyl-4-). and step 3 to obtain the 2-hydroxyethoxy) phenyl] fluorene, only including,
The aromatic hydrocarbon solvent used in the crystallization of the step 1 is one kind, and in the synthesis of 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene, crystallization and the like. Using the same one solvent,
The degree of vacuum of the vacuum oven is 133 to 4000 Pa, the drying temperature is 60 to 120 ° C., and the drying time is 18 to 40 hours .
A method for producing pelletized 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene.
ことを特徴とする請求項２に記載のペレット状９，９−ビス［３−フェニル−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。 The aromatic hydrocarbon solvent is benzene, toluene, xylene, or mesitylene .
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to claim 2.
ことを特徴とする請求項２に記載のペレット状９，９−ビス［３−フェニル−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。 The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to claim 2.
ことを特徴とする請求項２乃至４のいずれか１項に記載のペレット状９，９−ビス［３−フェニル−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。 The granulator is a vibration granulator,
The method for producing pellet-shaped 9,9-bis [3-phenyl-4- (2-hydroxyethoxy) phenyl] fluorene according to any one of claims 2 to 4.
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