JPH0337215A - Production of thermosetting hydrocarbon resin - Google Patents
Production of thermosetting hydrocarbon resinInfo
- Publication number
- JPH0337215A JPH0337215A JP17186489A JP17186489A JPH0337215A JP H0337215 A JPH0337215 A JP H0337215A JP 17186489 A JP17186489 A JP 17186489A JP 17186489 A JP17186489 A JP 17186489A JP H0337215 A JPH0337215 A JP H0337215A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic compound
- paraformaldehyde
- hydrocarbon resin
- thermosetting
- acid catalyst
- 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
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 28
- 239000013032 Hydrocarbon resin Substances 0.000 title claims abstract description 22
- 229920006270 hydrocarbon resin Polymers 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 18
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 17
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 17
- 125000004970 halomethyl group Chemical group 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- -1 polycyclic aromatic compound Chemical class 0.000 claims abstract description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003431 cross linking reagent Substances 0.000 abstract description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 6
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 abstract description 2
- SNGARVZXPNQWEY-UHFFFAOYSA-N phenylmethanediol Chemical compound OC(O)C1=CC=CC=C1 SNGARVZXPNQWEY-UHFFFAOYSA-N 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- GBROPGWFBFCKAG-UHFFFAOYSA-N picene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 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
- 239000002994 raw material 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
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 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
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 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〕
本発明は耐熱性の熱硬化性炭化水素樹脂の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a heat-resistant thermosetting hydrocarbon resin.
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−キシリレンゲルコールやｐ−キシリレンジクロ
ライドのような少なくとも２個のヒドロキシメチル基又
はハロメチル基を有する芳香族化合物を酸触媒の存在下
に反応させると熱硬化性炭化水素樹脂の製造方法が得ら
れることは特開昭６２−５２１号、６２−５２２号公報
等で知られている。この樹脂は縮合多環芳香族樹脂又は
Ｃ０ＰＮＡ樹脂とも称されている。A polycyclic aromatic compound mainly composed of a condensed polycyclic aromatic hydrocarbon and an aromatic compound having at least two hydroxymethyl groups or halomethyl groups such as p-xylylene gelcol or p-xylylene dichloride are combined with an acid catalyst. It is known from JP-A-62-521 and JP-A-62-522 that a method for producing a thermosetting hydrocarbon resin can be obtained by reacting in the presence of . This resin is also called fused polycyclic aromatic resin or C0PNA resin.
また、多環芳香族化合物とパラホルムアルデヒドを酸触
媒の存在下に反応させて熱硬化性炭化水素樹脂を製造す
ることは、特開昭６２−５７．４１３号公報に記載され
ている。しかしながら、この樹脂の製造方法はノボラッ
ク樹脂のそれに類似するため熱硬化性、耐熱性、機械的
性質等のいくつかの点でやや劣るという問題がある。Moreover, the production of a thermosetting hydrocarbon resin by reacting a polycyclic aromatic compound and paraformaldehyde in the presence of an acid catalyst is described in JP-A-62-57.413. However, since the method for producing this resin is similar to that of novolac resin, there is a problem that it is somewhat inferior in some respects such as thermosetting properties, heat resistance, and mechanical properties.
Ｃ０ＰＮＡ樹脂の硬化成形物は耐熱性に他、電気絶練性
、耐湿性等にも優れており、広い分野での利用が期待さ
れているが、架橋剤として用いる少なくとも２個のヒド
ロキシメチル基又はハロメチル基を有する芳香族化合物
が高価であるという問題がある。従って、このような優
れた性質を損なうことなく、他の架橋剤を用いることが
できれば実用上、極めて有意義なことである。Cured molded products of C0PNA resin have excellent heat resistance, electric resistance, moisture resistance, etc., and are expected to be used in a wide range of fields. There is a problem that aromatic compounds having a halomethyl group are expensive. Therefore, it would be extremely meaningful in practice if other crosslinking agents could be used without impairing these excellent properties.
