JPS6351419A - Production of thermosetting hydrocarbon resin - Google Patents
Production of thermosetting hydrocarbon resinInfo
- Publication number
- JPS6351419A JPS6351419A JP19602786A JP19602786A JPS6351419A JP S6351419 A JPS6351419 A JP S6351419A JP 19602786 A JP19602786 A JP 19602786A JP 19602786 A JP19602786 A JP 19602786A JP S6351419 A JPS6351419 A JP S6351419A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aromatic compound
- thermosetting resin
- resin
- crosslinking agent
- 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 32
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000013032 Hydrocarbon resin Substances 0.000 title description 7
- 229920006270 hydrocarbon resin Polymers 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- -1 polycyclic aromatic compound Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 125000004970 halomethyl group Chemical group 0.000 claims abstract description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract description 10
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 7
- 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 6
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000295 fuel oil Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011295 pitch Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct 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
- 239000011294 coal tar pitch Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-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
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DQJJXEZXOYPSNJ-UHFFFAOYSA-N [2,3-bis(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1CO DQJJXEZXOYPSNJ-UHFFFAOYSA-N 0.000 description 1
- CKYOUYSBIZYHNU-UHFFFAOYSA-N [2-(hydroxymethyl)-3,4-dimethylphenyl]methanol Chemical group CC1=CC=C(CO)C(CO)=C1C CKYOUYSBIZYHNU-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- JDPBLCQVGZLACA-UHFFFAOYSA-N benzo[a]perylene Chemical class C1=CC(C=2C3=CC=CC=C3C=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 JDPBLCQVGZLACA-UHFFFAOYSA-N 0.000 description 1
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000011301 petroleum pitch Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 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
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、熱硬化性縮合多環多核芳香族炭化水素樹脂の
製造方法に関し、更に詳しくは３環以上の縮合多環芳香
族化合物を主成分とする原料物質と、少くとも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
物を主成分とする架橋剤を、酸触媒の存在下に加熱反応
させる熱硬化性炭化水素樹脂の製造方法の改良に関する
。[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for producing a thermosetting condensed polycyclic polynuclear aromatic hydrocarbon resin, more specifically, the present invention relates to a method for producing a thermosetting condensed polycyclic polynuclear aromatic hydrocarbon resin, and more specifically, the present invention relates to a method for producing a thermosetting condensed polycyclic polynuclear aromatic hydrocarbon resin, and more specifically, the present invention relates to a method for producing a thermosetting condensed polycyclic polynuclear aromatic hydrocarbon resin, and more specifically, Related to improvements in the method for producing thermosetting hydrocarbon resins, in which a raw material and a crosslinking agent whose main component is an aromatic compound having at least two hydroxymethyl groups or halomethyl groups are heated and reacted in the presence of an acid catalyst. .
さきに本発明者らの一人は、縮合多環芳香族化合物を主
成分とする原料物質と少くとも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主成分とす
る架橋剤を酸触媒の存在下に加熱反応させることにより
、容易に且つ安価に製造される耐熱性の優れた。縮合多
環多核芳香族炭化水素樹脂を見出し、それをＣ０ＰＮＡ
樹脂と命名した（特願昭６０−３００５５号）。Previously, one of the inventors of the present invention has developed an acid-catalyzed method using a raw material mainly composed of a fused polycyclic aromatic compound and a crosslinking agent mainly composed of an aromatic compound having at least two hydroxymethyl groups or halomethyl groups. It has excellent heat resistance and can be produced easily and inexpensively by carrying out a heating reaction in the presence of. Discovered a condensed polycyclic polynuclear aromatic hydrocarbon resin and developed it into C0PNA.
It was named resin (Japanese Patent Application No. 60-30055).
ところで、このようなＣ０ＰＮＡ樹脂の製造法において
は１重合度の高い熱硬化性樹脂（Ｂステージ樹脂）を得
ようとすると、著しく長時間を要するという問題がある
。一方、反応時間を短縮するために、触媒量を増加し、
反応温度を高くして反応を促進させと、反応混合物は部
分的に発泡状態を示すようになり、そして、得られた熱
硬化性樹脂も多孔体となり加工性が悪くなるという欠点
が生じた。However, in this method of producing C0PNA resin, there is a problem in that it takes a very long time to obtain a thermosetting resin (B-stage resin) with a high degree of monopolymerization. On the other hand, in order to shorten the reaction time, the amount of catalyst was increased,
When the reaction temperature was increased to accelerate the reaction, the reaction mixture partially became foamed, and the resulting thermosetting resin also became porous, resulting in poor processability.
