JPH06116369A - Production of phenolic aralkyl resin - Google Patents
Production of phenolic aralkyl resinInfo
- Publication number
- JPH06116369A JPH06116369A JP26482792A JP26482792A JPH06116369A JP H06116369 A JPH06116369 A JP H06116369A JP 26482792 A JP26482792 A JP 26482792A JP 26482792 A JP26482792 A JP 26482792A JP H06116369 A JPH06116369 A JP H06116369A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- oxalic acid
- zinc chloride
- reaction
- phenol
- 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
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は硬化の速いフェノールア
ラルキル樹脂の製法に関するものである。本発明のフェ
ノールアラルキル樹脂は、電気的特性、耐熱性、耐薬品
性、耐摩耗性等に優れ、成形材、摩擦材等の基材として
有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fast curing phenol aralkyl resin. The phenol aralkyl resin of the present invention is excellent in electrical characteristics, heat resistance, chemical resistance, wear resistance and the like, and is useful as a base material for molding materials, friction materials and the like.
【0002】[0002]
【従来の技術】従来、フェノール性化合物とアラルキル
化合物の反応生成物であるフェノールアラルキル樹脂の
製法は多数の方法が公知となっている。この製造触媒に
関しては、例えば特公昭47−15111号公報では塩
化第二錫、塩化亜鉛、塩化第二鉄を用いる方法が開示さ
れ、特公昭48−10960号公報では、塩化亜鉛を含
むフリーデルクラフツ型触媒およびジエチル硫酸触媒を
用いてフェノールアラルキル樹脂を得る方法が開示され
ている。2. Description of the Related Art Conventionally, many methods are known for producing a phenol aralkyl resin which is a reaction product of a phenolic compound and an aralkyl compound. Regarding this production catalyst, for example, JP-B-47-15111 discloses a method using stannic chloride, zinc chloride and ferric chloride, and JP-B-48-10960 discloses a Friedel Crafts containing zinc chloride. A method for obtaining a phenol aralkyl resin using a type catalyst and a diethyl sulfuric acid catalyst is disclosed.
【0003】また塩化亜鉛を用いて得られるオルソ結合
の多い、所謂ハイオルソのフェノール樹脂(ノボラック
樹脂)はヘキサメチレンテトラミン(以下HMTAと略
称する)との反応性が高く、速硬性樹脂として公知であ
る。A so-called high ortho phenolic resin (novolak resin) having a large number of ortho bonds, which is obtained by using zinc chloride, has a high reactivity with hexamethylenetetramine (hereinafter abbreviated as HMTA) and is known as a fast hardening resin. .
【0004】[0004]
【発明が解決しようとする課題】しかしながら、これら
特公昭47−15111号公報、特公昭48−1096
0号公報に開示されている塩化亜鉛触媒は活性が低いた
め、フェノールアラルキル樹脂の製造においては、通常
の方法では樹脂が得られない。またジエチル硫酸等の活
性の高い触媒で得られるフェノールアラルキル樹脂は、
通常のフェノール樹脂(ノボラック樹脂)に比べ、電気
的特性、耐薬品性、耐摩耗性、耐熱性に優れた性能を備
えた樹脂であるが、HMTAで硬化を行った場合、硬化
速度が遅く成形性に劣るという欠点があり、その改良が
求められていた。However, these Japanese Examined Patent Publication Nos. 47-15111 and 48-1096.
Since the zinc chloride catalyst disclosed in JP-A-0 has a low activity, a resin cannot be obtained by an ordinary method in the production of a phenol aralkyl resin. The phenol aralkyl resin obtained with a highly active catalyst such as diethylsulfate is
Compared with ordinary phenolic resin (novolac resin), this resin has excellent electrical properties, chemical resistance, abrasion resistance, and heat resistance, but when cured with HMTA, the curing speed is slow and molding There is a drawback that it is inferior in sex, and its improvement has been demanded.
【0005】本発明の目的は、HMTAで硬化を行った
場合の硬化反応が速く、成形性が良好なフェノールアラ
ルキル樹脂の製造方法を提供することにある。An object of the present invention is to provide a method for producing a phenol aralkyl resin which has a fast curing reaction when cured with HMTA and has good moldability.
