JPS62240676A - Production of 3,3',4,4'-benzophenonetetracarboxylic dianhydrided - Google Patents
Production of 3,3',4,4'-benzophenonetetracarboxylic dianhydridedInfo
- Publication number
- JPS62240676A JPS62240676A JP61083420A JP8342086A JPS62240676A JP S62240676 A JPS62240676 A JP S62240676A JP 61083420 A JP61083420 A JP 61083420A JP 8342086 A JP8342086 A JP 8342086A JP S62240676 A JPS62240676 A JP S62240676A
- Authority
- JP
- Japan
- Prior art keywords
- benzophenonetetracarboxylic
- reaction
- acetic anhydride
- group
- periodic table
- 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
- 238000004519 manufacturing process Methods 0.000 title description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims abstract description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 abstract description 9
- 230000000737 periodic effect Effects 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract description 3
- 239000000347 magnesium hydroxide Substances 0.000 abstract description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229940011182 cobalt acetate Drugs 0.000 abstract description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920001721 polyimide Polymers 0.000 abstract description 2
- 239000009719 polyimide resin Substances 0.000 abstract description 2
- 239000011592 zinc chloride Substances 0.000 abstract description 2
- 235000005074 zinc chloride Nutrition 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006557 surface reaction 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
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は微粉状の３．３’ 、４．４’ −ベンゾフ
ェノンテトラカルボン酸二無水物（以下ＢＴＤ＾という
）の製造法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing finely powdered 3.3',4.4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTD). .
ＢＴＤ＾はポリイミド樹脂原料、エポキシ樹脂硬化剤等
、種々の用途に利用されている。BTD^ is used for various purposes such as polyimide resin raw material and epoxy resin curing agent.
従来のＩＩＴＤへの製法としては、３．３’ 、４．４
’ −ベンゾフェノンテトラカルボン酸（以下ＢＴＣへ
という）を高温で加熱し、溶融状態で無水化する方法、
あるいはＢＴＣ＾と無水酢酸とを反応させる方法が知ら
れている。The conventional manufacturing method for IITD is 3.3', 4.4
' - A method of heating benzophenonetetracarboxylic acid (hereinafter referred to as BTC) at high temperature to anhydride it in a molten state,
Alternatively, a method is known in which BTC^ and acetic anhydride are reacted.
しかし、これらの方法においては、微粉状物を得るため
にそれぞれ得られたフレークあるいは粗結晶状のＢＴＤ
＾を更に粉砕機等で粉砕することが必要であった。However, in these methods, flakes or coarse crystalline BTD are used to obtain fine powder.
It was necessary to further crush the ^ with a crusher or the like.
本発明はこのような粉砕工程を必要とせずに微粉状のＩ
ＩＴＤ＾を得ることを目的とするものである。The present invention does not require such a pulverization process and can produce finely powdered I.
The purpose is to obtain ITD^.
即ち、本発明は３．３’、４．４° −ベンゾフェノン
テトラカルボン酸と無水酢酸とを反応させ３．３’。That is, the present invention reacts 3.3', 4.4°-benzophenone tetracarboxylic acid with acetic anhydride to produce 3.3'.
４．４” −ベンゾフェノンテトラカルボン酸二無水物
を製造するに際し、周期律表第■族及び第１族から選ば
れる１種以上の金属イオンの存在下で反応を行うことを
特徴とする微粉状３．３’ 、４゜４′ −ベンゾフ
ェノンテトラカルボン酸二無水物の製造法に関するもの
である。4.4''-Fine powder characterized in that the reaction is carried out in the presence of one or more metal ions selected from Groups Ⅰ and 1 of the Periodic Table when producing benzophenonetetracarboxylic dianhydride. 3.3', 4°4'-Benzophenone tetracarboxylic dianhydride production method.
本発明の方法において用いられる周期律表第■族及び第
１族の金属イオンは、硝酸塩、酢酸塩あるいは水酸化物
、塩化物として使用される。The metal ions of Groups 1 and 1 of the periodic table used in the method of the present invention are used in the form of nitrates, acetates, hydroxides, and chlorides.
反応に際してはＢＴＣＡに対して無水酢酸（以下ＡＡと
いう）を２倍モル以上、好ましくは２．５〜４．５倍モ
ル使用するが、場合によっては溶媒として酢酸を使用し
ても良い。In the reaction, acetic anhydride (hereinafter referred to as AA) is used in an amount of at least 2 times the mole of BTCA, preferably 2.5 to 4.5 times, but acetic acid may be used as a solvent in some cases.