本発明は、縮合多環芳香族炭化水素を主成分とする多環
芳香族化合物とパラホルムアルデヒドを酸触媒の存在下
に反応させたのち、少なくとも２個のヒドロキシメチル
基又はハロメチル基を有する芳香族化合物を加えて酸触
媒の存在下に反応させることを特徴とする熱硬化性炭化
水素樹脂の製造方法である。The present invention produces an aromatic compound having at least two hydroxymethyl groups or halomethyl groups by reacting a polycyclic aromatic compound mainly composed of a condensed polycyclic aromatic hydrocarbon with paraformaldehyde in the presence of an acid catalyst. This is a method for producing a thermosetting hydrocarbon resin, which is characterized by adding a compound and reacting it in the presence of an acid catalyst.
本発明で原料とする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しては、ナフタレン、アセナフ
テン、フェナントレン、アントラセン、ピレン、クリセ
ン、ナフタセン、フルオラン、ペリレン、ピセンおよび
それるのアルキル誘導体等の単独又は混合物が挙げられ
る。また、これらを主成分とするアントラセン油等のタ
ール系重油、ピッチ類、石油系重質油類も使用すること
ができる。Polycyclic aromatic compounds mainly composed of fused polycyclic aromatic hydrocarbons used as raw materials in the present invention include naphthalene, acenaphthene, phenanthrene, anthracene, pyrene, chrysene, naphthacene, fluoran, perylene, picene, and their alkyls. Derivatives may be used alone or in mixtures. Further, tar-based heavy oils such as anthracene oil, pitches, and petroleum-based heavy oils containing these as main components can also be used.
本発明では、架橋剤としてパラホルムアルデヒドと少な
くとも２個のヒドロキシメチル基又はハロメチル基を有
する芳香族化合物とを使用する。In the present invention, paraformaldehyde and an aromatic compound having at least two hydroxymethyl or halomethyl groups are used as crosslinking agents.
この割合は、ホルムアルデヒドに換算したパラホルムア
ルデヒド１モルに対しヒドロキシメチル基又はハロメチ
ル基２個を有するジ置換体に換算した芳香族化合物０．
５〜２モルの範囲であり、より好ましくは１〜３モルの
範囲である。パラホルムアルデヒドと芳香族化合物の添
加順序は、先に多環芳香族化合物とパラホルムアルデヒ
ドとを反応させたのち、次に少なくとも２個のヒドロキ
シメチル基又はハロメチル基を有する芳香族化合物を加
えて反応させる必要がある。先に、パラホルムアルデヒ
ドを反応させ、次に芳香族化合物を反応させることによ
り、パラホルムアルデヒドを使用したことによる耐熱性
等の物性の低下を可及的に少なくとどめることができる
だけでなく、熱流動硬化特性でとらえられる成形性が向
上する。なお、２種類の架橋剤を同時に使用すると反応
性の大きい芳香族化合物が優先的に反応してしまう。This ratio is 1 mol of paraformaldehyde converted to formaldehyde to 0.0 mol of aromatic compound converted to a di-substituted product having two hydroxymethyl groups or halomethyl groups.
It is in the range of 5 to 2 moles, more preferably in the range of 1 to 3 moles. The order of addition of paraformaldehyde and the aromatic compound is that the polycyclic aromatic compound and paraformaldehyde are first reacted, and then the aromatic compound having at least two hydroxymethyl groups or halomethyl groups is added and reacted. There is a need. By reacting paraformaldehyde first and then reacting the aromatic compound, it is possible not only to minimize the decrease in physical properties such as heat resistance caused by the use of paraformaldehyde, but also to achieve thermal fluid curing. Improves moldability as measured by properties. Note that if two types of crosslinking agents are used simultaneously, the highly reactive aromatic compound will react preferentially.
