JPS6033124B2 - Production method of hexacyclic phenol formaldehyde resin - Google Patents
Production method of hexacyclic phenol formaldehyde resinInfo
- Publication number
- JPS6033124B2 JPS6033124B2 JP12351782A JP12351782A JPS6033124B2 JP S6033124 B2 JPS6033124 B2 JP S6033124B2 JP 12351782 A JP12351782 A JP 12351782A JP 12351782 A JP12351782 A JP 12351782A JP S6033124 B2 JPS6033124 B2 JP S6033124B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde resin
- mol
- hexacyclic
- phenol
- phenol formaldehyde
- 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
Links
- 229920001568 phenolic resin Polymers 0.000 title claims description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- -1 methylol groups Chemical group 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 101100537937 Caenorhabditis elegans arc-1 gene Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CURUTKGFNZGFSE-UHFFFAOYSA-N dicyclomine Chemical group C1CCCCC1C1(C(=O)OCCN(CC)CC)CCCCC1 CURUTKGFNZGFSE-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明は環状体フェノール・ホルムアルデヒド樹脂の製
造法に関するもので、さらに詳しくは６環状体フェノー
ル・ホルムアルデヒド樹脂を選択的にかつ高収率で製造
する方法に関するものである。
従来から各種廃水中に含まれる銅、水銀、ニッケルなど
の重金属イオンの吸着剤としては活性炭、けいそう士、
各種イオン交予期樹脂あるいはキレート能と有する樹脂
たとえばクラウンエーテル化合物などが挙げられる。
しかしこれらのうち活性炭、けいそう土、イオン交換樹
脂は、重金属イオンに対する選択性に劣り、またクラウ
ンェー７ル化合物は選択性はある程度あるものの耐熱性
に劣りかつ高価であり、汎用性に乏しい。本発明者らは
特定の置換基を導入したフェノ−ル類を原料とした環状
フェノール・ホルムアルデヒド樹脂が重金属イオンに対
して極めて優れた選択吸着能を有することを見し、出し
た。
しかしながら従釆の合成法（一段法）では各種環状体の
中の１つを選択的に合成することあるいは各種混合体を
高収率で得ることは出来なかった。本発明は以上の状況
を踏まえて鋭意検討した結果、完成したものである。
即ち、本発明はｐ−ァルキルフェノール類にホルムアル
デヒド類を反応させて得られる平均分子量（Ｍｎ）が７
００〜３０００で、反応したホルムアルデヒドの結合形
態がメチロール基が５〜２５モル％、ジメチレンェーテ
ル基７〜２３モル％、メチレン基が５２〜８８モル％で
あるフェノール・ホルムアルデヒド樹脂に非水系溶媒及
びＫ又はＲｂの水酸化物を加えて加熱反応させることを
特徴とする６環状体フェノール・ホルムアルデヒド樹脂
の製造法に関するものである。
本発明に用いられるフェノール・ホルムアルデヒド樹脂
の平均分子量が上記範囲外である場合は環状化反応が全
くおこらず線状のままである。
また樹脂中のホルムアルデヒドの結合形態についてはメ
チロール基 （一Ｃ墨ＯＨ）
５〜２５モル％
ジメチレンェーテル基（一ＣＱＯＣＨ２一）７〜２３モ
ル％メチレン基 （一Ｃ舷） ５２〜８８モル
％であることが必要で以上の構成以外の線状フェ／ール
・ホルムアルデヒド樹脂を使用した場合には環化反応お
こらない。
次に線状フェノール・ホルムアルデヒド樹脂の原料アル
キルフェノール類については、ｐ−位にァルキル基が置
換している化合物が用いられ、さらにァルキル基の種類
についてはメチル基、エチル基、ブチル基（ノルマルブ
チル基、セカンダリーブチル基、ターシヤルブチル基）
、ベンチル基、ヘプチル基、オクチル基、等の好ましく
は炭素数１〜１０のものが用いられる。
本発明に用いられる線状フェノール・ホルムアルデヒド