本発明は、Ｃ０ＰＮＡ樹脂の製造に見られる前記欠点を
克服することにある。The present invention seeks to overcome the aforementioned drawbacks found in the production of C0PNA resins.
本発明によれば、３環以上の縮合多環芳香族化合物を主
成分とする原料物質と、少くとも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主成分と
する架橋剤を、酸触媒の存在下に加熱反応させて熱硬化
性樹脂を製造するに当り、該反応混合物を減圧下に保持
して反応させた後、常圧ないし加圧下で降温し、反応を
停止することを特徴とする熱硬化性樹脂の製造方法が提
供される。According to the present invention, a raw material whose main component is a fused polycyclic aromatic compound having three or more rings, and a crosslinking agent whose main component is an aromatic compound having at least two hydroxymethyl groups or halomethyl groups, When producing a thermosetting resin by heating the reaction in the presence of an acid catalyst, the reaction mixture is kept under reduced pressure to react, and then the temperature is lowered under normal pressure or increased pressure to stop the reaction. A method for producing a characteristic thermosetting resin is provided.
以下本発明について詳述する。The present invention will be explained in detail below.
本発明で原料物質として用いる縮合多環芳香族化合物と
しては、３環以上の縮合多環芳香族化合物、又はこれを
主成分として含む混合物が用いられる。本発明で用いる
縮合多環芳香族化合物は、３〜５環のものが好ましく用
いられ、このようなものの具体例としては、例えば、フ
ェナントレン。As the fused polycyclic aromatic compound used as a raw material in the present invention, a fused polycyclic aromatic compound having three or more rings or a mixture containing this as a main component is used. The fused polycyclic aromatic compound used in the present invention preferably has 3 to 5 rings, and a specific example of such a compound is phenanthrene.
アントラセン、ピレン、クリセン、ナフタセン、フルオ
ランテン、ペリレン、ピセン及びそれらのアルキル誘導
体、各種ベンゾピレン、各種ベンゾペリレン等があり、
また、それらの縮合ベンゼン核がメチレン基や、フェニ
レン基、キシリレン基等で連結された多環多核構造の炭
化水素も包含される。本発明で原料物質として用いる前
記縮合多環芳香族化合物は必ずしも単独で用いる必要は
なく、それらの混合物を用いることもできるし、更にそ
れらの混合物を主成分として含むものも用いられる。Anthracene, pyrene, chrysene, naphthacene, fluoranthene, perylene, picene and their alkyl derivatives, various benzopyrenes, various benzoperylenes, etc.
Further, hydrocarbons having a polycyclic polynuclear structure in which these condensed benzene nuclei are connected by a methylene group, a phenylene group, a xylylene group, etc. are also included. The condensed polycyclic aromatic compound used as a raw material in the present invention does not necessarily need to be used alone; a mixture thereof can also be used, and a compound containing a mixture thereof as a main component can also be used.
このような多環芳香族化合物混合物を主成分とする原料
物質としては、石油又は石炭から得られる芳香族炭素分
率ｆａ値が０．６以上であって且つ芳香環水素量Ｈａ値
が２０％以上である重質油類又はピッチ類が挙げられる
。この場合のｆａ値及びＨａ値は次の式で定義されるも
のである。The raw material containing such a mixture of polycyclic aromatic compounds as a main component is one that is obtained from petroleum or coal and has an aromatic carbon fraction fa value of 0.6 or more and an aromatic ring hydrogen amount Ha value of 20%. Examples include the heavy oils and pitches listed above. The fa value and Ha value in this case are defined by the following equations.
但し、このｆａ値は元素分析値とＪｌ−ＮＭＲを用いて
Ｂｒｏｗｎ−Ｌａｄｎｃｒ法によって計算して得られる
値であり、またＨａ値は１）１−ＮＭＲを用いて得られ
る値である。However, this fa value is a value obtained by calculating by the Brown-Ladncr method using elemental analysis values and Jl-NMR, and the Ha value is a value obtained using 1) 1-NMR.
ｆａ値が０．６より小さい重質油類又はピッチ類を用い
た場合には、その芳香族分が少ないため耐熱性の優れた
熱硬化性樹脂は得られず、またＨａ値が２０％より小さ
い重質油類又はピンチ類を用いた場合には、その芳香環
水素置が少ないため架橋度の劣った樹脂を生成する。特
にｆａ値が０．７以上で且つ）Ｈａ値が３０％以上のも
のを用いるのが好ましい。If heavy oils or pitches with an fa value of less than 0.6 are used, a thermosetting resin with excellent heat resistance cannot be obtained due to the low aromatic content, and if the Ha value is less than 20%. When small heavy oils or pinch oils are used, a resin having a poor degree of crosslinking is produced because there are few hydrogen atoms in the aromatic ring. In particular, it is preferable to use a material having an fa value of 0.7 or more and a) Ha value of 30% or more.