また、少なくとも２個のヒドロキシメチル基又はハロメ
チル基を有する芳香族化合物としては、ジヒドロキシメ
チルベンゼン（キシリレングリコールともいう）、ジヒ
ロキシメチルキシレン、トリヒドロキシメチルベンゼン
、ジクロロメチルベンゼン（キシリレンジクロライドと
もいう）等が挙げられ、好適なものとしてｐ−キシリレ
ングリコールがある。In addition, examples of aromatic compounds having at least two hydroxymethyl groups or halomethyl groups include dihydroxymethylbenzene (also called xylylene glycol), dihydroxymethylxylene, trihydroxymethylbenzene, and dichloromethylbenzene (also called xylylene dichloride). ), and p-xylylene glycol is preferred.
架橋剤の使用割合は多環芳香族化合物１モルに対し、架
橋剤０．５〜５モル（パラホルムアルデヒドについては
ホルムアルデヒドに換算、芳香族化合物についてはヒド
ロキシメチル基又はハロメチル基２個有するジ置換体に
換算）の範囲が適当であり、より好ましくは１〜３モル
の範囲である。The ratio of crosslinking agent to be used is 0.5 to 5 moles of crosslinking agent per mole of polycyclic aromatic compound (for paraformaldehyde, converted to formaldehyde; for aromatic compounds, use a disubstituted compound having two hydroxymethyl groups or halomethyl groups). A suitable range is 1 to 3 moles, more preferably 1 to 3 moles.
酸触媒としては、有機スルフォン酸、硫酸、ＢＦ、、Ａ
ｌＣｌ３等が挙げられるが、トルエンスルフォン酸等の
有機スルフォン酸が好ましい。酸触媒の使用量は原料混
合物の０．２〜ｌｏｗｔ％の範囲、好ましくは１〜１０
ｗｔ％である。As the acid catalyst, organic sulfonic acid, sulfuric acid, BF, A
Examples include lCl3, but organic sulfonic acids such as toluenesulfonic acid are preferred. The amount of acid catalyst used is in the range of 0.2 to lowt% of the raw material mixture, preferably 1 to 10%.
It is wt%.
反応温度は、５０〜２００℃の範囲が適当であり、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。反応時間は、通常１〜１ｏｈｒである。The reaction temperature is suitably in the range of 50 to 200°C, and the reaction can be carried out in a molten state or in a state dissolved in a solvent. The reaction time is usually 1 to 1 ohr.
本発明の熱硬化性炭化水素樹脂は通常、中間縮合反応物
（Ｂステージ樹脂）を経て硬化樹脂とされる。硬化は中
間反応縮合物を更に、１００〜３５０℃に加熱する等の
方法によって行うことができる。当然のことであるが、
直接硬化樹脂とすることもできる。本発明の熱硬化性炭
化水素樹脂はこの中間縮合反応物および硬化樹脂の両者
を含む。The thermosetting hydrocarbon resin of the present invention is usually made into a cured resin through an intermediate condensation reaction product (B-stage resin). Curing can be carried out by further heating the intermediate reaction condensate to 100 to 350°C. Of course,
It can also be a directly cured resin. The thermosetting hydrocarbon resin of the present invention includes both this intermediate condensation reaction product and a cured resin.
実施例 ｌ
攪拌機、温度計、蒸留冷却機を備えた４ツロフラスコに
精製ナフタレン２５６ｇ、９２％パラホルムアルデヒド
４９ｇ１イソプロパノール（ＩＰＡ）２６ｇを仕込み、
９０℃に昇温し、溶解させたのち、ｐ−トルエンスルフ
ォン酸２５．６ｇを等量のＩＰＡに溶解して添加し、９
０〜９６°Ｃで６００分間反応せ、次いで１２０℃まで
昇温させた後、その温度で６００分間反応行い、−次反
応物とした。次いで、ｐ−キシリレングリコール２０７
゜０ｇを加え、１１５℃で１５分間反応した。反応中、
生成した水およびＩＰＡを留出除去し、４６１ｇの熱硬
化性炭化水素樹脂（Ｂ−ステージ）を得た。Example l A 4-tubular flask equipped with a stirrer, a thermometer, and a distillation condenser was charged with 256 g of purified naphthalene, 49 g of 92% paraformaldehyde, and 26 g of isopropanol (IPA).
