JPH0496915A - Production of polycyclic aromatic resin - Google Patents

Production of polycyclic aromatic resin

Info

Publication number
JPH0496915A
JPH0496915A JP21372990A JP21372990A JPH0496915A JP H0496915 A JPH0496915 A JP H0496915A JP 21372990 A JP21372990 A JP 21372990A JP 21372990 A JP21372990 A JP 21372990A JP H0496915 A JPH0496915 A JP H0496915A
Authority
JP
Japan
Prior art keywords
polycyclic aromatic
resin
added
aromatic compound
weight
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
Application number
JP21372990A
Other languages
Japanese (ja)
Inventor
Morio Kimura
木村 護男
Hiroshi Okamoto
弘 岡本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Chemical Co Ltd
Priority to JP21372990A priority Critical patent/JPH0496915A/en
Publication of JPH0496915A publication Critical patent/JPH0496915A/en
Pending legal-status Critical Current

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  • Phenolic Resins Or Amino Resins (AREA)

Abstract

PURPOSE:To obtain the subject resin, excellent in compatibility with urethane- based resins, water resistance, etc., and suitable as coating resins, etc., by mixing a polycyclic aromatic compound with phenols, adding a specific amount of a crosslinking agent thereto and further an acid catalyst and carrying out reaction. CONSTITUTION:With (A) 100 pts.wt. polycyclic aromatic compound such as naphthalene or biphenyl, is mixed (B) 5-50 pts.wt. phenols such as cresol. (C) A crosslinking agent of either (i) an aromatic compound having 2-hydroxymethyl groups or (ii) paraformaldehyde in a molar amount of 0.3-2 times (based on the mixture of A and B) expressed in terms of the hydroxymethyl groups in the component (i) or formaldehyde is added thereto. Furthermore, (D) an acid catalyst such as sulfuric acid is added to carry out reaction, preferably at 90-200 deg.C to afford the objective resin.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は熱可塑性多環芳香族樹脂の製造方法に関するも
のであり、この樹脂は塗料用樹脂等として有用である。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a thermoplastic polycyclic aromatic resin, and this resin is useful as a paint resin and the like.

〔従来の技術〕[Conventional technology]

縮合多環芳香族炭化水素を主成分とする多環芳香族化合
物とp−キシリレングリコールのような架橋剤とを酸触
媒の存在下に反応させると熱硬化性の炭化水素樹脂(C
OPNA樹脂と称されている)か得られることは、特開
昭62−521号、62−522号公報等で知られてい
る。また、多環芳香族化合物と架橋剤としてのパラホル
ムアルデヒドとを反応させて、炭化水素樹脂を得ること
も特開昭62−57.413号公報で知られている。更
に、多環芳香族化合物の他にフェノール類を加えたもの
と架橋剤とを反応させて熱硬化性の炭化水素樹脂を得る
ことも特開昭62−227.924号公報で知られてい
る。
A thermosetting hydrocarbon resin (C
It is known from JP-A-62-521, JP-A-62-522, etc. that OPNA resin (referred to as OPNA resin) can be obtained. It is also known from JP-A-62-57-413 to obtain a hydrocarbon resin by reacting a polycyclic aromatic compound with paraformaldehyde as a crosslinking agent. Furthermore, it is known from JP-A No. 62-227.924 that a thermosetting hydrocarbon resin can be obtained by reacting a polycyclic aromatic compound with phenols added and a crosslinking agent. .

このような樹脂は、成形用、接着用等には優れたもので
あるが、常温では脆いため、塗料用樹脂とするには不都
合がある。すなわち、塗膜形成性が悪く、これを改良す
るためウレタン系架橋樹脂、エポキシ系架橋樹脂等を混
合しようとしても相溶性が悪く、均一な塗膜を得ること
ができない。
Although such resins are excellent for molding, adhesion, etc., they are brittle at room temperature, so they are inconvenient for use as paint resins. That is, the coating film forming properties are poor, and even if an attempt is made to mix a urethane crosslinked resin, an epoxy crosslinked resin, etc. to improve this, the compatibility is poor and a uniform coating film cannot be obtained.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

