JPH0522693B2 - - Google Patents
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- Publication number
- JPH0522693B2 JPH0522693B2 JP59241799A JP24179984A JPH0522693B2 JP H0522693 B2 JPH0522693 B2 JP H0522693B2 JP 59241799 A JP59241799 A JP 59241799A JP 24179984 A JP24179984 A JP 24179984A JP H0522693 B2 JPH0522693 B2 JP H0522693B2
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- JP
- Japan
- Prior art keywords
- yield
- reaction
- except
- carried out
- same manner
- 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.)
- Expired - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 claims description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- -1 bisphenol compound Chemical class 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PMMUFDGWDXRPRQ-UHFFFAOYSA-N 2-hydroxy-5-[2-(4-hydroxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=C(O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(O)C=C1 PMMUFDGWDXRPRQ-UHFFFAOYSA-N 0.000 description 1
- ZGJWAHZJNZJTNH-UHFFFAOYSA-N 5-[2-(3-carboxy-4-hydroxyphenyl)propan-2-yl]-2-hydroxybenzoic acid Chemical compound C=1C=C(O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(O)C(C(O)=O)=C1 ZGJWAHZJNZJTNH-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Description
（産業上の利用分野）
本発明は、ビスフエノール類化合物の製造方法
に関するものである。
（従来の技術）
近年、熱的特性をはじめ機械的特性など各種物
性に優れたポリマーがプラスチツクの分野で広く
使用されていることはよく知られており、芳香族
ジカルボン酸とビスフエノール化合物から得られ
る芳香族ポリエステルも、その一つである。
ここで、芳香族ポリエステルを得るために使用
されているビスフエノール化合物の誘導体とて構
造式
(Industrial Application Field) The present invention relates to a method for producing bisphenol compounds. (Prior art) It is well known that in recent years, polymers with excellent physical properties such as thermal and mechanical properties have been widely used in the field of plastics. One such example is aromatic polyester. Here, the structural formula of the derivative of the bisphenol compound used to obtain the aromatic polyester is
【式】で示さ
れる化合物の誘導体で構造式
で示される化合物や、構造式
A derivative of the compound represented by [formula] with the structural formula Compounds represented by or structural formula
本発明における炭酸アルカリ化合物としては、
炭酸ナトリウム、炭酸カリウム、炭酸リチウム、
炭酸セシウムなどが用いられるが、特に炭酸カリ
ウムが好適に用いられる。
また、式〔〕で示されるBPの具体例として
は、２，２−ビス（４−ヒドロキシフエニル）プ
ロパンおよび４，4′−ジヒドロキシジフエニル、
２，2′−ジヒドロキシジフエニルなどがあげられ
る。
次に、BP、二酸化炭素及び炭酸アルカリ化合
物の仕込時のモル比は、通常BP1モルに対して二
酸化炭素は１〜10倍モル、とくに３〜８倍モル、
さらには４〜６倍モル程度が好ましく、炭酸アル