樹脂を製造するに際して、ホルムアルデヒド類の種類、
量、合成用触媒種、量、合成用溶媒、あるいは合成温度
、合成時間等の各種条件については何ら規定するもので
はないが、好ましくはアルキルフェノール類１モルに対
して１．２〜３．０モルのホルムアルデヒド類を加え、
０．６５〜０．４モルのアルカリ触媒を添加して６０〜
１１０ｏｏで反応させる。
なお線状フェノール・ホルムアルデヒド樹脂は予め、希
塩酸水溶液等で洗浄し溶剤等を減圧下で留去しておくこ
とが好ましい。線状フェノール・ホルムアルデヒド樹脂
に加えられる非水系溶媒としてはベンゼン、トルェン・
キシレン、ヘプタン、ジオキサン等が用いられ、使用量
は好ましくは線状フェノール・ホルムアルデヒド樹脂の
５〜３０重量倍である。
Ｋ又はＲｂの水酸化物はアルキルフェノール類１モルに
対して０．１〜１．０モル相当量用いるのが好ましい。
１．０モルを越えると環化反応が起りにくく、また、０
．１モル未満では反応速度が小さく好ましくない。
尚、水の添加量については、非水系溶媒の使用量の０．
５〜２．の重量％が好ましい。反応温度は１００〜１５
０ｑｏで反応可能であり、さらに好ましくは１３０〜１
４０ｑｏが良い。
尚、反応時間は３〜３畑時間が良い。以上に述べたよう
な本発明の方法（二段法）は従来の一段法に比べて選択
的に６環状体フェノール・ホルムアルデヒド樹脂を得る
ことができる。
以下本発明を参考例、実施例に基いて説明する。参考例
（一段法）
ｐ−ｔｅｎーブチルフエノール６０夕（０．４モル）を
とパラホルムアルデヒド３０夕（０．８モル）をキシレ
ン２００泌に懸濁させ水酸化カリウム４．４８（０．０
８モル）を水２の上に溶解して加え還流温度で５時間反
応させた。
反応後、希塩酸を加え塩酸および水で繰り返し洗浄し、
減圧乾燥した。得られた固体をメタノールで抽出し、メ
タノール不溶物をクロロホルムーメタノール混合溶媒を
用いて分別再結晶し、３種のオリゴマー（以下〔１〕〔
０〕〔ｍ〕とする）を単離した。さらに正成物をＧＰＣ
、マススベクトル、 ′日 ＮＭＲ、ＩＲスペクトル
によって分析した。第１図は、線状フェノール・ホルム
アルデヒド樹脂のアセチル化物、〔１〕，The present invention relates to a method for producing a cyclic phenol/formaldehyde resin, and more particularly to a method for producing a hexacyclic phenol/formaldehyde resin selectively and in high yield. Activated carbon, diaphragm,
Examples include various ion exchange resins or resins having chelating ability, such as crown ether compounds. However, among these, activated carbon, diatomaceous earth, and ion exchange resins have poor selectivity for heavy metal ions, and crown wal compounds have some selectivity but are poor in heat resistance, expensive, and lack versatility. The present inventors have discovered that a cyclic phenol/formaldehyde resin made from phenols into which specific substituents have been introduced has an extremely excellent selective adsorption ability for heavy metal ions. However, with the secondary synthesis method (one-step method), it was not possible to selectively synthesize one of the various cyclic bodies or to obtain various mixtures in high yield. The present invention was completed as a result of intensive studies based on the above circumstances. That is, in the present invention, the average molecular weight (Mn) obtained by reacting p-alkylphenols with formaldehyde is 7.