多環芳香族樹脂は耐熱性の他、耐水性にも優れており、
広い分野での利用か期待されているか、これらの耐水性
等の性能を損なうことなく塗膜形成性が改良された樹脂
が提供できれば、より広い分野での利用が期待できるこ
とになる。本発明はこのような樹脂を提供することを目
的とする。
Polycyclic aromatic resins have excellent heat resistance and water resistance.
Whether it is expected to be used in a wide range of fields, if a resin with improved film forming properties without impairing performance such as water resistance can be provided, it can be expected to be used in a wider range of fields. An object of the present invention is to provide such a resin.

〔課題を解決するための手段〕[Means to solve the problem]

本発明は多環芳香族炭化水素を主成分とする多環芳香族
化合物100重量部に対しフェノール類5〜50重量部
を混合してなる混合物に、少なくとも2個のヒドロキシ
メチル基を有する芳香族化合物及びパラホルムアルデヒ
ドからなる群れから選ばれた少なくとも1種の架橋剤を
該混合物に対してヒドロキシメチル基又はホルムアルデ
ヒドに換算して0.3〜2倍モル添加して、酸触媒の存
在下に反応させる熱可塑性多環芳香族樹脂の製造方法で
ある。
In the present invention, an aromatic compound having at least two hydroxymethyl groups is added to a mixture obtained by mixing 5 to 50 parts by weight of a phenol to 100 parts by weight of a polycyclic aromatic compound mainly composed of a polycyclic aromatic hydrocarbon. At least one crosslinking agent selected from the group consisting of a compound and paraformaldehyde is added to the mixture in moles of 0.3 to 2 times in terms of hydroxymethyl group or formaldehyde, and the mixture is reacted in the presence of an acid catalyst. This is a method for producing a thermoplastic polycyclic aromatic resin.

多環芳香族炭化水素を主成分とする多環芳香族化合物と
しては、ナフタレン、ビフェニル、アセナフテン、アン
トラセン、ピレン、クリセン等の単独又は混合物あるい
はこれらを50重量%以上、好ましくは70重量%以上
含む混合物やタール重油、タールピッチなどが挙げられ
る。ジフェニルエーテル、ジベンゾフラン等も多環芳香
族化合物として、望ましい化合物である。
Polycyclic aromatic compounds containing polycyclic aromatic hydrocarbons as main components include naphthalene, biphenyl, acenaphthene, anthracene, pyrene, chrysene, etc. alone or in mixtures, or at least 50% by weight, preferably at least 70% by weight. Examples include mixtures, heavy tar oil, and tar pitch. Diphenyl ether, dibenzofuran, etc. are also desirable compounds as polycyclic aromatic compounds.

フェノール類としては、フェノール、クレシル、キシレ
ノール、t−ブチルフェノール等の単独又は混合物か挙
げられる。
Examples of phenols include phenol, cresyl, xylenol, t-butylphenol, etc., singly or in mixtures.

多環芳香族化合物とフェノール類の混合割合は、多環芳
香族化合物100重量部に対してフェノール類5〜50
重量部、好ましくは10〜40重量部である。フェノー
ル類の混合割合が少ないとウレタン系架橋樹脂等との相
溶性が悪くなり、多いと耐水性が低下する。
The mixing ratio of the polycyclic aromatic compound and phenols is 5 to 50 parts by weight of the phenol to 100 parts by weight of the polycyclic aromatic compound.
Parts by weight, preferably 10 to 40 parts by weight. If the mixing ratio of phenols is small, the compatibility with urethane crosslinked resin etc. will be poor, and if it is large, water resistance will be reduced.