カリ化合物は0.5〜20倍モル、とくに１〜10倍モ
ル、さらには２〜６倍モルが好ましい。
反応はオートクレーブ中で行うのが好適であ
り、その際の反応温度は120〜220℃である必要が
ある。120℃未満では反応はほとんど進まず、ま
た220℃をこえると分解が起こりともに好ましく
ない。
反応圧力は１Kg／cm2以上が必要であり、１Kg／
cm2未満では反応はほとんど進行せず好ましくな
い。反応圧力が30Kg／cm2以上では反応速度は飽和
状態となるので通常30Kg／cm2程度で反応させるの
が好適である。
この反応は条件によつて選択性があり、比較的
低温、低圧ではカルボキシル基が１個、高温、高
圧では２個置換した化合物が選択的に生成するの
で、目的に応じて反応条件を定めればよい。
本発明における反応時間は通常数十分〜数時
間、好ましくは１〜６時間、最適には１〜４時間
である。
また、反応中は撹拌混合しつつ反応するのが好
適で撹拌速度は100〜500rpmもあれば十分であ
る。
（実施例）
以下、実施例をあげて本発明をさらに詳しく説
明する。
実施例 １
300c.c.のオートクレーブに２，２−ビス（４−
ヒドロキシフエニル）プロパン（以下BAと略称
する。）0.3モル（68.4ｇ）、炭酸カリウム0.9モル
（124.2ｇ）を仕込み、オートクレーブ内部を二酸
化炭素で二度置換した後、オートクレーブ内部の
圧力が30Kg／cm2になるように二酸化炭素で加圧し
た。その後160℃まで昇温し、160℃に達してから
２時間反応させた。反応終了後20℃に冷却し反応
生成物を取り出した。次いで、水を300c.c.加え撹
拌後、固体分を過で除き、液を希硫酸でPH２
以下にして白色結晶の生成物を得た。
この生成物の収量は90.4ｇであり、赤外線吸収
スペクトルの3.40μ、5.95μ、6.95μ、8.20μ等の吸
収、また第１図の核磁気共鳴スペクトル、第１表
の元素分析の結果から、２，２−ビス（３−カル
ボキシ−４−ヒドロキシフエニル）プロパン（以
下BA−2Cと略称する。）であることがわかつた。
よつて得られたBA−2Cの収率はBAの仕込みモ
ル数に対し95.4％であつた。また、同時に２−
（３−カルボキシ４−ヒドロキシフエニル）−２−
（4′−ヒドロキシフエニル）プロパン（以下BA−
1Cと略称する。）が2.3％得られた。
実施例 ２
反応温度を150℃にした以外は実施例１と全く
同様に反応を行つた結果、BA−2Cの収量は58.6
ｇであり、収率は61.7％であつた。また、BA−
1Cの収率は24.3％であつた。
実施例 ３
反応温度を180℃にした以外は実施例１と全く
同様に反応を行つた結果、BA−2Cの収量は64.9
ｇであり、収率は68.4％であつた。BA−1Cの収
率は0.9％であつた。
実施例 ４
反応圧力を20Kg／cm2にした以外は実施例１と全
く同様に反応を行つた結果、BA−2Cの収量は
57.3ｇで、収率は60.4％であつた。またBA−1C
の収率は11.3％であつた。
比較例 １
反応温度を100℃にした以外は実施例１と全く
同様に反応を行つた結果、BA−2Cの収量は12.6
ｇで、収率は13.3％であつた。またBA−1Cの収
率は14.4％であつた。
比較例 ２
反応温度を230℃にした以外は実施例１と全く
同様に反応を行つた結果、BA−2Cの収量は13.9
ｇで、収率は14.6％であつた。またBA−1Cの収
率は0.5％であつた。
比較例 ３
反応圧力を0.5Kg／cm2にした以外は実施例１と
全く同様に反応を行つた結果、BA−2Cの収量は
8.6ｇで、収率は9.0％であつた。また、BA−1C
の収率は10.6％であつた。
実施例 ５
BAを0.08モル（18.2ｇ）、炭酸カリウムを1.25
モル（172.5ｇ）にした以外は実施例１と全く同
様に反応を行つた結果、BA−2Cの収量は21.9ｇ
で、収率は86.8％であつた。またBA−1Cの収率
は9.1％であつた。
実施例 ６
BAを0.29モル（66.1ｇ）、炭酸カリウムを0.88
モル（121.4ｇ）にした以外は実施例１と全く同
様に反応を行つた結果、BA−2Cの収量は78.4ｇ
で、収率は85.5％であつた。またBA−1Cの収率
は8.9％であつた。
実施例 ７
アルカリ金属化合物として炭酸ナトリウムを用
い、その仕込み量を0.9モル（95.4ｇ）とした以
外は実施例１と全く同様に反応を行つた結果、
BA−2Cの収量は61.9ｇで、収率は67.5％であつ
た。またBA−1Cの収率は12.2％であつた。
実施例 ８
BAを0.11モル（25.1ｇ）、炭酸カリウムを0.72
モル（99.4ｇ）、反応圧力を15Kg／cm2、反応温度
を135℃にした以外は実施例１と全く同様に反応
を行つた。その結果、白色結晶の生成物が26.3ｇ
得られ、この生成物は赤外線吸収スペクトルの
3.45μ、5.95μ、6.62μ、6.95μ、8.20μ等の吸収、ま
た第２表の元素分析の結果から、BA−1Cである
ことがわかつた。よつて、得られたBA−1Cの収
率はBAの仕込みモル数に対し87.9％であつた。
またBA−2Cの収率は9.9％であつた。
実施例 ９
反応温度を150℃にした以外は実施例８と全く
同様に反応を行つた結果、BA−1Cの収量は16.2
ｇで、収率は54.0％であつた。またBA−2Cの収
率は38.8％であつた。