なお、重質油類及びピッチ類としては、分子電が約２０
０以上のものを用いるのが好ましい。このような重質油
類及びピッチ類としては、コールタールピッチ、石油系
重質芳香族成分、石油系ピッチ又はそれからの分画成分
などが挙げられる。In addition, heavy oils and pitches have a molecular charge of approximately 20
It is preferable to use 0 or more. Examples of such heavy oils and pitches include coal tar pitch, petroleum-based heavy aromatic components, petroleum-based pitch, and fractionated components thereof.
コールタールピッチは、３〜５環の縮合多環芳香族化合
物を主体とする曵雑な混合物であり、平均分子址は３０
０前後で、純粋な３〜４環の縮合多環芳香族化合物のそ
れよりは一般に太きい。Coal tar pitch is a complex mixture mainly composed of fused polycyclic aromatic compounds with 3 to 5 rings, and has an average molecular mass of 30
It is around 0, and is generally thicker than that of a pure 3- to 4-ring condensed polycyclic aromatic compound.
石油系重質油類及びピッチ類としては、例えば減圧軽油
の接触分解残渣油、ナフサの熱分解残渣油、これらから
調製されたピッチ及びピッチの製造過程で生成する重質
油留分などが好んで用いられる。As petroleum-based heavy oils and pitches, for example, catalytic cracking residual oil of vacuum gas oil, thermal cracking residual oil of naphtha, pitch prepared from these, and heavy oil fractions generated in the pitch manufacturing process are preferable. It is used in
架橋剤としては、ヒドロキシメチル基（ＨＯＣＨ２−）
又はハロメチル基（ＸＣＩＩ、−１Ｘ：ハロゲン）を少
なくとも２個、通常２〜３個有する芳香族化合物が用い
られ、この場合、芳香族化合物としては、縮合環芳香族
化合物及び非縮合芳香族化合物を問わず使用可能である
が、一般には、そのベンゼン核数が。As a crosslinking agent, hydroxymethyl group (HOCH2-)
Alternatively, an aromatic compound having at least 2, usually 2 to 3 halomethyl groups (XCII, -1X: halogen) is used. In this case, the aromatic compound includes a fused ring aromatic compound and a non-fused aromatic compound. It can be used regardless of the number of benzene nuclei, but in general, the number of benzene nuclei.
１〜５、好ましくは、１〜４のものが使用される。この
ような芳香族化合物から誘導される架橋剤の具体例とし
ては、例えば、ベンゼン、キシレン、ナフタレン、アン
トラセン、ピレン、又はそれらのアルキル誘導体等のポ
リ（ヒドロキシメチル）化合物や、ポリ（ハロメチル）
化合物が挙げられる。また、前記芳香族化合物を含むコ
ールタール留分や石油留分のポリ（ヒドロキシメチル）
化物や、ポリ（ハロメチル）化物も使用可能である。本
発明で用いる架橋剤のうち、ジ（ヒドロキシメチル）ベ
ンゼン、ジ（ヒドロキシメチル）キシレン及びトリ（ヒ
ドロキシメチル）ベンゼンは特に好ましいものである。1 to 5, preferably 1 to 4 are used. Specific examples of crosslinking agents derived from such aromatic compounds include poly(hydroxymethyl) compounds such as benzene, xylene, naphthalene, anthracene, pyrene, or their alkyl derivatives, and poly(halomethyl) compounds.
Examples include compounds. In addition, poly(hydroxymethyl) from coal tar fractions and petroleum fractions containing the above-mentioned aromatic compounds.
Compounds and poly(halomethyl) compounds can also be used. Among the crosslinking agents used in the present invention, di(hydroxymethyl)benzene, di(hydroxymethyl)xylene and tri(hydroxymethyl)benzene are particularly preferred.
前記原料縮合多環芳香族化合物と前記架橋剤とを酸触媒
の存在下に加熱反応させることにより、所望の熱硬化性
樹脂（Ｂステージ樹脂）が得られる。A desired thermosetting resin (B-stage resin) is obtained by subjecting the raw material condensed polycyclic aromatic compound and the crosslinking agent to a heating reaction in the presence of an acid catalyst.
この場合、原料物質に対する架橋剤の混合比は、モル比
挽算で０．２〜１０の範囲内で、目的とする熱硬化性樹
脂の性状に合せて選択される。In this case, the mixing ratio of the crosslinking agent to the raw material is selected within the range of 0.2 to 10 based on the molar ratio, depending on the properties of the desired thermosetting resin.