00 to 3000, and the bonding form of the reacted formaldehyde is 5 to 25 mol% of methylol groups, 7 to 23 mol% of dimethylene ether groups, and 52 to 88 mol% of methylene groups. The present invention relates to a method for producing a hexacyclic phenol formaldehyde resin, which is characterized by adding a solvent and a hydroxide of K or Rb and carrying out a heating reaction. When the average molecular weight of the phenol-formaldehyde resin used in the present invention is outside the above range, the cyclization reaction does not occur at all and the resin remains linear. Regarding the bonding form of formaldehyde in the resin, methylol group (1C ink OH) 5-25 mol% dimethylene ether group (1CQOCH2-) 7-23 mol% methylene group (1C side) 52-88 mol %, and if a linear phenol formaldehyde resin other than the above configuration is used, the cyclization reaction will not occur. Next, regarding the raw material alkylphenols for linear phenol/formaldehyde resin, compounds in which an alkyl group is substituted at the p-position are used, and the types of alkyl groups are methyl, ethyl, butyl (n-butyl), etc. , secondary butyl group, tertiary butyl group)
, a bentyl group, a heptyl group, an octyl group, and the like, preferably those having 1 to 10 carbon atoms are used. When producing the linear phenol formaldehyde resin used in the present invention, the type of formaldehyde,
There are no restrictions on various conditions such as amount, type of catalyst for synthesis, amount, solvent for synthesis, synthesis temperature, synthesis time, etc., but preferably 1.2 to 3.0 mol per mol of alkylphenol. Add formaldehyde of
60~ by adding 0.65~0.4 mol of alkali catalyst
React at 110oo. Note that it is preferable to wash the linear phenol formaldehyde resin with a dilute aqueous hydrochloric acid solution or the like in advance and distill off the solvent and the like under reduced pressure. Examples of nonaqueous solvents added to linear phenol/formaldehyde resins include benzene, toluene, and
Xylene, heptane, dioxane, etc. are used, and the amount used is preferably 5 to 30 times the weight of the linear phenol formaldehyde resin. The K or Rb hydroxide is preferably used in an amount equivalent to 0.1 to 1.0 mol per mol of the alkylphenol.
If the amount exceeds 1.0 mol, the cyclization reaction will be difficult to occur;
．． If it is less than 1 mole, the reaction rate will be low, which is not preferable. Note that the amount of water added is 0.0% of the amount of non-aqueous solvent used.
5-2. % by weight is preferred. The reaction temperature is 100-15
It is possible to react at 0 qo, more preferably 130 to 1
40qo is good. In addition, the reaction time is preferably 3 to 3 field hours. The method of the present invention (two-stage method) as described above can selectively obtain a hexacyclic phenol formaldehyde resin compared to the conventional one-stage method. The present invention will be explained below based on reference examples and examples. Reference example (one-step method) 60 moles (0.4 moles) of p-ten-butylphenol and 30 moles (0.8 moles) of paraformaldehyde were suspended in 200 moles of xylene, and 4.48 moles (0.0 moles) of potassium hydroxide were suspended.
8 mol) was dissolved on water 2 and reacted at reflux temperature for 5 hours. After the reaction, add dilute hydrochloric acid and wash repeatedly with hydrochloric acid and water.
Dry under reduced pressure. The obtained solid was extracted with methanol, and the methanol-insoluble matter was fractionally recrystallized using a chloroform-methanol mixed solvent to obtain three types of oligomers (hereinafter referred to as [1]