【0006】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、触媒として塩化亜鉛
とシュウ酸を併用することにより、目的を達成できるこ
とを見出し本発明に到った。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the object can be achieved by using zinc chloride and oxalic acid together as a catalyst, and arrived at the present invention. It was
【0007】即ち、本発明は、下記一般式(1)〔化
3〕That is, the present invention provides the following general formula (1)
【0008】[0008]
【化3】 (上式中、R1、R2は水素原子、アルキル基、フェニル
基、ハロゲン原子を示し、同一でも異なっても良い。)
で示されるフェノール性化合物と下記一般式(2)〔化
4〕[Chemical 3] (In the above formula, R 1 and R 2 represent a hydrogen atom, an alkyl group, a phenyl group or a halogen atom, and may be the same or different.)
And a phenolic compound represented by the following general formula (2)
【0009】[0009]
【化4】 (上式中、R3は炭素数が1〜6のアルキル基を示し、
x、yは1または2の整数であり、x+y=3であ
る。)で示されるアラルキルエーテルを反応させて、フ
ェノールアラルキル樹脂を製造する際に、触媒として塩
化亜鉛とシュウ酸を併用することを特徴とするフェノー
ルアラルキル樹脂の製法である。[Chemical 4] (In the above formula, R 3 represents an alkyl group having 1 to 6 carbon atoms,
x and y are integers of 1 or 2 and x + y = 3. ) The aralkyl ether represented by the formula (1) is reacted to produce a phenol aralkyl resin, and zinc chloride and oxalic acid are used together as a catalyst in the process for producing the phenol aralkyl resin.
【0010】以下本発明を詳細に説明する。The present invention will be described in detail below.
【0011】本発明で使用するフェノール性化合物は、
一般式(1)〔化5〕The phenolic compound used in the present invention is
General formula (1) [Chemical formula 5]
【0012】[0012]
【化5】 (上式中、R1、R2は水素原子、アルキル基、フェニル
基、ハロゲン原子を示し、同一でも異なっても良い。)
で示され、芳香核に結合した1個の水酸基を含有する。
具体的には、芳香核の炭素原子に結合した置換基が全体
で3個以下の芳香族化合物、またはそれらの混合物であ
り、フェノール、o−クレゾール、m−クレゾール、p
−クレゾール、2,6−キシレノール、p−tert−
ブチルフェノール、p−フェニルフェノール、等が挙げ
られる。特に好ましいフェノール性化合物はフェノー
ル、o−クレゾール、p−クレゾール等である。[Chemical 5] (In the above formula, R 1 and R 2 represent a hydrogen atom, an alkyl group, a phenyl group or a halogen atom, and may be the same or different.)
And contains one hydroxyl group bonded to the aromatic nucleus.
Specifically, it is an aromatic compound having a total of 3 or less substituents bonded to carbon atoms of an aromatic nucleus, or a mixture thereof, and phenol, o-cresol, m-cresol, p
-Cresol, 2,6-xylenol, p-tert-
Butylphenol, p-phenylphenol, etc. are mentioned. Particularly preferred phenolic compounds are phenol, o-cresol, p-cresol and the like.
【0013】本発明で使用するアラルキルエーテルは、
一般式(2)〔化6〕The aralkyl ether used in the present invention is
General formula (2) [Chemical formula 6]
【0014】[0014]
【化6】 (上式中、R3は炭素数が1〜6のアルキル基を示し、
x、yは1または2の整数であり、x+y=3であ
る。)で示され、具体的にはα,α’−ジメトキシ−p
−キシレン(以下PXDMと略称する)、α,α’−ジ
エトキシ−p−キシレン、α,α’−ジメトキシ−o−
キシレン、α,α−ジメトキシ−m−キシレン、α,
α,α’−トリメトキシ−p−キシレン等が挙げられ、
特に好ましいアラルキルエーテルはPXDMである。[Chemical 6] (In the above formula, R 3 represents an alkyl group having 1 to 6 carbon atoms,
x and y are integers of 1 or 2 and x + y = 3. ), Specifically, α, α′-dimethoxy-p
-Xylene (hereinafter abbreviated as PXDM), α, α'-diethoxy-p-xylene, α, α'-dimethoxy-o-
Xylene, α, α-dimethoxy-m-xylene, α,
α, α'-trimethoxy-p-xylene and the like,
A particularly preferred aralkyl ether is PXDM.