実施例 10
反応温度を120℃にした以外は実施例８と全く
同様に反応を行つた結果、BA−1Cの収量は19.6
ｇで、収率は65.3％であつた。またBA−2Cの収
率は11.1％であつた。
実施例 11
反応圧力を20Kg／cm2にした以外は実施例８と全
く同様に反応を行つた結果、BA−1Cの収量は
14.9ｇで、収率は49.6％であつた。またBA−2C
の収率は16.3％であつた。
実施例 12
反応圧力を１Kg／cm2にした以外は実施例８と全
く同様に反応を行つた結果、BA−1Cの収量は
19.9ｇで、収率は66.2％であつた。またBA−2C
の収率は2.1％であつた。
比較例 ４
反応温度を100℃にした以外は実施例８と全く
同様に反応を行つた結果、BA−1Cの収量は2.6
ｇで、収率は8.6％であつた。またBA−2Cの収
率は0.8％であつた。
比較例 ５
反応温度を230℃にした以外は実施例８と全く
同様に反応を行つた結果、BA−1Cの収量は4.0
ｇで、収率は13.2％であつた。またBA−2Cの収
率は14.3％であつた。
比較例 ６
反応温度を110℃、反応圧力を30Kg／cm2にした
以外は実施例８と全く同様に反応を行つた結果、
BA−1Cの収量は4.2ｇで、収率は13.9％であつ
た。またBA−2Cの収率は4.3％であつた。
比較例 ７
反応圧力を0.5Kg／cm2にした以外は実施例８と
全く同様に反応を行つた結果、BA−1Cの収量は
2.2ｇで、収率は7.3％であつた。またBA−2Cの
収率は0.6％であつた。
実施例 13
300c.c.のオートクレーブに4.4′−ジヒドロキシ
ジフエニル（以下4.4′−DHPと略称する。）0.3モ
ル（5.59ｇ）、炭酸カリウム0.9モル（124.2ｇ）を
仕込み、オートクレーブ内部を二酸化炭素で二度
置換した後、オートクレーブ内部の圧力が30Kg／
cm2になるように二酸化炭素で加圧した。その後
180℃まで昇温し、180℃に達してから２時間反応
させた。反応終了後20℃に冷却し、反応生成物を
取り出した。次いで、水を300c.c.加え撹拌後、固
体分を過で除き、液を希硫酸でPH２以下にし
て白色結晶の生成物を得た。
この生成物の収量は77.4ｇであり、赤外線吸収
スペクトルの3.30μ、5.98μ、6.70μ、8.00μ等の吸
収、また第３表の元素分析の結果から、4.4′−ジ
ヒドロキシ−３，3′−ジカルボキシジフエニル
（以下4.4′−DHP−2Cと略称する。）であること
がわかつた。よつて、得られた4.4′−DHP−2C
の収率は4.4′−DHPの仕込みモル数に対し94.1％
であつた。また同時に、4.4′−ジヒドロキシ−３
−カルボキシジフエニルが1.8％得られた。
実施例 14
300c.c.のオートクレーブに２，2′−ジヒドロキ
シジフエニル（以下２，2′−DHPと略称する。）
0.3モル（55.9ｇ）、炭酸カリウム0.9モル（124.2
ｇ）を仕込み、オートクレーブ内部を二酸化炭素
で二度置換した後、オートクレーブ内部の圧力が
30Kg／cm2になるように二酸化炭素で加圧した。そ
の後180℃まで昇温し、180℃に達してから２時間
反応させた。反応終了後20℃に冷却し、反応生成
物を取り出した。次いで、水を300c.c.加え撹拌後、
固体分を過で除き、液を希硫酸でPH２以下に
して白色結晶の生成物を得た。
この生成物の収量は73.2ｇであり、赤外線吸収
スペクトルの3.49μ、6.20μ、6.85μ、11.95μ等の吸
収、また第４表の元素分析の結果から、２，2′−
ジヒドロキシ−３，3′−ジカルボキシジフエニル
であることがわかつた。よつて、得られた２，
2′−DHP−2Cの収率は２，2′−DHPの仕込みモ
ル数に対し88.4％であつた。また同時に、２，
2′−ジヒドロキシ−３−カルボキシジフエニルが
3.6％得られた。
（発明の効果）
本発明は、熱的特性や機械的特性等、各種物性
にすぐれた芳香族ポリエステルを製造するに際
し、極めて良好な結果をもたらす原料であるビス
フエノール類化合物を工業的に、安全性、操業性
あるいは経済性よく製造しうる方法である。
As the alkali carbonate compound in the present invention,
Sodium carbonate, potassium carbonate, lithium carbonate,
Although cesium carbonate and the like are used, potassium carbonate is particularly preferably used. Further, specific examples of BP represented by the formula [] include 2,2-bis(4-hydroxyphenyl)propane and 4,4'-dihydroxydiphenyl,
Examples include 2,2'-dihydroxydiphenyl. Next, the molar ratio of BP, carbon dioxide, and alkali carbonate compound at the time of preparation is usually 1 to 10 times the mole of carbon dioxide, especially 3 to 8 times the mole of carbon dioxide to 1 mole of BP.