After heating to 90°C and dissolving it, 25.6 g of p-toluenesulfonic acid was dissolved in an equal amount of IPA and added.
The reaction was carried out at 0 to 96°C for 600 minutes, then the temperature was raised to 120°C, and the reaction was carried out at that temperature for 600 minutes to obtain the next reaction product. Next, p-xylylene glycol 207
0 g was added and reacted at 115° C. for 15 minutes. During the reaction,
The produced water and IPA were removed by distillation to obtain 461 g of thermosetting hydrocarbon resin (B-stage).
この熱硬化性炭化水素樹脂１８ｇにガラス短繊維（約５
ｆｆｌｌｌ＋）１２ｇを混合し、ラボプラストミル（＠
東洋精機製作新製：ミキサータイプＲ−３０、測定条件
１６０℃、回転速度３０ ｒｐｍ、サンプル量３０ｇ）
を用いて熱硬化反応評価試験を行った。Add 18g of this thermosetting hydrocarbon resin to short glass fibers (approximately 5
Mix 12g of ffllll +
Newly manufactured by Toyo Seiki: Mixer type R-30, measurement conditions 160℃, rotation speed 30 rpm, sample amount 30g)
A thermosetting reaction evaluation test was conducted using
結果を第１表に示す。The results are shown in Table 1.
第１表に示すとおり、本発明の熱硬化性炭化水素樹脂は
フェノール樹脂相当の熱流動硬化特性を有し、成形性が
優れている。As shown in Table 1, the thermosetting hydrocarbon resin of the present invention has thermofluidic curing properties comparable to phenolic resin and has excellent moldability.
実施例 ２
実施例１と同様にして、精製アセナフテン３０８．０ｇ
、９２％パラホルムアルデヒド４５．７ｇ、ＩＰＡ３１
ｇを仕込み、ｐ−トルエンスルホン酸２７．３ｇを等量
のＩＰＡに溶解して添加し、９０〜９６°Ｃで６００分
間反応て一次反応物とした。次いで、ｐ−キシリデング
リコール１９３．２ｇを加え、１１５℃で１５分間反応
した。反応中、生成した水およびＩＰＡを留出除去し、
５２６ｇの熱硬化性炭化水素樹脂（Ｂ−ステージ）を得
た。Example 2 Purified acenaphthene 308.0 g in the same manner as Example 1
, 92% paraformaldehyde 45.7g, IPA31
27.3 g of p-toluenesulfonic acid dissolved in an equal amount of IPA was added thereto, and the mixture was reacted at 90 to 96° C. for 600 minutes to obtain a primary reaction product. Next, 193.2 g of p-xylidene glycol was added and reacted at 115°C for 15 minutes. During the reaction, water and IPA produced are removed by distillation,
526 g of thermosetting hydrocarbon resin (B-stage) was obtained.
この熱硬化性炭化水素樹脂について、実施例１と同様に
熱硬化反応評価試験を行った。結果を第１表に示す。A thermosetting reaction evaluation test was conducted on this thermosetting hydrocarbon resin in the same manner as in Example 1. The results are shown in Table 1.
比較例 ｌ
実施例１と同様にして、精製ナフタレン２５６ｇ１９２
％バラホルムアルデヒド４９ｇ、ｐ−キシリレングリコ
ール２０７ｇ、、ＩＰＡ２６ｇを仕込み、９０℃に昇温
し、溶解させたのち、ｐ−トルエンスルホン酸２５．６
ｇを等量のＩＰＡに溶解して添加し、１２０℃で６００
分間反応た。反応中、生成した水およびＩＰＡを留出除
去し、４４３ｇの熱硬化性炭化水素樹脂（Ｂ−ステージ
）を得た。Comparative Example 1 Purified naphthalene 256g 192g in the same manner as in Example 1
% formaldehyde, 207 g of p-xylylene glycol, and 26 g of IPA were heated to 90°C and dissolved, followed by 25.6 g of p-toluenesulfonic acid.
g was dissolved in an equal amount of IPA, added, and heated at 120°C for 600 min.