【0015】フェノール性化合物のアラルキルエーテル
に対する使用比率は、目的とする樹脂の分子量或いは用
途に応じて広範囲に変化させることができるが、好まし
くは反応系の最終モル比が1.3以上である。1.3未
満ではゲル化の恐れがある。主触媒である塩化亜鉛は工
業用、試薬のいずれでも構わない。使用範囲はフェノー
ル性化合物とアラルキルエーテルの重量和に対して、
0.01重量%以上用いるのが好ましく、0.1〜0.
5重量%が更に好ましい。0.01重量%未満では極端
に反応が遅くなり、得られる樹脂はヘキサミンとの反応
性が悪く、硬化の速い樹脂が得られない。The ratio of the phenolic compound to the aralkyl ether used can be varied over a wide range depending on the molecular weight of the desired resin or the intended use, but the final molar ratio of the reaction system is preferably 1.3 or more. If it is less than 1.3, gelation may occur. Zinc chloride, which is the main catalyst, may be industrial or reagent. The range of use is based on the weight sum of the phenolic compound and the aralkyl ether.
It is preferable to use 0.01% by weight or more, and 0.1 to 0.
5% by weight is more preferable. If it is less than 0.01% by weight, the reaction becomes extremely slow, the resulting resin has poor reactivity with hexamine, and a resin which cures quickly cannot be obtained.
【0016】一方の主触媒であるシュウ酸は工業品、試
薬のいずれも使用でき、用いる量に特に制限は無いが、
使用する塩化亜鉛のモル数に対して、0.2〜1.1倍
モルが好ましい。また添加する触媒の形状は、固形でも
構わないが、水溶液のほうが取扱やすい。添加の方法
は、少量の触媒を有効に使い、安定した反応と樹脂を得
るために、分割または連続的に添加することが好まし
い。一括して添加すると一時的に激しく反応が起こり、
反応条件のコントロールが出来なくなり、また、シュウ
酸は熱分解を起こし長時間の触媒効果を維持できない。On the other hand, oxalic acid, which is the main catalyst, can be used either as an industrial product or as a reagent, and the amount used is not particularly limited,
It is preferably 0.2 to 1.1 times the moles of zinc chloride used. The shape of the catalyst to be added may be solid, but an aqueous solution is easier to handle. Regarding the method of addition, it is preferable to use a small amount of the catalyst effectively and to add it in portions or continuously in order to obtain a stable reaction and resin. When added all at once, a violent reaction occurs temporarily,
It becomes impossible to control the reaction conditions, and oxalic acid undergoes thermal decomposition and cannot maintain the catalytic effect for a long time.
【0017】上記、主原料以外の成分として、反応初期
の反応熱の蓄積を抑えるために、回分、または連続反応
では、反応条件下で飽和に達する量のメタノール(以
下、敷きメタノールと略称)を、反応が始まる以前に装
入しておくことが好ましい。またメタノール以外の、フ
ェノール性化合物とアラルキルエーテルの反応により副
生するアルコールと、同種のアルコールを用いることも
好ましい。As a component other than the above-mentioned main raw material, in order to suppress the accumulation of reaction heat at the initial stage of the reaction, in batch or continuous reaction, an amount of methanol (hereinafter abbreviated as spread methanol) which reaches saturation under the reaction conditions is used. It is preferable to charge before the reaction starts. It is also preferable to use an alcohol other than methanol, which is a by-product of the reaction of the phenolic compound and the aralkyl ether, and the same type of alcohol.
【0018】本発明の製法の一例を示すと、フェノール
性化合物、アラルキルエーテル、敷きメタノールおよび
塩化亜鉛を反応器に装入して、反応温度まで昇温し、シ
ュウ酸を間欠的または連続的に添加して、留出するアル
コールとフェノール性化合物およびアラルキルエーテル
の混合物から、フェノール性化合物およびアラルキルエ
ーテルを分縮しながら反応を続け、更に、副生アルコー
ルの留出が無くなるまで熟成反応を行った後、減圧下で
未反応のフェノール性化合物を除去してフェノールアラ
ルキル樹脂が得られる。As an example of the production method of the present invention, a phenolic compound, aralkyl ether, spread methanol and zinc chloride are charged into a reactor and heated to a reaction temperature to intermittently or continuously add oxalic acid. From the mixture of the alcohol and the phenolic compound and the aralkyl ether to be distilled off, the reaction was continued while the phenolic compound and the aralkyl ether were condensed, and further the aging reaction was carried out until the distillation of the by-product alcohol disappeared. Then, the unreacted phenolic compound is removed under reduced pressure to obtain a phenol aralkyl resin.
