JPH0496915A - Production of polycyclic aromatic resin - Google Patents
Production of polycyclic aromatic resinInfo
- 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
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000203 mixture Substances 0.000 claims abstract description 13
- -1 polycyclic aromatic compound Chemical class 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 7
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 150000002989 phenols Chemical class 0.000 abstract description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004305 biphenyl Substances 0.000 abstract description 3
- 235000010290 biphenyl Nutrition 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract 1
- 229930003836 cresol Natural products 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000008199 coating composition Substances 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 5
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- SNGARVZXPNQWEY-UHFFFAOYSA-N phenylmethanediol Chemical compound OC(O)C1=CC=CC=C1 SNGARVZXPNQWEY-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UZJQAPIBSXPJON-UHFFFAOYSA-N (2,3-dimethylphenyl)methanediol Chemical group CC1=CC=CC(C(O)O)=C1C UZJQAPIBSXPJON-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
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.
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.
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.
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)
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
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)
| 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 |
-
1990
- 1990-08-14 JP JP21372990A patent/JPH0496915A/en active Pending
Cited By (3)
| 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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