架橋剤としては、少なくとも2個のヒドロキシメチル基
を有する芳香族化合物又はパラホルムアルデヒドが使用
でき、この芳香族化合物としてはジヒドロキシメチルベ
ンゼン、ジヒドロキシメチルキシレン、トリヒドロキシ
メチルベンゼン等が挙げられる。好ましくはp−キシリ
レングリコールとも称されるp−ジヒドロキシメチルベ
ンセン及びパラホルムアルデヒドである。架橋剤の添加
割合は、多環芳香族化合物とフェノール類の混合物に対
しヒドロキシメチル基又はホルムアルデヒドに換算して
0.3〜2倍モル、好ましくは0.8〜1.6倍モルで
ある。架橋剤の使用量が2倍モルを越えると熱硬化性樹
脂の性質が現れやすくなる。
As the crosslinking agent, an aromatic compound having at least two hydroxymethyl groups or paraformaldehyde can be used, and examples of the aromatic compound include dihydroxymethylbenzene, dihydroxymethylxylene, trihydroxymethylbenzene, and the like. Preferred are p-dihydroxymethylbenzene, also called p-xylylene glycol, and paraformaldehyde. The addition ratio of the crosslinking agent is 0.3 to 2 moles, preferably 0.8 to 1.6 moles, in terms of hydroxymethyl group or formaldehyde, relative to the mixture of the polycyclic aromatic compound and phenol. If the amount of the crosslinking agent used exceeds 2 times the mole, the properties of a thermosetting resin tend to appear.

酸触媒としては、プロトン酸が使用可能であり、例えば
有機スルホン酸、硫酸、しゅう酸、塩酸等が挙げられ、
好ましくはp−トルエンスルホン酸、しゅう酸である。
As the acid catalyst, protonic acids can be used, such as organic sulfonic acids, sulfuric acid, oxalic acid, hydrochloric acid, etc.
Preferred are p-toluenesulfonic acid and oxalic acid.

この使用量は前記混合物とフェノール類の合計に対し0
゜1〜30重量%、好ましくは065〜20重量%であ
る。
This usage amount is 0 for the total of the mixture and phenols.
It is 1 to 30% by weight, preferably 0.65 to 20% by weight.

反応は、90〜200℃、好ましくは100〜150℃
の範囲の反応温度で行うことが適当であり、溶融状態の
他、溶媒に溶解させた状態で実施することができる。反
応が進行するにつれ、重縮合反応が生じ、分子量が増大
する。はぼ1〜10時間で所定の反応が終了する。反応
終了後、トルエン又はトルエンとテトラヒドロフラン混
合液を加え、触媒分離ができるようにして、水洗、脱触
媒を行い、次いで減圧蒸留により溶剤、未反応成分等を
除去するなどの方法により熱可塑性多環芳香族樹脂を得
る。
The reaction is carried out at 90-200°C, preferably 100-150°C.
It is appropriate to carry out the reaction at a temperature within the range of 200 to 3000, and the reaction can be carried out in a molten state or in a state dissolved in a solvent. As the reaction progresses, a polycondensation reaction occurs and the molecular weight increases. The predetermined reaction is completed in about 1 to 10 hours. After the reaction is completed, toluene or a mixture of toluene and tetrahydrofuran is added to enable catalyst separation, followed by washing with water and decatalyst, followed by distillation under reduced pressure to remove the solvent, unreacted components, etc. to form a thermoplastic polycyclic ring. Obtain aromatic resin.

〔実施例〕〔Example〕

実施例1 攪拌機、温度計、コンデンサーを備えたフラスコに、ア
セナフテン215.6g、フェノール56.4g、92
X−パラホルムアルデヒド52.2g。
Example 1 In a flask equipped with a stirrer, a thermometer, and a condenser, 215.6 g of acenaphthene, 56.4 g of phenol, 92
52.2 g of X-paraformaldehyde.

しゅう酸27.7gを加え、110〜112°Cで4時
間反応を行った。
27.7 g of oxalic acid was added, and the reaction was carried out at 110 to 112°C for 4 hours.

次いで、トルエン200gを加え、内容物を溶解し、水
洗を3回行い、触媒を除去したのち、減圧蒸留を行い、
トルエン及び未反応物を除去して熱可塑性多環芳香族樹
脂275g (軟化点123℃)を得た。
Next, 200 g of toluene was added to dissolve the contents, washed with water three times to remove the catalyst, and then distilled under reduced pressure.
Toluene and unreacted substances were removed to obtain 275 g of a thermoplastic polycyclic aromatic resin (softening point: 123°C).