【0019】反応温度は通常120〜200℃の範囲で
行われるが、好ましくは130〜160℃である。12
0℃未満では極端に反応が遅くなり、200℃を超える
と反応で副生するアルコールの凝縮が困難となる。The reaction temperature is usually in the range of 120 to 200 ° C, preferably 130 to 160 ° C. 12
If the temperature is lower than 0 ° C, the reaction becomes extremely slow, and if the temperature exceeds 200 ° C, it becomes difficult to condense alcohol by-produced in the reaction.
【0020】また、分縮温度は副生アルコールの沸点〜
150℃の範囲であるが、好ましくは65〜100℃で
ある。副生アルコールの沸点未満では副生アルコールの
蓄積が起こり、反応温度の低下、反応の長時間化をきた
す。150℃を超えると高濃度のフェノール化合物を含
有したアルコールが抜き出され、反応系のモル比に影響
する。Further, the partial condensation temperature is from the boiling point of the by-product alcohol to
The temperature is in the range of 150 ° C, preferably 65 to 100 ° C. If the boiling point of the by-produced alcohol is lower than the boiling point of the by-produced alcohol, the by-produced alcohol accumulates, which lowers the reaction temperature and prolongs the reaction. When the temperature exceeds 150 ° C, alcohol containing a high concentration of phenol compound is extracted, which affects the molar ratio of the reaction system.
【0021】反応は加圧、常圧のいずれでも良いが、常
圧あるいは1000mmH2O以下の僅かな加圧が好ま
しい。著しい加圧下の反応では、反応条件を安定させる
ことが困難となる。The reaction may be carried out under pressure or atmospheric pressure, but atmospheric pressure or slight pressurization of 1000 mmH 2 O or less is preferred. It becomes difficult to stabilize the reaction conditions in the reaction under significantly increased pressure.
【0022】尚、触媒の併用により塩酸が発生するため
反応器をはじめ凝縮器等の製造設備はガラス等の腐食さ
れない材質が好ましい。Since hydrochloric acid is generated by the combined use of a catalyst, it is preferable to use glass or other non-corrosive materials for manufacturing equipment such as a reactor and a condenser.
【0023】[0023]
【実施例】以下、実施例により更に詳細に本発明を説明
する。 実施例1 229.0g(2.433モル)のフェノールと、30
0g(1.805モル)のPXDMと、8.0gのメタ
ノールおよび0.976gの塩化亜鉛を含有する2.6
36gの塩化亜鉛水溶液を、70℃の冷却水を通した凝
縮器を備えた反応器に装入し、撹拌しながらオイルバス
で昇温した。液温が140℃に達したところで、0.2
54gのシュウ酸を含有する1.054gのシュウ酸水
溶液を反応器に添加して、2.5時間反応を行った後、
一回目と同量のシュウ酸水溶液を添加した。更に、1.
5時間反応した後、一回目と同量のシュウ酸水溶液を添
加し、150℃に昇温後3時間かけてメタノールの留出
が無くなるまで反応を行った。次いで液温を160℃に
昇温し、減圧下で未反応のフェノールを除去して、僅か
に白濁した軟化点94℃の樹脂400.2gを得た。こ
れを化合物Aとする。The present invention will be described in more detail with reference to the following examples. Example 1 229.0 g (2.433 mol) of phenol, 30
2.6 containing 0 g (1.805 mol) of PXDM and 8.0 g of methanol and 0.976 g of zinc chloride.
36 g of zinc chloride aqueous solution was charged into a reactor equipped with a condenser through which cooling water at 70 ° C. was passed, and the temperature was raised in an oil bath while stirring. When the liquid temperature reached 140 ° C, 0.2
After adding 1.054 g of an oxalic acid aqueous solution containing 54 g of oxalic acid to the reactor and conducting the reaction for 2.5 hours,
The same amount of oxalic acid aqueous solution as the first time was added. Furthermore, 1.