酸触媒しては、ルイス酸、ブレンステッド酸のいずれも
使用可能であるが、通常は、トルエンスルホン酸、キシ
レンスルホン酸、硫酸などのブレンステッド酸が用いら
れる。酸触媒の使用量は原料物質と架橋剤との合計量に
対して、０．２〜２０重量％、好ましくは１〜１０重量
％の範囲内で、反応条件及び原料物質の反応性を加味し
て調整される。反応温度は約７０〜約３００℃、好まし
くは１００〜２００℃である。As the acid catalyst, both Lewis acids and Bronsted acids can be used, but Bronsted acids such as toluenesulfonic acid, xylenesulfonic acid, and sulfuric acid are usually used. The amount of the acid catalyst to be used is within the range of 0.2 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the raw material and crosslinking agent, taking into account the reaction conditions and the reactivity of the raw material. It is adjusted accordingly. The reaction temperature is about 70 to about 300°C, preferably 100 to 200°C.
本発明においては、反応混合物を減圧下に保持して反応
を行う。本発明においては、反応を絶対圧力０−７５０
ｍｍ１１ｇ、好ましくは１−３００１−３Ｏ０で行う。In the present invention, the reaction is carried out while maintaining the reaction mixture under reduced pressure. In the present invention, the reaction is carried out at an absolute pressure of 0-750
mm11g, preferably 1-3001-3O0.
このようにして反応を進める時には１反応混合物は重縮
合反応を受けて分子量を増大して行くが、反応系が減圧
下に保持されていることがら重縮合反応で副生する低分
子量物質は反応系外に除去され、その反応は著しく促進
される。加熱反応をさらに進めると、不溶不融性の硬化
体となるが、本発明では、不溶不融性の硬化体が生成す
る以前に常圧又は加圧下で降温させて反応を停止する。When the reaction proceeds in this way, one reaction mixture undergoes a polycondensation reaction and its molecular weight increases, but since the reaction system is maintained under reduced pressure, low molecular weight substances that are by-produced in the polycondensation reaction do not react. It is removed from the system and the reaction is significantly accelerated. If the heating reaction is further advanced, an insoluble and infusible cured product is produced, but in the present invention, the reaction is stopped by lowering the temperature at normal pressure or under increased pressure before an insoluble and infusible cured product is produced.
減圧下の反応において副生した低分子量物質の揮散によ
り生じていた発泡状態は、反応系を常圧又は加圧に保持
すると消失する。従って、降温に際しては、反応生成物
は非発泡の状態で降温され、反応停止されることとなり
、その結果、得られる熱硬化性樹脂は多孔体とならず、
緻密な固体状物となる。The foaming state caused by volatilization of low molecular weight substances produced as by-products during the reaction under reduced pressure disappears when the reaction system is maintained at normal pressure or increased pressure. Therefore, when the temperature is lowered, the reaction product is cooled in a non-foamed state and the reaction is stopped, and as a result, the obtained thermosetting resin does not become a porous body.
It becomes a dense solid.
反応を停止させるには、反応生成物を、通常、７０℃以
下の温度に降下させればよい。In order to stop the reaction, the temperature of the reaction product should generally be lowered to 70° C. or lower.
前記のようにして得られる反応生成物は未だ加熱溶融性
を残した熱硬化性樹脂であり、未硬化中間縮合物である
。本発明によれば、高軟化点（高重合度）の熱硬化性樹
脂を得ることができるが、本発明は、殊に軟化点８０℃
以上、好ましくは８０〜１６０℃を有する韮軟化点熱硬
化性樹脂の製造に好適である。このような高軟化点熱硬
化性樹脂は、すぐれた成形性を有し、成形材料として各
種の分野に有利に利用される。The reaction product obtained as described above is a thermosetting resin that still has heat-melting properties and is an uncured intermediate condensate. According to the present invention, a thermosetting resin with a high softening point (high degree of polymerization) can be obtained, but the present invention particularly provides a thermosetting resin with a softening point of 80°C.
As described above, it is suitable for producing a thermosetting resin with a softening point preferably having a temperature of 80 to 160°C. Such high softening point thermosetting resins have excellent moldability and are advantageously used as molding materials in various fields.
本発明で得られる熱硬化性樹脂は、熱溶融性を示すと共
に、Ｎ−メチル−２−ピロリドン等の有機溶媒に対して
溶解性を示すもので、各種複合材料の結合剤や、接着剤
、成形物材料として利用される。The thermosetting resin obtained in the present invention exhibits heat melting properties and is soluble in organic solvents such as N-methyl-2-pyrrolidone, and can be used as a binder for various composite materials, adhesives, etc. Used as a molding material.