この樹脂5.8gをトルエン/MEK=1/1の混合シ
ンナー5.8gに溶解し、1級OH含有エポキシポリオ
ール(旭電化:EP−6050) 5. 5 gとTD
I系イソシアネート(式日薬品:D−103) 3゜4
gを加え、十分に混合して塗料組成物とした。
5.8 g of this resin was dissolved in 5.8 g of mixed thinner of toluene/MEK = 1/1, and a primary OH-containing epoxy polyol (Asahi Denka: EP-6050) was added. 5 g and TD
I-based isocyanate (Shikinichi Yakuhin: D-103) 3゜4
g was added and thoroughly mixed to prepare a coating composition.

この塗料組成物をテフロン板上に塗布し、室温で7日間
硬化、乾燥したのち、得られた約400趨厚みの塗膜を
はぎとり、自動水蒸気透過度テスターを用いて耐水性の
評価を行った。
This coating composition was applied onto a Teflon plate, cured and dried at room temperature for 7 days, and then the resulting coating film, approximately 400 mm thick, was peeled off and water resistance was evaluated using an automatic water vapor permeability tester. .

実施例2 α−メチルナフタレン21重量%、β−メチルナフタレ
ン38重量%、ビフェニル21重量%、ジメチルナフタ
レン10重量%を含有するメチルナフタレン油198.
8gXp−t−プチルフエノル90.0g、92%−パ
ラホルムアルデヒド65゜2g1しゅう酸57.8gを
加え、110〜112℃で4時間反応を行った。次いで
、実施例1と同様にして熱可塑性多環芳香族樹脂259
g (軟化点86°C)を得た。また、実施例1と同様
にして塗料組成物を得、これについて耐水性の評価を行
った。
Example 2 Methylnaphthalene oil containing 21% by weight of α-methylnaphthalene, 38% by weight of β-methylnaphthalene, 21% by weight of biphenyl, and 10% by weight of dimethylnaphthalene.
8 g x 90.0 g of p-t-butylphenol, 65.2 g of 92% paraformaldehyde, 57.8 g of oxalic acid were added, and the reaction was carried out at 110 to 112°C for 4 hours. Next, thermoplastic polycyclic aromatic resin 259 was prepared in the same manner as in Example 1.
g (softening point 86°C) was obtained. Further, a coating composition was obtained in the same manner as in Example 1, and its water resistance was evaluated.

実施例3 ナフタレン107.5g、p−t−ブチルフェノール5
4.0g、I)−キシリレングリコール99.4gを加
え、100°Cに昇温、p−トルエンスルホン酸1.6
gをイソプロパツール1.6gに溶かした溶液を10分
間で滴下したのち、150°Cで1゜5時間反応を行っ
た。次いで、実施例1と同様にして熱可塑性多環芳香族
樹脂189g (軟化点122°C)を得た。また、実
施例1と同様にして塗料組成物を得、これについて耐水
性の評価を行った。
Example 3 107.5 g of naphthalene, 5 g of pt-butylphenol
4.0 g, 99.4 g of I)-xylylene glycol was added, the temperature was raised to 100°C, and 1.6 g of p-toluenesulfonic acid was added.
A solution prepared by dissolving 1.5 g of isopropanol in 1.6 g of isopropanol was added dropwise over 10 minutes, and the reaction was then carried out at 150°C for 1.5 hours. Next, 189 g of a thermoplastic polycyclic aromatic resin (softening point: 122°C) was obtained in the same manner as in Example 1. Further, a coating composition was obtained in the same manner as in Example 1, and its water resistance was evaluated.

比較例1 アセナフテン308.0g、92X−パラホルムアルデ
ヒド49.0g、Lゆう酸30.8gを加え、110〜
112℃で4時間反応を行った。
Comparative Example 1 Added 308.0 g of acenaphthene, 49.0 g of 92X-paraformaldehyde, and 30.8 g of L oxalic acid, and
The reaction was carried out at 112°C for 4 hours.