After reacting for 5 hours, the same amount of oxalic acid aqueous solution as in the first reaction was added, and the temperature was raised to 150 ° C., and the reaction was continued for 3 hours until the distillation of methanol disappeared. Next, the liquid temperature was raised to 160 ° C. and unreacted phenol was removed under reduced pressure to obtain 400.2 g of a slightly cloudy resin having a softening point of 94 ° C. This is designated as Compound A.
【0024】実施例2 158.59g(1.685モル)のフェノールと、2
00g(1.203モル)のPXDMと、4.76gの
メタノールおよび1.076gの塩化亜鉛を含有する
3.076gの塩化亜鉛水溶液を、70℃の冷却水を通
した凝縮器を備えた反応器に装入し、撹拌しながらオイ
ルバスで昇温した。液温が140℃に達したところで、
0.906gのシュウ酸を含有する10.906gの水
溶液を2時間20分かけて連続的に添加した。次いで、
液温を150℃に昇温後3時間熟成を行い、反応を完結
した。次いで液温を160℃に昇温し、減圧下で未反応
のフェノールを除去して、僅かに白濁した軟化点93.
5℃の樹脂248.5gを得た。これを化合物Bとす
る。Example 2 158.59 g (1.685 mol) of phenol and 2
Reactor equipped with a condenser in which 00 g (1.203 mol) of PXDM and 3.076 g of an aqueous zinc chloride solution containing 4.76 g of methanol and 1.076 g of zinc chloride were passed through cooling water at 70 ° C. The mixture was charged into and heated with an oil bath while stirring. When the liquid temperature reaches 140 ° C,
10.906 g of an aqueous solution containing 0.906 g of oxalic acid was continuously added over 2 hours and 20 minutes. Then
After raising the liquid temperature to 150 ° C., aging was carried out for 3 hours to complete the reaction. Next, the liquid temperature was raised to 160 ° C., unreacted phenol was removed under reduced pressure, and the slightly softened softening point 93.
248.5 g of resin at 5 ° C. was obtained. This is designated as Compound B.
【0025】実施例3 634.44g(6.741モル)のフェノールと、1
9.0gのメタノールおよび5.511gの塩化亜鉛を
含有した15.511gの塩化亜鉛水溶液を、70℃の
冷却水を通した凝縮器を備えた反応器に装入し、撹拌し
ながらオイルバスで昇温した。液温が145℃に達した
ところで、800.0g(4.813モル)のPXDM
と5.101gのシュウ酸を含有した55.101gの
シュウ酸水溶液を同時に3時間かけて連続的に添加し
た。次いで、液温を155℃に昇温して2時間熟成を行
い、反応を完結した。次いで液温を160℃に昇温し、
減圧下で未反応のフェノールを除去して、僅かに白濁し
た軟化点93.0℃の樹脂1050.5gを得た。これ
を化合物Cとする。Example 3 634.44 g (6.741 mol) of phenol and 1
15.511 g of zinc chloride aqueous solution containing 9.0 g of methanol and 5.511 g of zinc chloride was charged into a reactor equipped with a condenser through which cooling water of 70 ° C. was passed, and stirred in an oil bath. The temperature was raised. When the liquid temperature reached 145 ° C, 800.0 g (4.813 mol) of PXDM
And 55.101 g of oxalic acid aqueous solution containing 5.101 g of oxalic acid were continuously added simultaneously over 3 hours. Next, the liquid temperature was raised to 155 ° C. and aging was carried out for 2 hours to complete the reaction. Then, raise the liquid temperature to 160 ° C.,
Unreacted phenol was removed under reduced pressure to obtain 1050.5 g of a slightly cloudy resin having a softening point of 93.0 ° C. This is designated as Compound C.
【0026】実施例4 634.19g(6.739モル)のフェノールと、1
9.03gのメタノールおよび5.495gの塩化亜鉛
を含有した15.495gの塩化亜鉛水溶液を、70℃
の冷却水を通した凝縮器を備えた反応器に装入し、撹拌
しながらオイルバスで昇温した。液温が145℃に達し
たところで、800.0g(4.813モル)のPXD
Mを3時間かけて連続的に添加した。並行して1.01
3gのシュウ酸を含有した11.013gのシュウ酸水
溶液を13分割して30分に一回づつ、即ち6時間かけ
て添加した。次いで、液温を155℃に昇温して2時間
20分間熟成を行い、反応を完結した。次いで液温を1
60℃に昇温し、減圧下で未反応のフェノールを除去し
て、僅かに白濁した軟化点93.0℃の樹脂1029.