It reacted for a minute. During the reaction, water and IPA produced were removed by distillation to obtain 443 g of thermosetting hydrocarbon resin (B-stage).
この熱硬化性炭化水素樹脂について、実施例１と同様に
熱硬化反応評価試験を行った。結果を第１表に示す。A thermosetting reaction evaluation test was conducted on this thermosetting hydrocarbon resin in the same manner as in Example 1. The results are shown in Table 1.
比較例 ２
実施例１と同様にして、精製ナフタレン２５６ｇ１ｐ−
キシリレングリコール４１４ｇ、テトラハイドロフラン
（ＴＨＦ）２６ｇを仕込み、１１０℃に昇温し、溶解さ
せたのち、ｐ−トルエンスルホン酸３３．５ｇを等量の
ＴＨＦに溶解して添加し、１２５℃で６００分間反応た
。反応中、生成した水およびＴＨＦを留出除去し、６０
９ｇの熱硬化性炭化水素樹脂（Ｂ−ステージ）を得た。Comparative Example 2 In the same manner as in Example 1, purified naphthalene 256g1p-
414 g of xylylene glycol and 26 g of tetrahydrofuran (THF) were charged, heated to 110°C and dissolved, and then 33.5 g of p-toluenesulfonic acid dissolved in an equal amount of THF was added, and the mixture was heated at 125°C. The reaction was carried out for 600 minutes. During the reaction, water and THF produced were removed by distillation, and 60
9 g of thermosetting hydrocarbon resin (B-stage) was obtained.
この熱硬化性炭化水素樹脂について、実施例１と同様に
熱硬化反応評価試験を行った。結果を第１表に示す。A thermosetting reaction evaluation test was conducted on this thermosetting hydrocarbon resin in the same manner as in Example 1. The results are shown in Table 1.
比較例 ３
実施例１と同様にして、精製アセナフテン３０８ｇ、９
−キシリレングリコール３８０．９ｇ、テトラハイドロ
フラン（ＴＨＦ）３１ ｇを仕込み、１１０℃に昇温し
、溶解させたのち、ｐ−トルエンスルホン酸３４．５ｇ
を等量のＴＨＦに溶解して添加し、１１０−１１６℃で
１００分間反応した。Comparative Example 3 In the same manner as in Example 1, 308 g of purified acenaphthene, 9
- 380.9 g of xylylene glycol and 31 g of tetrahydrofuran (THF) were charged, heated to 110°C and dissolved, and then 34.5 g of p-toluenesulfonic acid.
was dissolved in an equal amount of THF and added, and reacted at 110-116°C for 100 minutes.
反応中、生成した水およびＴＨＦを留出除去し、６４９
ｇの熱硬化性炭化水素樹脂（Ｂ−ステージ）を得た。During the reaction, water and THF produced are removed by distillation, and 649
A thermosetting hydrocarbon resin (B-stage) of g was obtained.
この熱硬化性炭化水素樹脂について、実施例１と同様に
熱硬化反応評価試験を行った。結果を第１表に示す。A thermosetting reaction evaluation test was conducted on this thermosetting hydrocarbon resin in the same manner as in Example 1. The results are shown in Table 1.
第 ｌ 表
硬化終了の判定は、材料の破壊が起こりトルクが０ 、
５ ｋｇ−ｍになったときとした。Table 1 Judgment of completion of hardening is made when the material is destroyed and the torque is 0.
5 kg-m.
なお、代表的なフェノールランダムノボラック−へキサ
メチレンテトラミン系の最低トルクはＯ１５ ｋｇ−ｍ
であり、硬化終了時間は６分である。The minimum torque of a typical phenol random novolak-hexamethylenetetramine system is O15 kg-m.
The curing completion time is 6 minutes.