More preferably, the amount is about 4 to 6 times the mole, and the alkali carbonate compound is preferably 0.5 to 20 times the mole, particularly 1 to 10 times the mole, and even more preferably 2 to 6 times the mole. The reaction is preferably carried out in an autoclave, and the reaction temperature at that time needs to be 120 to 220°C. At temperatures below 120°C, the reaction hardly progresses, and at temperatures above 220°C, decomposition occurs, both of which are undesirable. The reaction pressure needs to be 1Kg/cm2 or more ;
If it is less than cm 2 , the reaction will hardly proceed, which is not preferable. If the reaction pressure is 30 Kg/cm 2 or more, the reaction rate will reach a saturated state, so it is usually preferable to carry out the reaction at about 30 Kg/cm 2 . This reaction is selective depending on the conditions; at relatively low temperatures and low pressures, compounds with one carboxyl group are selectively produced, while at high temperatures and pressures, compounds with two substituted carboxyl groups are selectively produced, so the reaction conditions must be determined depending on the purpose. Bye. The reaction time in the present invention is usually several tens of minutes to several hours, preferably 1 to 6 hours, most preferably 1 to 4 hours. Further, during the reaction, it is preferable to carry out the reaction while stirring and mixing, and a stirring speed of 100 to 500 rpm is sufficient. (Example) Hereinafter, the present invention will be explained in more detail by giving examples. Example 1 2,2-bis (4-
After charging 0.3 mol (68.4 g) of hydroxyphenyl)propane (hereinafter abbreviated as BA) and 0.9 mol (124.2 g) of potassium carbonate and purging the inside of the autoclave twice with carbon dioxide, the pressure inside the autoclave reached 30 kg/ It was pressurized with carbon dioxide to a volume of cm2 . Thereafter, the temperature was raised to 160°C, and after reaching 160°C, the reaction was continued for 2 hours. After the reaction was completed, it was cooled to 20°C and the reaction product was taken out. Next, 300 c.c. of water was added and stirred, the solid content was removed by filtration, and the liquid was adjusted to pH 2 with dilute sulfuric acid.