6gを得た。これを化合物Dとする。Example 4 634.19 g (6.739 mol) of phenol and 1
An aqueous solution of 15.495 g of zinc chloride containing 9.03 g of methanol and 5.495 g of zinc chloride was added at 70 ° C.
It was charged into a reactor equipped with a condenser through which the cooling water of (1) was passed, and the temperature was raised in an oil bath while stirring. When the liquid temperature reached 145 ° C, 800.0 g (4.813 mol) of PXD
M was added continuously over 3 hours. 1.01 in parallel
11.013 g of oxalic acid aqueous solution containing 3 g of oxalic acid was divided into 13 portions and added every 30 minutes, that is, over 6 hours. Then, the liquid temperature was raised to 155 ° C. and aging was carried out for 2 hours and 20 minutes to complete the reaction. Then set the liquid temperature to 1
The temperature was raised to 60 ° C., unreacted phenol was removed under reduced pressure, and a slightly cloudy resin 1029.
6 g was obtained. This is designated as Compound D.
【0027】実施例5 229.0g(2.433モル)のフェノールと、30
0g(1.805モル)のPXDMと、8.0gのメタ
ノールおよび0.976gの塩化亜鉛を、70℃の冷却
水を通した凝縮器を備えた反応器に装入し、撹拌しなが
らオイルバスで昇温した。液温が140℃に達したとこ
ろで、0.255gのシュウ酸を含有した1.255g
のシュウ酸水溶液を反応器に添加した。1時間反応を行
った後、一回目と同量のシュウ酸水溶液を添加した。更
に、1時間反応した後、一回目と同量のシュウ酸水溶液
を添加し、155℃に昇温後、3時間かけてメタノール
の留出が無くなるまで反応を行った。次いで液温を16
0℃に昇温し、減圧下で未反応のフェノールを除去し
て、僅かに白濁した軟化点92.5℃の樹脂398.2
gを得た。これを化合物Eとする。Example 5 229.0 g (2.433 mol) of phenol, 30
0 g (1.805 mol) of PXDM, 8.0 g of methanol and 0.976 g of zinc chloride were charged into a reactor equipped with a condenser through which cooling water at 70 ° C. was added, and an oil bath was added while stirring. The temperature was raised. When the liquid temperature reached 140 ° C, 1.255 g containing 0.255 g of oxalic acid
Of oxalic acid in water was added to the reactor. After reacting for 1 hour, the same amount of oxalic acid aqueous solution as the first time was added. Furthermore, after reacting for 1 hour, the same amount of oxalic acid aqueous solution as the first time was added, the temperature was raised to 155 ° C., and the reaction was continued for 3 hours until the distillation of methanol disappeared. Next, raise the liquid temperature to 16
The temperature was raised to 0 ° C., unreacted phenol was removed under reduced pressure, and a slightly cloudy resin 398.2 having a softening point of 92.5 ° C.
g was obtained. This is designated as Compound E.
【0028】比較例1 229.0g(2.433モル)のフェノールと、30
0g(1.805モル)のPXDMと、8.0gのメタ
ノールおよび0.261gの塩化亜鉛を70℃の冷却水
を通した凝縮器を備えた反応器に装入し、撹拌しながら
オイルバスで昇温した。液温が150℃に達したところ
で1時間撹拌したが留出物はなかった。次いで、0.2
51gの塩化亜鉛を追加して1時間撹拌したが留出物は
なかった。更に、0.510gの塩化亜鉛を追加して2
時間撹拌したが留出物はなかった。最後に、0.510
gの塩化亜鉛を追加して160℃に昇温して2時間撹拌
したが留出物はなかった。反応液をガスクロマトグラフ
ィで分析したところ、多量のフェノール、PXDMが検
出され、実質的に反応は行われなかった。Comparative Example 1 229.0 g (2.433 mol) of phenol and 30
Charge 0 g (1.805 mol) of PXDM, 8.0 g of methanol and 0.261 g of zinc chloride into a reactor equipped with a condenser passing through cooling water at 70 ° C., and stir in an oil bath. The temperature was raised. When the liquid temperature reached 150 ° C, the mixture was stirred for 1 hour, but there was no distillate. Then 0.2
51 g of zinc chloride was added and the mixture was stirred for 1 hour, but there was no distillate. Add 0.510 g of zinc chloride and add 2
There was no distillate after stirring for hours. Finally, 0.510
g zinc chloride was added, the temperature was raised to 160 ° C. and the mixture was stirred for 2 hours, but there was no distillate. When the reaction liquid was analyzed by gas chromatography, a large amount of phenol and PXDM were detected, and the reaction was substantially not performed.