本発明の製造方法によれば、耐熱性、成形性のすぐれた
熱硬化性炭化水素樹脂を得ることができる。また、高価
な架橋剤の使用量を減少させることもできる。According to the production method of the present invention, a thermosetting hydrocarbon resin with excellent heat resistance and moldability can be obtained. It is also possible to reduce the amount of expensive crosslinking agents used.
Claims (2)
族化合物とパラホルムアルデヒドを酸触媒の存在下に反
応させたのち、少なくとも２個のヒドロキシメチル基又
はハロメチル基を有する芳香族化合物を加えて酸触媒の
存在下に反応させることを特徴とする熱硬化性炭化水素
樹脂の製造方法。(1) An aromatic compound having at least two hydroxymethyl groups or halomethyl groups obtained by reacting a polycyclic aromatic compound mainly composed of fused polycyclic aromatic hydrocarbons with paraformaldehyde in the presence of an acid catalyst. A method for producing a thermosetting hydrocarbon resin, which comprises adding and reacting the resin in the presence of an acid catalyst.
キシメチル基又はハロメチル基を有する芳香族化合物と
の割合が、ホルムアルデヒドに換算したパラホルムアル
デヒド１モルに対しヒドロキシメチル基又はハロメチル
基２個を有するジ置換体に換算した芳香族化合物０．５
〜２モルである請求項１記載の熱硬化性炭化水素樹脂の
製造方法。(2) The ratio of paraformaldehyde and an aromatic compound having at least two hydroxymethyl groups or halomethyl groups to a disubstituted compound having two hydroxymethyl groups or halomethyl groups per mol of paraformaldehyde converted to formaldehyde. Converted aromatic compound 0.5
2. The method for producing a thermosetting hydrocarbon resin according to claim 1, wherein the amount is 2 mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17186489A JPH0337215A (en) | 1989-07-05 | 1989-07-05 | Production of thermosetting hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17186489A JPH0337215A (en) | 1989-07-05 | 1989-07-05 | Production of thermosetting hydrocarbon resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0337215A true JPH0337215A (en) | 1991-02-18 |
Family
ID=15931204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17186489A Pending JPH0337215A (en) | 1989-07-05 | 1989-07-05 | Production of thermosetting hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0337215A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110098759A (en) * | 2008-12-25 | 2011-09-01 | 후지텍크가부시키가이샤 | Method and device for managing/controlling group of elevators |
| WO2014203867A1 (en) * | 2013-06-18 | 2014-12-24 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin, and epoxy resin, and method for producing said resins |
| JP2015000969A (en) * | 2013-06-18 | 2015-01-05 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin and modified aromatic hydrocarbon formaldehyde resin |
| US9278828B2 (en) | 2011-01-26 | 2016-03-08 | Mitsubishi Electric Corporation | Group management control device for elevator |
-
1989
- 1989-07-05 JP JP17186489A patent/JPH0337215A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110098759A (en) * | 2008-12-25 | 2011-09-01 | 후지텍크가부시키가이샤 | Method and device for managing/controlling group of elevators |
| US9278828B2 (en) | 2011-01-26 | 2016-03-08 | Mitsubishi Electric Corporation | Group management control device for elevator |
| WO2014203867A1 (en) * | 2013-06-18 | 2014-12-24 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin, and epoxy resin, and method for producing said resins |
| JP2015000969A (en) * | 2013-06-18 | 2015-01-05 | 三菱瓦斯化学株式会社 | Aromatic hydrocarbon formaldehyde resin and modified aromatic hydrocarbon formaldehyde resin |
| US20160130383A1 (en) * | 2013-06-18 | 2016-05-12 | Mitsubishi Gas Chemical Company, Inc. | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin, and epoxy resin, and method for producing these |
| US9725551B2 (en) * | 2013-06-18 | 2017-08-08 | Mitsubishi Gas Chemical Company, Inc. | Aromatic hydrocarbon formaldehyde resin, modified aromatic hydrocarbon formaldehyde resin and epoxy resin, and method for producing these |
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