反応方法はＢＴＣＡとＡＡを仕込んだ後、室温から昇温
を開始し、７０〜１３０℃に昇温する。昇温速度は特に
制限は無いが１．０〜１．５時間でも十分である。In the reaction method, after charging BTCA and AA, heating is started from room temperature and then raised to 70 to 130°C. There is no particular restriction on the heating rate, but 1.0 to 1.5 hours is sufficient.
触媒の使用方法はその種類によって異なるが、例えばＭ
ｇ（Ｏｉｌ）ｚの場合、固体状態でも昇温直前の添加で
十分その効果を発揮する。硝酸コバルトの場合は酢酸あ
るいはＡＡ等に溶解して添加するか、固体状態で添加す
る場合は数時間攪拌した後、昇温する必要が有る。The method of using the catalyst varies depending on its type, but for example, M
In the case of g(Oil)z, even in a solid state, its effect is sufficiently exerted by adding it just before the temperature rises. In the case of cobalt nitrate, it must be added after being dissolved in acetic acid or AA, or if it is added in a solid state, it must be stirred for several hours and then heated.
触媒の使用量は、反応系中の濃度が１０ｐｐｍ以上有れ
ば良く特に上限は無いが、２００ｐｐｍ以上の添加は不
必要である。There is no particular upper limit to the amount of catalyst used as long as the concentration in the reaction system is 10 ppm or more, but addition of 200 ppm or more is unnecessary.
ｒｌＴｃＡと面の反応よりＢＴＤＡを得る際に、無触媒
の場合、通常は平均粒子径１００μ以上の粒度分布を持
つものが得られるが、本発明の方法により、触媒を使用
した場合、平均粒子径１０〜３０μのＢＴＤＡが得られ
る。これは通常品をハンマーミルで粉砕したものと同等
の粒度であり、粉砕工程なしでも微粉状のＢＴＤＡが得
られる。When BTDA is obtained from the surface reaction with rlTcA, if no catalyst is used, a particle size distribution with an average particle size of 100μ or more is usually obtained, but when a catalyst is used according to the method of the present invention, the average particle size is A BTDA of 10-30μ is obtained. This particle size is equivalent to that of a regular product pulverized with a hammer mill, and fine powder BTDA can be obtained without the pulverization step.
以下に実施例を挙げて本発明の詳細な説明するが、本発
明はこれらに限定されるものではない。The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.
比較例
ＢＴＣＡ１５０ｇ及び無水酢酸１８４ｇをフラスコに秤
り込み１５０ｒｐｍの攪拌速度で１時間で１０５℃に昇
温し、その後４時間、１０５℃を保った後、２５℃まで
冷却した。反応スラリーを濾過し、得られた湿結晶を減
圧乾燥した。得られた結晶の粒度分布を第３図に示す。Comparative Example 150 g of BTCA and 184 g of acetic anhydride were weighed into a flask, and the temperature was raised to 105°C in 1 hour at a stirring speed of 150 rpm. After that, the temperature was maintained at 105°C for 4 hours, and then cooled to 25°C. The reaction slurry was filtered, and the obtained wet crystals were dried under reduced pressure. The particle size distribution of the obtained crystals is shown in FIG.
尚、粒度分布はコールタ−カウンターＴＡ■型を用いて
測定した。平均粒子径は１１５μであり、嵩密度は０．
７５ｇ／ｍｌであった。Incidentally, the particle size distribution was measured using a Coulter Counter TA type. The average particle diameter is 115μ, and the bulk density is 0.
It was 75g/ml.
また顕微鏡写真を第４図に示す。Further, a micrograph is shown in Fig. 4.
実施例１
ＢＴＣＡ１５０ｇ、無水酢酸１８４ｇおよび酢酸コバル
ト９ｍｇをフラスコに秤り込み室温で４時間攪拌した後
、比較例と同じ方法で実験を行った。得られた結晶の粒
度分布を第１図に、ａｉｍ鏡写真を第２図に示す。平均
粒子径は１９．７μで嵩密度は０．４５ｇ／ｍｌであっ
た。又、硝酸ニッケル１５ｍｇを用いて同様に反応した
ところ、得られた結晶の平均粒子径は２０．５μであっ
た。Example 1 150 g of BTCA, 184 g of acetic anhydride, and 9 mg of cobalt acetate were weighed into a flask and stirred at room temperature for 4 hours, and then an experiment was conducted in the same manner as in the comparative example. The particle size distribution of the obtained crystals is shown in Fig. 1, and the aim mirror photograph is shown in Fig. 2. The average particle diameter was 19.7μ and the bulk density was 0.45g/ml. Further, when a similar reaction was carried out using 15 mg of nickel nitrate, the average particle size of the obtained crystals was 20.5 μm.