0] [m]) was isolated. Furthermore, the positive product was subjected to GPC
, mass vector, NMR, and IR spectroscopy. Figure 1 shows the acetylated product of linear phenol formaldehyde resin, [1],
〔０〕，〔ｍ
〕の ＨＮＭ旧スーベクトル、第２図は線状フェノール
・ホルムアルデヒド樹脂、〔１〕，[0], [m
]'s HNM former souvector, Figure 2 is a linear phenol formaldehyde resin, [1],
〔０〕，〔ｍ〕のＩ
Ｒスペクトルである。
１：ＧＰＣ溶出容量２４．２泌
アセチル化物のＶＰＵによる分子量１６３００：ＧＰＣ
溶出容量２５．７の【Ｍ／Ｚ ９７２
ｍ；○ＰＣ溶出容量３７．６舷
ＩＲにおいて−ＯＨの吸収が線状フェノール・ホルムア
ルデヒド樹脂では３４００ｃの１にでるのに比べて〔１
〕〔ロ〕〔ｍ〕では３２００ｃの‐１に見られ水素結合
していることを示している。
また〔血〕にはＩＲでは１１００弧‐１に、ＮＭＲでは
４．＆阿付近にエーテル結合の吸収が見られる。
また、〔１〕〔ロ〕はメチレン結合のみの環状構造であ
る。上記のデータを合せると〔１〕〔ロ〕〔ｍ〕は以下
の構造であることがわかる。
ｌ但し
実施例 １
ｐ−ｔｅｒｔ−ブチルフエノール６０夕（０．４モル）
と３７％ホルマリン６４．９夕（０．８モル）水酸化カ
リウム４．４８夕（０．０８モル）を配合して１００ｏ
ｏで５時間反応させた。
反応後希塩酸と水で充分に洗浄し減圧し平均分子量Ｍｎ
＝１８１０、メチロール基１０％、ジメチレンューテル
基１２％、メチレン基７８％の線状フェノール・ホルム
アルデヒド樹脂を得た。ついでこの緑状フェノール・ホ
ルムアルデヒド樹脂１５のこキシレン１００の‘を加え
、さらに水酸化ルビジウム２．１夕（０．０２モル）を
１泌の水に溶解して加えて１４０ｏｏで５時間反応させ
た。
得られた反応物をメタノールで抽出しメタノール不溶物
をクロロホルムーメタノール混合溶媒を用いて分別再結
晶した。その結果I of [0], [m]
This is the R spectrum. 1: GPC elution capacity 24.2 Molecular weight according to VPU of secreted acetylate 16300: GPC
With an elution capacity of 25.7 [M/Z 972 m; ○ PC elution capacity 37.6 ships] -OH absorption at IR is 3400c compared to 1 in linear phenol formaldehyde resin [1
] [B] [m] is seen at -1 of 3200c, indicating a hydrogen bond. Also, [blood] is 1100 arc-1 in IR and 4. Absorption of ether bond is seen near &a. Moreover, [1] [b] is a cyclic structure containing only methylene bonds. Combining the above data, it can be seen that [1] [b] [m] has the following structure. However, Example 1 p-tert-butylphenol 60 molar (0.4 mol)
100o
The reaction was carried out at o for 5 hours. After the reaction, wash thoroughly with dilute hydrochloric acid and water and reduce the pressure to reduce the average molecular weight Mn.
= 1810, a linear phenol formaldehyde resin containing 10% methylol groups, 12% dimethylene ether groups, and 78% methylene groups was obtained. Next, 15 parts of this green phenol-formaldehyde resin and 100 parts of xylene were added, and 2.1 parts (0.02 mol) of rubidium hydroxide dissolved in 1 part of water was added, and the mixture was reacted at 140°C for 5 hours. . The obtained reaction product was extracted with methanol, and the methanol-insoluble material was fractionally recrystallized using a chloroform-methanol mixed solvent. the result
〔０〕のみが単離された。単離したオ
リゴマーをＧＰＣ、 ′日 ＮＭＲ、ＩＲスペクトル、
マススベクトル測定した結果、参考例Ｄの分析値と完全
に一致した。実施例 ２
ｐ−ｔｅ比−ブチルフエノール６０夕（０．４モル）と
３７％ホルマリン６４．９夕（０．８モル）水酸化カリ
ウム４．４８夕（０．００８モル）を配合して９０ｏｏ
で５時間反応させた後、希塩酸と水で充分に洗浄し減圧
乾燥し平均分子量Ｍｎ＝１１４０メチロール基１３％、
ジメチレンヱーテル基１６％、メチレン基７１％、の線
状フェノール・ホルムアルデヒド樹脂を得た。
ついでこの糠状フェノール・ホルムァルデヒド樹脂３の
こキシレン１００のとを加え、さらに水酸化カリウム０
．６夕（０．０１モル）を１の‘の水に溶解して加えて
１３５午０で８時間反応させた。得られた反応物をメタ
ノールで抽出し、メタノール不溶物をクロロホルムーメ
タノール混合溶媒を用いて分別再結晶した。その結果〔
ロ〕相当の化合物のみが単離された。単離したオリゴマ
ーをＧＰＣ、 ′ＨＮＭＲ，ＩＲスペクトル、マススベ
クトルを測定した。その結果マススベクトルによる分子
量９７２、ＧＰＣ溶出容量２５．７の‘でありＩＲにお
いて−ＯＨの吸収が３２００肌‐１付近にシフトしてお
り水素結合していることが確認された。従って、得られ
た化合物は参考例で示したOnly [0] was isolated. The isolated oligomers were analyzed by GPC, NMR, IR spectra,
The mass vector measurement results completely matched the analytical values of Reference Example D. Example 2 P-TE ratio - Butylphenol 60 mol (0.4 mol), 37% formalin 64.9 mol (0.8 mol) and potassium hydroxide 4.48 mol (0.008 mol) were blended to make 90 mol.
After reacting for 5 hours at
A linear phenol formaldehyde resin containing 16% dimethylene ether groups and 71% methylene groups was obtained. Next, 3 parts of this bran-like phenol-formaldehyde resin and 100 parts of xylene were added, and then 0 parts of potassium hydroxide was added.