【0029】比較例2 229.0g(2.433モル)のフェノールと、30
0g(1.805モル)のPXDMと、8.0gのメタ
ノールおよび0.530gのシュウ酸を70℃の冷却水
を通した凝縮器を備えた反応器に装入し、撹拌しながら
オイルバスで昇温した。液温が140℃に達したところ
で1時間撹拌したが留出物はなかった。次いで、0.5
30gのシュウ酸を追加して1時間撹拌したが留出物は
なかった。更に、0.530gのシュウ酸を追加して2
時間撹拌したが留出物はなかった。反応液をガスクロマ
トグラフィで分析したところ、多量のフェノール、PX
DMが検出され、実質的に反応は行われなかった。Comparative Example 2 229.0 g (2.433 mol) of phenol and 30
Charge 0 g (1.805 mol) of PXDM, 8.0 g of methanol and 0.530 g of oxalic acid into a reactor equipped with a condenser through which cooling water at 70 ° C. was charged, and with stirring in an oil bath. The temperature was raised. When the liquid temperature reached 140 ° C., the mixture was stirred for 1 hour, but there was no distillate. Then 0.5
An additional 30 g of oxalic acid was added and stirred for 1 hour, but there was no distillate. Add 0.530g of oxalic acid to add 2
There was no distillate after stirring for hours. When the reaction liquid was analyzed by gas chromatography, a large amount of phenol, PX
DM was detected with virtually no reaction.
【0030】比較例3 229.0g(2.433モル)のフェノールと、8.
0gのメタノールおよび0.536gのジエチル硫酸を
70℃の冷却水を通した凝縮器を備えた反応器に装入
し、撹拌しながらオイルバスで昇温した。液温が140
℃に達したところで、300g(1.805モル)のP
XDMを3時間かけて連続的に添加した。添加終了後、
1.5時間熟成反応を行った。次いで液温を160℃に
昇温し、減圧下で未反応のフェノールを除去して、軟化
点93.5℃の樹脂377.5gを得た。これを化合物
Fとする。Comparative Example 3 229.0 g (2.433 mol) of phenol;
0 g of methanol and 0.536 g of diethyl sulfuric acid were charged into a reactor equipped with a condenser through which cooling water at 70 ° C was passed, and the temperature was raised in an oil bath while stirring. Liquid temperature is 140
When the temperature reached ℃, 300 g (1.805 mol) of P
XDM was added continuously over 3 hours. After the addition is complete
The maturing reaction was performed for 1.5 hours. Then, the liquid temperature was raised to 160 ° C. and unreacted phenol was removed under reduced pressure to obtain 377.5 g of a resin having a softening point of 93.5 ° C. This is designated as Compound F.
【0031】比較例4 470.5g(4.999モル)のフェノールと、8.
0gのメタノールと、1.046gのジエチル硫酸、5
90g(3.550モル)のPXDMを使用した他は比
較例3と同様にして、軟化点93.0℃の樹脂740g
を得た。これを化合物Gとする。Comparative Example 4 470.5 g (4.999 mol) of phenol;
0 g of methanol and 1.046 g of diethylsulfate, 5
740 g of resin having a softening point of 93.0 ° C. in the same manner as in Comparative Example 3 except that 90 g (3.550 mol) of PXDM was used.
Got This is designated as Compound G.
【0032】実施例及び比較例で使用した塩化亜鉛は試
薬一級品(純度91%以上)、シュウ酸は試薬特級品
(純度99.5%以上、2水和物)を使用した。The zinc chloride used in Examples and Comparative Examples was a reagent first-grade product (purity: 91% or more), and oxalic acid was a reagent special-grade product (purity: 99.5% or more, dihydrate).