次いで、実施例1と同様にして熱可塑性多環芳香族樹脂
314g(軟化点112°C)を得た。また、実施例1
と同様にして塗料組成物を得、これについて塗膜の形成
を行ったが、乾燥の途中で樹脂が分離し、均一な塗膜は
得られなかった。
Next, in the same manner as in Example 1, 314 g of a thermoplastic polycyclic aromatic resin (softening point: 112°C) was obtained. In addition, Example 1
A coating composition was obtained in the same manner as above, and a coating film was formed thereon, but the resin separated during drying and a uniform coating film could not be obtained.

比較例2 本発明の熱可塑性多環芳香族樹脂に代えて、(A)キシ
レン樹脂(三菱ガス化学二カノール旧、(B)クマロン
樹脂(新日鐵化学:V−120)又は(C)石油樹脂(
日本七オン:クイントン1500)を用いた他は実施例
1と同様にして塗料組成物を得、これについて耐水性の
評価を行った。
Comparative Example 2 In place of the thermoplastic polycyclic aromatic resin of the present invention, (A) xylene resin (old Mitsubishi Gas Chemical dikanol), (B) coumaron resin (Nippon Steel Chemical: V-120), or (C) petroleum resin(
A coating composition was obtained in the same manner as in Example 1, except that Nippon Shichion (Quinton 1500) was used, and the water resistance was evaluated.

各実施例及び比較例の結果を第1表に示す。Table 1 shows the results of each example and comparative example.

第  1  表 食用塗料用樹脂等に好適である。Table 1 Suitable for resins for edible paints, etc.

Claims (1)

【特許請求の範囲】[Claims] (1)多環芳香族炭化水素を主成分とする多環芳香族化
合物100重量部に対しフェノール類5〜50重量部を
混合してなる混合物に、少なくとも2個のヒドロキシメ
チル基を有する芳香族化合物及びパラホルムアルデヒド
からなる群れから選ばれた少なくとも1種の架橋剤を該
混合物に対してヒドロキシメチル基又はホルムアルデヒ
ドに換算して0.3〜2倍モル添加して、酸触媒の存在
下に反応させることを特徴とする熱可塑性多環芳香族樹
脂の製造方法
(1) An aromatic compound having at least two hydroxymethyl groups is added to a mixture of 5 to 50 parts by weight of a phenol to 100 parts by weight of a polycyclic aromatic compound whose main component is a polycyclic aromatic hydrocarbon. At least one crosslinking agent selected from the group consisting of a compound and paraformaldehyde is added to the mixture in moles of 0.3 to 2 times in terms of hydroxymethyl group or formaldehyde, and the mixture is reacted in the presence of an acid catalyst. A method for producing a thermoplastic polycyclic aromatic resin, characterized by
JP21372990A 1990-08-14 1990-08-14 Production of polycyclic aromatic resin Pending JPH0496915A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21372990A JPH0496915A (en) 1990-08-14 1990-08-14 Production of polycyclic aromatic resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21372990A JPH0496915A (en) 1990-08-14 1990-08-14 Production of polycyclic aromatic resin

Publications (1)

Publication Number Publication Date
JPH0496915A true JPH0496915A (en) 1992-03-30

Family

ID=16644037

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21372990A Pending JPH0496915A (en) 1990-08-14 1990-08-14 Production of polycyclic aromatic resin

Country Status (1)

Country Link
JP (1) JPH0496915A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001016199A1 (en) * 1999-08-31 2001-03-08 Nippon Steel Chemical Co., Ltd. Aromatic oligomer and use thereof
JP5134752B2 (en) * 2000-07-13 2013-01-30 大日本塗料株式会社 Hydrogenated aromatic oligomer and method for producing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001016199A1 (en) * 1999-08-31 2001-03-08 Nippon Steel Chemical Co., Ltd. Aromatic oligomer and use thereof
US6713591B1 (en) 1999-08-31 2004-03-30 Nippon Steel Chemicals Co., Ltd. Aromatic oligomer and use thereof
JP5134752B2 (en) * 2000-07-13 2013-01-30 大日本塗料株式会社 Hydrogenated aromatic oligomer and method for producing the same

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