．． 6 mol (0.01 mol) was dissolved in 1 ml of water and added, and the mixture was reacted at 135 pm for 8 hours. The obtained reaction product was extracted with methanol, and the methanol-insoluble material was fractionally recrystallized using a chloroform-methanol mixed solvent. the result〔
b) Only the corresponding compound was isolated. The isolated oligomer was subjected to GPC, 'HNMR, IR spectrum, and mass vector measurements. As a result, the mass vector molecular weight was 972, the GPC elution capacity was 25.7', and the -OH absorption was shifted to around 3200 skin-1 in IR, confirming hydrogen bonding. Therefore, the obtained compound is as shown in the reference example.
〔０〕式の化合物であること
がわかる。
表１に参考例、実施例における各オリゴマ−の収率を示
す。
表Ｉ
本発明により６環状体フェノール・ホルムアルデヒドオ
リゴマーが選択的に合成できるようになつた。
図面の筒里な説明
第１図は綾状フェノール・ホルムアルデヒド樹脂のアセ
チル化物、〔１〕，It can be seen that it is a compound of formula [0]. Table 1 shows the yield of each oligomer in Reference Examples and Examples. Table I The present invention has made it possible to selectively synthesize hexacyclic phenol formaldehyde oligomers. Brief explanation of the drawings Figure 1 shows the acetylated product of twilled phenol/formaldehyde resin, [1],
〔０〕，〔ｍ〕のＮＭ町スペクトル
、第２図は線状フェノール・ホルムアルデヒド樹脂、〔
１），〔ロ〕，〔ｍ〕のＩＲスペクトルである。
第１図
第２図NM town spectrum of [0], [m], Figure 2 shows linear phenol formaldehyde resin, [
1), [b], and [m]. Figure 1 Figure 2
Claims (1)
反応させて得られる平均分子量で７００〜３０００で、
反応したホルムアルデヒドの結合形態がメチロール基が
５〜２５モル％、ジメチレンエーテル基が７〜２３モル
％、メチレン基が５２〜８８モル％であるフエノールホ
ルムアルデヒド樹脂に非水系溶媒及びＫ又はＲｂの水酸
化物を加えて反応させることを特徴とする６環状体のフ
エノール・ホルムアルデヒド樹脂の製造法。 ２ ｐ−アルキルフエノールがｐ−ｔｅｒｔ−ブチルフ
エノールである特許請求の範囲第１項記載の６環状体フ
エノール・ホルムアルデヒド樹脂の製造法。[Claims] 1. An average molecular weight of 700 to 3000 obtained by reacting p-alkylphenols with formaldehyde,
A non-aqueous solvent and K or Rb water are added to a phenol formaldehyde resin in which the bond form of the reacted formaldehyde is 5 to 25 mol% of methylol groups, 7 to 23 mol% of dimethylene ether groups, and 52 to 88 mol% of methylene groups. A method for producing a hexacyclic phenol-formaldehyde resin, which comprises adding an oxide and causing a reaction. 2. The method for producing a hexacyclic phenol/formaldehyde resin according to claim 1, wherein the p-alkylphenol is p-tert-butylphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12351782A JPS6033124B2 (en) | 1982-07-15 | 1982-07-15 | Production method of hexacyclic phenol formaldehyde resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12351782A JPS6033124B2 (en) | 1982-07-15 | 1982-07-15 | Production method of hexacyclic phenol formaldehyde resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5912914A JPS5912914A (en) | 1984-01-23 |
| JPS6033124B2 true JPS6033124B2 (en) | 1985-08-01 |
Family
ID=14862567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12351782A Expired JPS6033124B2 (en) | 1982-07-15 | 1982-07-15 | Production method of hexacyclic phenol formaldehyde resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6033124B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62120930U (en) * | 1986-01-27 | 1987-07-31 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61293238A (en) * | 1985-06-21 | 1986-12-24 | Hitachi Chem Co Ltd | Novel ultraviolet absorber |
| US5547194A (en) * | 1994-01-19 | 1996-08-20 | Daiwa Seiko, Inc. | Golf club head |
-
1982
- 1982-07-15 JP JP12351782A patent/JPS6033124B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62120930U (en) * | 1986-01-27 | 1987-07-31 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5912914A (en) | 1984-01-23 |
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