【0033】軟化点の測定 測定方法はJIS K2207による。Measurement of softening point The measuring method is according to JIS K2207.
【0034】硬化時間の測定 実施例1〜5で得られた樹脂A、B、C、D、Eおよび
比較例3〜4で得られた樹脂F、Gそれぞれ100重量
部に対して、HMTA12重量部を添加して、粉砕器で
微粉化して、その0.5gを用い、今中機械工業(株)
製のJRS型キュラストメーターを使用して、170℃
で最大トルクに達するまでの時間を測定した。結果を
〔表1〕に示す。Measurement of Curing Time For 100 parts by weight of each of the resins A, B, C, D and E obtained in Examples 1 to 5 and the resins F and G obtained in Comparative Examples 3 to 4, 12 parts by weight of HMTA was used. Part, and pulverized with a pulverizer, 0.5 g of which was used, Imanaka Machinery Co., Ltd.
170 ° C using a JRS type curlastometer manufactured by
The time required to reach the maximum torque was measured. The results are shown in [Table 1].
【0035】[0035]
【表1】 [Table 1]
【0036】[0036]
【発明の効果】本発明の、フェノールアラルキル樹脂は
従来のフェノールアラルキル樹脂に比べ、ヘキサメチレ
ンテトラミンとの硬化反応が著しく改良された樹脂であ
る。更に、弱い触媒を用いるので、樹脂の中に微量残っ
たたとしても、熱安定性が高く、また製造時に発生する
釜かすが少ない等の特徴が期待できる製造方法である。INDUSTRIAL APPLICABILITY The phenol aralkyl resin of the present invention is a resin having a significantly improved curing reaction with hexamethylenetetramine as compared with the conventional phenol aralkyl resin. Furthermore, since a weak catalyst is used, even if a trace amount remains in the resin, the thermal stability is high, and it is a production method that can be expected to have features such as less kettle residue generated during production.
Claims (2)
基、ハロゲン原子を示し、同一でも異なっても良い。)
で示されるフェノール性化合物と下記一般式(2)〔化
2〕 【化2】 (上式中、R3は炭素数が1〜6のアルキル基を示し、
x、yは1または2の整数であり、x+y=3であ
る。)で示されるアラルキルエーテルを反応させて、フ
ェノールアラルキル樹脂を製造する際に、触媒として塩
化亜鉛とシュウ酸を併用することを特徴とするフェノー
ルアラルキル樹脂の製法。1. The following general formula (1) [Chemical formula 1] (In the above formula, R 1 and R 2 represent a hydrogen atom, an alkyl group, a phenyl group or a halogen atom, and may be the same or different.)
And a phenolic compound represented by the following general formula (2) [Chemical Formula 2] (In the above formula, R 3 represents an alkyl group having 1 to 6 carbon atoms,
x and y are integers of 1 or 2 and x + y = 3. ) The method for producing a phenol aralkyl resin, characterized by using zinc chloride and oxalic acid as a catalyst together when a phenol aralkyl resin is produced by reacting the aralkyl ether represented by the formula (1).
のフェノールアラルキル樹脂の製法。2. The method for producing a phenol aralkyl resin according to claim 1, which is carried out in the presence of alcohol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26482792A JPH06116369A (en) | 1992-10-02 | 1992-10-02 | Production of phenolic aralkyl resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26482792A JPH06116369A (en) | 1992-10-02 | 1992-10-02 | Production of phenolic aralkyl resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06116369A true JPH06116369A (en) | 1994-04-26 |
Family
ID=17408762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26482792A Pending JPH06116369A (en) | 1992-10-02 | 1992-10-02 | Production of phenolic aralkyl resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06116369A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003002956A (en) * | 2001-06-19 | 2003-01-08 | Dainippon Ink & Chem Inc | Phenol resin, epoxy resin, epoxy resin composition and cured product thereof |
JP2015189924A (en) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | Phenol aralkyl resin and manufacturing method therefor |
-
1992
- 1992-10-02 JP JP26482792A patent/JPH06116369A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003002956A (en) * | 2001-06-19 | 2003-01-08 | Dainippon Ink & Chem Inc | Phenol resin, epoxy resin, epoxy resin composition and cured product thereof |
JP2015189924A (en) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | Phenol aralkyl resin and manufacturing method therefor |
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