A white crystal product was obtained as follows. The yield of this product was 90.4 g, and from the infrared absorption spectrum of 3.40μ, 5.95μ, 6.95μ, 8.20μ, etc., the nuclear magnetic resonance spectrum in Figure 1, and the elemental analysis results in Table 1, It was found to be 2,2-bis(3-carboxy-4-hydroxyphenyl)propane (hereinafter abbreviated as BA-2C).
The yield of BA-2C thus obtained was 95.4% based on the number of moles of BA charged. Also, at the same time 2-
(3-carboxy4-hydroxyphenyl)-2-
(4'-Hydroxyphenyl)propane (BA-
Abbreviated as 1C. ) was obtained by 2.3%. Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 150°C. As a result, the yield of BA-2C was 58.6
g, and the yield was 61.7%. Also, BA-
The yield of 1C was 24.3%. Example 3 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 180°C. As a result, the yield of BA-2C was 64.9
g, and the yield was 68.4%. The yield of BA-1C was 0.9%. Example 4 The reaction was carried out in the same manner as in Example 1 except that the reaction pressure was 20 Kg/cm 2 . As a result, the yield of BA-2C was
The amount was 57.3g, and the yield was 60.4%. Also BA−1C
The yield was 11.3%. Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 100°C. As a result, the yield of BA-2C was 12.6
g, yield was 13.3%. Moreover, the yield of BA-1C was 14.4%. Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 230°C. As a result, the yield of BA-2C was 13.9
g, yield was 14.6%. Moreover, the yield of BA-1C was 0.5%. Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that the reaction pressure was 0.5 Kg/cm 2 . As a result, the yield of BA-2C was
The yield was 9.0% at 8.6 g. Also, BA−1C
The yield was 10.6%. Example 5 0.08 mol (18.2 g) of BA, 1.25 mol of potassium carbonate
The reaction was carried out in exactly the same manner as in Example 1 except that the amount was changed to mol (172.5 g). As a result, the yield of BA-2C was 21.9 g.
The yield was 86.8%. Moreover, the yield of BA-1C was 9.1%. Example 6 0.29 mol (66.1 g) of BA, 0.88 potassium carbonate
The reaction was carried out in exactly the same manner as in Example 1 except that the amount was changed to mol (121.4 g). As a result, the yield of BA-2C was 78.4 g.
The yield was 85.5%. Moreover, the yield of BA-1C was 8.9%. Example 7 A reaction was carried out in exactly the same manner as in Example 1, except that sodium carbonate was used as the alkali metal compound and the amount charged was 0.9 mol (95.4 g).
The yield of BA-2C was 61.9 g, and the yield was 67.5%. Moreover, the yield of BA-1C was 12.2%. Example 8 0.11 mol (25.1 g) of BA, 0.72 mol of potassium carbonate
The reaction was carried out in exactly the same manner as in Example 1, except that the mole (99.4 g), the reaction pressure was 15 Kg/cm 2 , and the reaction temperature was 135°C. As a result, 26.3g of white crystalline product
This product has an infrared absorption spectrum of
From the absorptions of 3.45μ, 5.95μ, 6.62μ, 6.95μ, 8.20μ, etc., and the results of elemental analysis shown in Table 2, it was found to be BA-1C. Therefore, the yield of BA-1C obtained was 87.9% based on the number of moles of BA charged.
Moreover, the yield of BA-2C was 9.9%. Example 9 The reaction was carried out in the same manner as in Example 8 except that the reaction temperature was 150°C. As a result, the yield of BA-1C was 16.2
g, yield was 54.0%. Moreover, the yield of BA-2C was 38.8%. Example 10 The reaction was carried out in the same manner as in Example 8 except that the reaction temperature was 120°C. As a result, the yield of BA-1C was 19.6
g, yield was 65.3%. Moreover, the yield of BA-2C was 11.1%. Example 11 The reaction was carried out in the same manner as in Example 8 except that the reaction pressure was 20 Kg/cm 2 . As a result, the yield of BA-1C was
The yield was 49.6% at 14.9g. Also BA-2C
The yield was 16.3%. Example 12 The reaction was carried out in the same manner as in Example 8 except that the reaction pressure was 1 Kg/cm 2 . As a result, the yield of BA-1C was
The amount was 19.9g, and the yield was 66.2%. Also BA-2C
The yield was 2.1%. Comparative Example 4 The reaction was carried out in the same manner as in Example 8 except that the reaction temperature was 100°C. As a result, the yield of BA-1C was 2.6
g, yield was 8.6%. Moreover, the yield of BA-2C was 0.8%. Comparative Example 5 The reaction was carried out in the same manner as in Example 8 except that the reaction temperature was 230°C. As a result, the yield of BA-1C was 4.0
g, yield was 13.2%. Moreover, the yield of BA-2C was 14.3%. Comparative Example 6 The reaction was carried out in exactly the same manner as in Example 8 except that the reaction temperature was 110°C and the reaction pressure was 30Kg/cm 2 .
The yield of BA-1C was 4.2 g, and the yield was 13.9%. Moreover, the yield of BA-2C was 4.3%. Comparative Example 7 The reaction was carried out in the same manner as in Example 8 except that the reaction pressure was 0.5 Kg/cm 2 . As a result, the yield of BA-1C was
The yield was 7.3% at 2.2g. Moreover, the yield of BA-2C was 0.6%. Example 13 0.3 mol (5.59 g) of 4.4'-dihydroxydiphenyl (hereinafter abbreviated as 4.4'-DHP) and 0.9 mol (124.2 g) of potassium carbonate were placed in a 300 c.c. autoclave, and the inside of the autoclave was filled with carbon dioxide. After replacing the autoclave twice with
It was pressurized with carbon dioxide to a volume of cm2 . after that
The temperature was raised to 180°C, and after reaching 180°C, the reaction was continued for 2 hours. After the reaction was completed, it was cooled to 20°C and the reaction product was taken out. Next, 300 c.c. of water was added and after stirring, the solid content was removed by filtration, and the liquid was adjusted to pH 2 or less with dilute sulfuric acid to obtain a white crystal product. The yield of this product was 77.4 g, and from the infrared absorption spectra of 3.30μ, 5.98μ, 6.70μ, 8.00μ, etc., and the results of elemental analysis in Table 3, 4.4′-dihydroxy-3,3′ -dicarboxydiphenyl (hereinafter abbreviated as 4.4'-DHP-2C). Therefore, the obtained 4.4′−DHP−2C
The yield is 94.1% based on the number of moles of 4.4′-DHP charged.
It was hot. At the same time, 4,4'-dihydroxy-3
-1.8% carboxydiphenyl was obtained. Example 14 2,2'-dihydroxydiphenyl (hereinafter abbreviated as 2,2'-DHP) was placed in a 300 c.c. autoclave.