実施例２
実施例１と同様の方法で室温での攪拌を２０時間行った
。得られた結晶の平均粒子径は１４．２μであった。Example 2 Stirring at room temperature was performed for 20 hours in the same manner as in Example 1. The average particle diameter of the obtained crystals was 14.2μ.
実施例３
比較例と同様の方法で水酸化マグネシウムを２５ｍｇ添
加して反応を行った。得られた結晶の嵩密度は０．３９
ｇ／ｍｌで実施例１で得られた結晶より更に細かな粒度
分布を有していた。Example 3 A reaction was carried out in the same manner as in the comparative example by adding 25 mg of magnesium hydroxide. The bulk density of the obtained crystal is 0.39
It had a finer particle size distribution than the crystals obtained in Example 1 in terms of g/ml.
実施例４
無水塩化亜鉛を３０ａ＋ｇ添加した他は比較例と同様の
反応を行った。得られた結晶の嵩密度は０．３９ｇ／ｍ
ｌで、粒度分布は水酸化マグネシウムを使用した場合（
実施例３）と同程度であった。Example 4 The same reaction as in Comparative Example was carried out except that 30a+g of anhydrous zinc chloride was added. The bulk density of the obtained crystals was 0.39 g/m
l, and the particle size distribution is as follows when using magnesium hydroxide (
It was comparable to Example 3).
第１図、第２図はそれぞれ実施例１で得られた結晶の粒
度分布、顕微鏡写真を示し、第３図、第４図はそれぞれ
比較例で得られた結晶の粒度分布、顕微鏡写真を示す。
第５図は第２図、第４図の写真の倍率を示す図である。Figures 1 and 2 respectively show the particle size distribution and micrograph of the crystal obtained in Example 1, and Figures 3 and 4 respectively show the particle size distribution and micrograph of the crystal obtained in Comparative Example. . FIG. 5 is a diagram showing the magnification of the photographs in FIGS. 2 and 4.
Claims (1)
と無水酢酸とを反応させ３，３’，４，４′−ベンゾフ
ェノンテトラカルボン酸二無水物を製造するに際し、周
期律表第II族及び第VIII族から選ばれる１種以上の金属
イオンの存在下で反応を行うことを特徴とする微粉状３
，３′，４，４′−ベンゾフェノンテトラカルボン酸二
無水物の製造法。When producing 3,3',4,4'-benzophenonetetracarboxylic dianhydride by reacting 3,3',4,4'-benzophenonetetracarboxylic acid and acetic anhydride, Fine powder 3 characterized in that the reaction is carried out in the presence of one or more metal ions selected from Group VIII
, 3',4,4'-benzophenonetetracarboxylic dianhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61083420A JPH0631203B2 (en) | 1986-04-11 | 1986-04-11 | Method for producing 3,3 '", 4,4"'-benzophenone tetracarboxylic dianhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61083420A JPH0631203B2 (en) | 1986-04-11 | 1986-04-11 | Method for producing 3,3 '", 4,4"'-benzophenone tetracarboxylic dianhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62240676A true JPS62240676A (en) | 1987-10-21 |
| JPH0631203B2 JPH0631203B2 (en) | 1994-04-27 |
Family
ID=13801943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61083420A Expired - Lifetime JPH0631203B2 (en) | 1986-04-11 | 1986-04-11 | Method for producing 3,3 '", 4,4"'-benzophenone tetracarboxylic dianhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0631203B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060300A (en) * | 2003-08-12 | 2005-03-10 | Mitsubishi Rayon Co Ltd | Method for producing carboxylic acid anhydride |
-
1986
- 1986-04-11 JP JP61083420A patent/JPH0631203B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060300A (en) * | 2003-08-12 | 2005-03-10 | Mitsubishi Rayon Co Ltd | Method for producing carboxylic acid anhydride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0631203B2 (en) | 1994-04-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |