JPH04164919A - Production of phenolic resin - Google Patents
Production of phenolic resinInfo
- Publication number
- JPH04164919A JPH04164919A JP29076090A JP29076090A JPH04164919A JP H04164919 A JPH04164919 A JP H04164919A JP 29076090 A JP29076090 A JP 29076090A JP 29076090 A JP29076090 A JP 29076090A JP H04164919 A JPH04164919 A JP H04164919A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- reaction
- phenolic resin
- acid
- heteropolyacid
- 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.)
- Pending
Links
- 239000005011 phenolic resin Substances 0.000 title abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 7
- 229920001568 phenolic resin Polymers 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 239000011964 heteropoly acid Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 abstract 2
- 150000001993 dienes Chemical class 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000012262 resinous product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 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 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- UQSASSBWRKBREL-UHFFFAOYSA-K 2-hydroxyethyl(trimethyl)azanium;iron(3+);2-oxidopropane-1,2,3-tricarboxylate;trihydrate Chemical compound O.O.O.[Fe+3].C[N+](C)(C)CCO.[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O UQSASSBWRKBREL-UHFFFAOYSA-K 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 241001442654 Percnon planissimum Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、次記一般式（■）（式中Ｒは炭素数１〜１２
のアルキル基または水素原子を示し、ｎ＝１〜１５であ
る）で示されるフェノール樹脂の製造方法に間する。Detailed Description of the Invention (Industrial Field of Application) The present invention is based on the following general formula (■) (wherein R is a carbon number of 1 to 12
represents an alkyl group or a hydrogen atom, and n=1 to 15).
本発明の方法で製造される一般式（１）で示されるフェ
ノール樹脂は、エポキシ樹脂やエポキシ樹脂硬化剤の原
料となる有用な化合物である。The phenolic resin represented by the general formula (1) produced by the method of the present invention is a useful compound that is a raw material for epoxy resins and epoxy resin curing agents.
（従来の技術）
フェノール類とシンクロペンタジエンとを反応させフェ
ノール樹脂組成物を製造する方法としては、三フッ化ホ
ウ素のようなルイス酸（Ｂ Ｆ３． ＡｌＣｌ３．Ｚ
ｎＣｌ２．Ｈ２Ｓ０ａ、、Ｔ １ｃｉａ、Ｈ２ＰＯ４等
）を触媒とする方法が知られている（特開昭６３−９９
２２４号公報）。しかしながら、この方法では、腐食性
を有する三フッ化ホウ素のようなルイス酸を触媒として
使用するため、ステンレス鋼のような工業的に汎用され
ている反応装置では、装置の腐食が著しいという欠点が
あった。(Prior art) As a method for producing a phenolic resin composition by reacting phenols and synchropentadiene, a Lewis acid such as boron trifluoride (BF3.AlCl3.Z
nCl2. A method using H2SOa, T1cia, H2PO4, etc.) as a catalyst is known (Japanese Unexamined Patent Application Publication No. 63-99
Publication No. 224). However, since this method uses a corrosive Lewis acid such as boron trifluoride as a catalyst, it has the disadvantage that the equipment is severely corroded in industrially used reaction equipment such as stainless steel. there were.
（発明が解決しようとする課題）
腐食性のない酸触媒としては、例えは強酸性イオン交換
樹脂や活性白土の桟な固体酸触媒が使用されるが、本発
明者らが実際に強酸性イオン交換樹脂を用いて同様に反
応を行フたところ（比較例１参＠）、一般式（１） ｌ
こおいて、ｎ＝ｏのものの割合が高い樹脂しか得られず
、反応が十分に進行しないという欠点があることがわか
った。(Problem to be Solved by the Invention) As non-corrosive acid catalysts, for example, strong acid ion exchange resins or solid acid catalysts made of activated clay are used. When a similar reaction was carried out using an exchange resin (see Comparative Example 1@), the general formula (1) l
It has been found that this method has the drawback that only a resin with a high proportion of n=o can be obtained, and the reaction does not proceed sufficiently.
本発明は、上述のような腐食性を有する触媒を（発明を
解決するための手段）
本発明者らは、ヘテロポリ酸を触媒に用いることにより
、従来の技術に比へ腐食性のルイス酸を使用することな
く、フェノール類とシンクロペンタジエンから一般式（
Ｉ）で示されるフェノール樹脂を製造する方法を見いだ
し本発明に至った。The present invention utilizes a corrosive catalyst as described above (Means for Solving the Invention) By using a heteropolyacid as a catalyst, the present inventors have realized that a corrosive Lewis acid can be used as a catalyst compared to the conventional technology. The general formula (
The present invention was achieved by discovering a method for producing the phenolic resin shown in I).
ヘテロポリ酸は、かなり強い多塩基酸であり、染料、顔
料、印刷インキ、表面処理剤として広く用いられること
かある。Heteropolyacids are fairly strong polybasic acids and are widely used as dyes, pigments, printing inks, and surface treatment agents.
作りえは、特開平２−４５４３９号公報ではフェノール
類とケトンを反応させてビスフェノールを製造するに際
し、・′＼テロポリ該を酸性縮合剤として用いる方法が
開示されている。As for how to make it, JP-A-2-45439 discloses a method of using telopoly as an acidic condensing agent when producing bisphenol by reacting phenols with ketones.
すなわち本発明は、フェノール類とシンクロペンタジエ
ンとをへテロポリ酸の存在下反応させろことを特徴とす
る、一般式（Ｉ）（式中Ｒは炭素数１〜１２のアルキル
基または水素原子を示し、ｎ＝１〜１５である）で表さ
れるフェノール樹脂の製造方法である。That is, the present invention is characterized in that phenols and synchropentadiene are reacted in the presence of a heteropolyacid, and is characterized in that phenols and synchropentadiene are reacted in the presence of a heteropolyacid. n=1 to 15).
（発明の詳細な説明）
工ＬＬユＬ１
本発明の方法に使用されるフェノール類としては、次記
の一般式（ＩＩ）で示される
Ｈ
Ｒが炭素数１〜１２のアルキル基または水素原子である
フェノール類で、例えは、フェノール、フレソール、エ
チルフェノール、イソプロピルフェノール、 ｔｅｒｔ
−ブチルフェノール、５ｅｃ−ブチルフェノール、 ｔ
ｅｒｔ−アミルフェノール、ノニルフェノール、１・″
デシルフェノール等を例示することができろ。これらは
、車−組成物でも、置換基の位置が異なるものの混合物
でも、あるいは異なったアルキル基を有するフェノール
類の混合物でもいずれも使用することができる。(Detailed Description of the Invention) The phenols used in the method of the present invention include those represented by the following general formula (II) where HR is an alkyl group having 1 to 12 carbon atoms or a hydrogen atom. Certain phenols, such as phenol, fresol, ethylphenol, isopropylphenol, tert
-butylphenol, 5ec-butylphenol, t
ert-amylphenol, nonylphenol, 1・″
Can you give an example of decylphenol? These can be used both in car compositions, in mixtures with different positions of substituents, or in mixtures of phenols with different alkyl groups.
フェノール類の使用量は、シンクロペンタジエン１モル
に対し、２〜１５モル、好ましくは３〜１０モルである
。フェノール類の使用量がこれ以下だと、反応の進行と
共に反応混合物の粘度が増大し攪拌が困難となり好まし
くなく、またこれ以上使用すると反応速度は向上するが
、未反応フェノール類の回収量が増大し生産性が倣下す
るので実用的でない。The amount of phenol used is 2 to 15 mol, preferably 3 to 10 mol, per 1 mol of synchropentadiene. If the amount of phenols used is less than this, the viscosity of the reaction mixture will increase as the reaction progresses, making stirring difficult, which is undesirable. If more than this amount is used, the reaction rate will improve, but the amount of unreacted phenols recovered will increase. However, it is not practical because productivity will be affected.
パパ ａべゝ ・１゛ ゝ
本発明の方法に使用されるシンクロペンタジエンは、蒸
留等により精製された高純度のものでも、あるいは飽和
炭化水素や芳香族炭化水素なとて希釈されたものでもど
ちらでも使用することができる。Papa abe ・１゛ゝThe synchropentadiene used in the method of the present invention may be either a high-purity one purified by distillation or the like, or a diluted one such as a saturated hydrocarbon or an aromatic hydrocarbon. It can also be used.
△上り旦コ拉ユ乙散
本発明において用いろヘテロポリ酸は、モリアゾン、タ
ングステン、バナジウムから選はれた少なくとも１種の
酸化物とリン、ケイ素、ヒ素及びゲルマニウムから選は
れたオキシ酸が縮合した構造で、後者に対する前者の原
子比が２．５〜１２である。これらのｌ＼テロホリ酸と
しては、例えはリンタングステン酸、リンモリブデン酸
、リンモリ７Ｆタングステン酸、リンモリブドバナジン
酸、リンモリブドタングストバナジン酸、ワンタングス
トバナジン酸、リンモリブドニオブ該、ケイタングステ
ン酸、ケイモリブデン酸、ケイモリブドタングステン酸
、ケイモリブドタングストバナジン酸、ゲルマニウムタ
ングステン酸、ヒ素モリブデン酸、ヒ素タングステン酸
なとである。The heteropolyacid used in the present invention is a condensation of at least one oxide selected from moriazone, tungsten, and vanadium and an oxyacid selected from phosphorus, silicon, arsenic, and germanium. In this structure, the atomic ratio of the former to the latter is 2.5 to 12. These terophoric acids include, for example, phosphotungstic acid, phosphomolybdic acid, phosphomolybdotungstic acid, phosphomolybdovanadate, phosphomolybdotungstovanadate, wontungstovanadate, phosphomolybdoniobium, and silicotungsten. acids, such as di-silicomolybdic acid, di-molybdotungstic acid, di-molybdotungstovanadic acid, germanium-tungstic acid, arsenic-molybdic acid, and arsenic-tungstic acid.
これらのへテロポリ酸はそのまま用（９ることができる
が、活性炭、アルミナ、シリカ−アルミナ、ケイソウ土
なとの担体に担持したものを用いてもよい。These heteropolyacids can be used as they are, but they may also be supported on a carrier such as activated carbon, alumina, silica-alumina, or diatomaceous earth.
ヘテロポリ酸の使用量は、ジンクロベ〕ノダジエンに対
し好ましくは０．０１〜１０モル％、特に好まし・くは
０．０５〜５モル％の範囲である。The amount of heteropolyacid used is preferably in the range from 0.01 to 10 mol%, particularly preferably from 0.05 to 5 mol%, based on the amount of zinclobene]nodadiene.
Ｗ泄
本発明の方法では、反応の形態に特に制限はないが、−
船釣にはフェノール類、シンクロペンタジエン及びヘテ
ロポリ酸を一括して反応器に仕込み加熱攪拌する回分操
作で行われる。また、フェノール類とへテロポリ酸を予
め反応器に仕込み、シンクロペンタジエンを連続的に供
給する方法で行ってもよい。W excretion In the method of the present invention, there is no particular restriction on the form of the reaction, but -
Boat fishing is carried out in a batch operation in which phenols, synchropentadiene, and heteropolyacids are charged all at once into a reactor and heated and stirred. Alternatively, the reaction may be carried out by charging phenols and heteropolyacids in advance into a reactor and continuously supplying synchropentadiene.
反応温度は４０〜２００℃、好ましくは６０〜１６０℃
の範囲である。Reaction temperature is 40-200°C, preferably 60-160°C
is within the range of
反応時間は触媒量や反応温度によって異なるが、通常は
２〜２４時間である。反応圧力は、常圧でも加圧でもよ
い。The reaction time varies depending on the amount of catalyst and reaction temperature, but is usually 2 to 24 hours. The reaction pressure may be normal pressure or increased pressure.
本発明の方法で得られるフェノール樹脂は一般式（１）
で示されるものであるが、エポキシ樹脂やエポキシ樹脂
硬化剤の原料として用ｔする場合ζこは、本発明の方法
で得られる混合物をそのまま用いることができる。The phenolic resin obtained by the method of the present invention has the general formula (1)
However, when used as a raw material for an epoxy resin or an epoxy resin curing agent, the mixture obtained by the method of the present invention can be used as is.
（実施例）
以下に実施例及び比較例を挙げ本発明をさらζこ具体的
に説明する。(Example) The present invention will be explained in more detail below with reference to Examples and Comparative Examples.
実施例１
温度計、ジムロート冷却器を備えた２ ００ ｍ １三
ロフラスコにフェノール４７．０７ｇ（５００ミリモル
）、シンクロペンタジエン１６．５３ｇ（１２５ミリモ
ル）を仕込み、１００℃で減圧乾燥し結晶水を飛ばした
ケイタングステン９１（ＨａＳｉＷ＋ ２０ 直ｓ）
１． ４１ｇ （０，５ミ ｉ） モ
ル ） を加えて常圧下１００℃で８時間攪拌をｔテ
つた。Example 1 47.07 g (500 mmol) of phenol and 16.53 g (125 mmol) of synchropentadiene were placed in a 200 m 1 three-ring flask equipped with a thermometer and a Dimroth condenser, and dried under reduced pressure at 100°C to remove crystallization water. Silicon tungsten 91 (HaSiW+ 20 directs)
1. 41g (0.5mi i) mo
The mixture was stirred at 100° C. for 8 hours under normal pressure.
反応混合物にトルエン６５ｇを加え触媒を濾！！１し、
８０℃に加熱し洗液のｐＨが４以上ζこなるまで、水洗
を行った。水洗後、水及びトルエンを常圧蒸留によって
回収し、次いて減圧蒸留によりフェノールの大部分を回
収した。さらに水蒸気蒸留によりフェノールを完全に回
収し、赤褐色の樹脂状生成物３１．４６ｇを得た。この
生成物のゲルバーミュージョンクロマトグラフィー（以
下ＧＰＣと略称する）及び高速液体クロマトグラフィー
（以下ＨＰＬＣと略称する）で分析した結果を表１に示
した。Add 65g of toluene to the reaction mixture and filter the catalyst! ! 1 and
It was heated to 80° C. and washed with water until the pH of the washing solution became 4 or more. After washing with water, water and toluene were recovered by atmospheric distillation, and then most of the phenol was recovered by vacuum distillation. Furthermore, phenol was completely recovered by steam distillation, and 31.46 g of a reddish brown resinous product was obtained. Table 1 shows the results of analysis of this product by gel vermusion chromatography (hereinafter referred to as GPC) and high performance liquid chromatography (hereinafter referred to as HPLC).
実施例２
ヘテロポリ酸として１００℃で減圧乾燥し結晶水を飛ば
したリンタングステン酸（Ｈ３Ｐ Ｗ １２０ ａｓ）
２． ８５ｇ （１，０ミリモル）を使用した以外は
実施例１と同じ条件で反応及び後処理を行った。Example 2 Phosphortungstic acid (H3P W 120 as) dried under reduced pressure at 100°C to remove crystallization water as a heteropolyacid
2. The reaction and post-treatment were carried out under the same conditions as in Example 1, except that 85 g (1.0 mmol) was used.
赤褐色の樹脂状生成物３２．２７ｇを得た。この生成物
のＧＰＣ及びＨＰＬＣの分析結果を表１に示した。32.27 g of a reddish-brown resinous product were obtained. The results of GPC and HPLC analysis of this product are shown in Table 1.
実施例３
フェノールの代わりにオルソクレゾール５４゜０７ｇ
（５００ミリモル）を使用した以外は実施例１と同じ条
件で反応及び後処理を行った。赤褐色の樹脂状生成物３
４．２８ｇを得た。この生成物のＧＰＣ及びＨＰＬＣの
分析結果を表１に示した。Example 3 Orthocresol 54°07g instead of phenol
The reaction and post-treatment were carried out under the same conditions as in Example 1 except that (500 mmol) was used. Reddish brown resinous product 3
4.28g was obtained. The results of GPC and HPLC analysis of this product are shown in Table 1.
実施例４
フェノールの代わりにパラクレゾール５４．０７ｇ（５
００ミリモル）を使用した以外は実施例１と同じ条件で
反応及び後処理を行った。赤褐色の樹脂状生成物３４．
９１ｇを得た。この生成物のＧＰＣ及びＨＰＬＣの分析
結果を表１に示した。Example 4 54.07g (54.07g) of para-cresol instead of phenol
The reaction and post-treatment were carried out under the same conditions as in Example 1 except that 00 mmol) was used. Red-brown resinous product 34.
91g was obtained. The results of GPC and HPLC analysis of this product are shown in Table 1.
比較例１
ヘテロポリ酸の代わりに強酸性イオン交換樹脂アンバー
リスト１５（ロームアンドハース社製品名）４．７ｇを
使用し反応時間を２４時間とした以外は実施例１と同じ
条件で反応及び後処理を行った。赤褐色の樹脂状生成物
３３．８２ｇを得た。Comparative Example 1 Reaction and post-treatment were carried out under the same conditions as in Example 1, except that 4.7 g of strongly acidic ion exchange resin Amberlyst 15 (product name of Rohm and Haas Co., Ltd.) was used instead of the heteropolyacid and the reaction time was 24 hours. I did it. 33.82 g of a reddish-brown resinous product were obtained.
この生成物のＧＰＣ及びＨＰＬＣの分析結果を表１に示
した。The results of GPC and HPLC analysis of this product are shown in Table 1.
実施例及び比較例から明かなように、強酸性イオン交換
樹脂のような従来知られている腐食性のない酸触媒では
反応が十分に進行せず、低分子量の生成物が大量に残存
する。As is clear from the Examples and Comparative Examples, the reaction does not proceed sufficiently with conventionally known non-corrosive acid catalysts such as strongly acidic ion exchange resins, and a large amount of low molecular weight products remain.
（発明の効果）
本発明の方法を用いれば、腐食性を有する触媒を用いる
ことなく、フェノール類とシンクロペンタジエンからエ
ポキシ樹脂やエポキシ樹脂硬化剤に適したフェノール樹
脂を製造することができる。(Effects of the Invention) By using the method of the present invention, a phenol resin suitable for epoxy resins and epoxy resin curing agents can be produced from phenols and synchropentadiene without using corrosive catalysts.
Claims (1)
ポリ酸の存在下反応させることを特徴とする、次記一般
式（ I ）（式中Ｒは炭素数１〜１２のアルキル基また
は水素原子を示し、ｎ＝１〜１５である）で表されるフ
ェノール樹脂の製造方法。 ▲数式、化学式、表等があります▼（ I ）(1) The following general formula (I) (wherein R represents an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, n = 1 to 15). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29076090A JPH04164919A (en) | 1990-10-30 | 1990-10-30 | Production of phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29076090A JPH04164919A (en) | 1990-10-30 | 1990-10-30 | Production of phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04164919A true JPH04164919A (en) | 1992-06-10 |
Family
ID=17760179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29076090A Pending JPH04164919A (en) | 1990-10-30 | 1990-10-30 | Production of phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04164919A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060977A (en) * | 2009-11-13 | 2011-05-18 | 南亚塑胶工业股份有限公司 | Brominated epoxy resin with highly symmetrical or saturated aliphatic heterocyclic ring and preparation method thereof |
| CN103421273A (en) * | 2012-05-22 | 2013-12-04 | 中山台光电子材料有限公司 | Halogen-free resin composition |
| WO2022124252A1 (en) * | 2020-12-07 | 2022-06-16 | 日鉄ケミカル＆マテリアル株式会社 | Polyhydric hydroxy resin, epoxy resin, and their production methods, and epoxy resin composition and cured product thereof |
-
1990
- 1990-10-30 JP JP29076090A patent/JPH04164919A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060977A (en) * | 2009-11-13 | 2011-05-18 | 南亚塑胶工业股份有限公司 | Brominated epoxy resin with highly symmetrical or saturated aliphatic heterocyclic ring and preparation method thereof |
| CN103421273A (en) * | 2012-05-22 | 2013-12-04 | 中山台光电子材料有限公司 | Halogen-free resin composition |
| WO2022124252A1 (en) * | 2020-12-07 | 2022-06-16 | 日鉄ケミカル＆マテリアル株式会社 | Polyhydric hydroxy resin, epoxy resin, and their production methods, and epoxy resin composition and cured product thereof |
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