0.3 mol (55.9 g), potassium carbonate 0.9 mol (124.2
After charging g) and replacing the inside of the autoclave with carbon dioxide twice, the pressure inside the autoclave is
It was pressurized with carbon dioxide to a pressure of 30 kg/cm 2 . Thereafter, the temperature was raised to 180°C, and after reaching 180°C, the reaction was continued for 2 hours. After the reaction was completed, it was cooled to 20°C and the reaction product was taken out. Next, after adding 300 c.c. of water and stirring,
The solid content was removed by filtration, and the liquid was adjusted to pH 2 or less with dilute sulfuric acid to obtain a white crystal product. The yield of this product was 73.2 g, and from the infrared absorption spectra of 3.49μ, 6.20μ, 6.85μ, 11.95μ, etc., and the results of elemental analysis in Table 4, 2,2'-
It was found to be dihydroxy-3,3'-dicarboxydiphenyl. Therefore, the obtained 2,
The yield of 2'-DHP-2C was 88.4% based on the number of moles of 2,2'-DHP charged. At the same time, 2,
2'-dihydroxy-3-carboxydiphenyl
3.6% was obtained. (Effects of the Invention) The present invention provides industrial and safe use of bisphenol compounds, which are raw materials that produce extremely good results when producing aromatic polyesters with excellent physical properties such as thermal properties and mechanical properties. This is a method that can be manufactured with good efficiency, operability, and economy.
【表】【table】
【表】【table】
【表】【table】
第１図は実施例１で得られた生成物の核磁気共
鳴スペクトルを示す。
FIG. 1 shows the nuclear magnetic resonance spectrum of the product obtained in Example 1.
Claims (1)
化合物と二酸化炭素から、下記一般式〔〕で示
されるビスフエノール類化合物を製造するに際
し、反応系に炭酸アルカリ化合物を存在させ、実
質的に水および有機溶剤を添加することなく、か
つ、下記式〔〕および〔〕を満足する条件で
反応させることを特徴とするビスフエノール類化
合物の製造方法。 （式中、Ｒは−Ｃ（CH3）2−を表し、ｋは０また
は１の整数である。） （式中、Ｒおよびｋは式〔〕と同じであり、
ｎ、ｍは整数で、かつ、ｎ＋ｍが１または２であ
る。） 120≦Ｔ≦220 〔〕 １≦Ｐ 〔〕 〔ただし、Ｔは反応温度（℃）であり、Ｐは反応
圧力（Kg／cm2）である。〕[Claims] 1. When producing a bisphenol compound represented by the following general formula [] from a bisphenol compound represented by the following general formula [] and carbon dioxide, an alkali carbonate compound is present in the reaction system, 1. A method for producing bisphenol compounds, which comprises reacting substantially without adding water or an organic solvent and under conditions that satisfy the following formulas [] and []. (In the formula, R represents -C( CH3 ) 2- , and k is an integer of 0 or 1.) (In the formula, R and k are the same as the formula [],
n and m are integers, and n+m is 1 or 2. ) 120≦T≦220 [] 1≦P [] [However, T is the reaction temperature (° C.) and P is the reaction pressure (Kg/cm 2 ). ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24179984A JPS61122246A (en) | 1984-11-16 | 1984-11-16 | Production of bisphenol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24179984A JPS61122246A (en) | 1984-11-16 | 1984-11-16 | Production of bisphenol compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61122246A JPS61122246A (en) | 1986-06-10 |
| JPH0522693B2 true JPH0522693B2 (en) | 1993-03-30 |
Family
ID=17079681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24179984A Granted JPS61122246A (en) | 1984-11-16 | 1984-11-16 | Production of bisphenol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61122246A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63225336A (en) * | 1987-12-23 | 1988-09-20 | Nippon Steel Corp | Production of 2,2'-dihydroxybiphenylmonocarboxylic acid |
| WO2023189498A1 (en) * | 2022-03-30 | 2023-10-05 | 上野製薬株式会社 | Method for producing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid |
| WO2023189499A1 (en) * | 2022-03-30 | 2023-10-05 | 上野製薬株式会社 | Method for producing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3515695A (en) * | 1967-10-06 | 1970-06-02 | Us Air Force | Polydisalicylide polymers |
-
1984
- 1984-11-16 JP JP24179984A patent/JPS61122246A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3515695A (en) * | 1967-10-06 | 1970-06-02 | Us Air Force | Polydisalicylide polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61122246A (en) | 1986-06-10 |
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