そして１本発明の熱硬化性樹脂を用いて得られた製品に
おいては、これを約１５０〜約３００℃に加熱し、熱硬
化性樹脂の重縮合反応を完結させることにより、その熱
硬化性樹脂を不溶不融性の硬化体とすることができる。In products obtained using the thermosetting resin of the present invention, the thermosetting resin is heated to about 150 to about 300°C to complete the polycondensation reaction of the thermosetting resin. can be made into an insoluble and infusible cured product.
この熱硬化処理は、良好な硬化体を得るために、加圧下
で行うのが望ましい。また、この硬化物の物性向」−の
ために、ポストキュアーを行うこともできる。このポス
トキュアーは、一般に約１５０〜約４００°Ｃの温度で
実施される・〔効 果〕
本発明によれば、前記のように、高軟化点（高重合度）
熱硬化性樹脂を短縮された時間で得ることができ、しか
も、得られる樹脂は高軟化点を有するにもかかわらず、
均一で緻密な形態を有する。This heat curing treatment is preferably carried out under pressure in order to obtain a good cured product. Further, post-curing can be performed due to the physical properties of the cured product. This post-curing is generally carried out at a temperature of about 150 to about 400°C. [Effect] According to the present invention, as described above, a high softening point (high degree of polymerization)
Although thermosetting resins can be obtained in a shortened time and the resulting resins have a high softening point,
It has a uniform and dense morphology.
その上、本発明では１反応が減圧下で行われることから
、反応系に存在する水分あるいは副生ずる水分等は除去
され、水分の殆んどない、微粉砕性の良い製品を得るこ
とができる利点がある。Furthermore, in the present invention, since one reaction is carried out under reduced pressure, water existing in the reaction system or by-product water is removed, and a product with almost no water content and good pulverization properties can be obtained. There are advantages.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ピレン、フェナントレン、Ｐ−キシリレングリコール（
ＰＸＧ）、Ｐ−トルエンスルホン酸（Ｐ丁Ｓ）を表−１
に示した割合で配合し、乳鉢で混合後ガラス容器に入れ
、減圧ポンプに接続したロータリーエバポレーターにセ
ットした。ガラス容器を１２０°Ｃの油浴に浸漬し、撹
拌しながら、絶対圧１１０ｍｍｔ（ｇの減圧下で２時間
加熱反応した後、ガラス容器内を常圧に戻し、内容物を
冷却して熱硬化性樹脂を得た４表−１
ピレン １５０ｇ（０，７４３ｍ
ｏｌ）フェナントレン ５７ｇ（０，３
２０ｍｏｌ）Ｐ Ｘ Ｇ １
ｇ３．５ｇ（１，３３ｍｏｌ）ＰＸＧ／縮合多環芳香族
モル比 １．２５Ｐ Ｔ ３
９．８ｇ（２，５重量％）前記で得た熱硬化性樹脂
は８９℃の軟化点（高化式フローテスターで測定）を有
した６また前記反応では９反応容器内部及び生成樹脂に
は水分の付着は見られず、また樹脂も透明であった。さ
らにこの樹脂は粉砕も容易であり、粉砕後乾燥工程を経
ることなく「ふるい」にかけることができた。Example 1 Pyrene, phenanthrene, P-xylylene glycol (
PXG), P-toluenesulfonic acid (P-S)
They were mixed in a mortar, placed in a glass container, and placed in a rotary evaporator connected to a vacuum pump. The glass container was immersed in an oil bath at 120°C, and while stirring, the reaction was heated under reduced pressure of 110 mmt (g) for 2 hours, and then the inside of the glass container was returned to normal pressure, and the contents were cooled and thermoset. Table 4-1 Pyrene 150g (0,743m
ol) Phenanthrene 57g (0,3
20 mol) P X G 1
g3.5g (1,33mol) PXG/fused polycyclic aromatic molar ratio 1.25P T 3
9.8 g (2.5% by weight) of the thermosetting resin obtained above had a softening point of 89°C (measured with a Koka type flow tester). No moisture was observed, and the resin was transparent. Furthermore, this resin was easily pulverized and could be sieved without a drying process after pulverization.
次に、この樹脂粉末を金型に入れ、２００ｋｇ／１−ｆ
ｆ１Ｇの加圧下、２００℃で１時間保持することにより
、不溶不融性の成形体が得られた。Next, put this resin powder into a mold and weigh 200 kg/1-f.
An insoluble and infusible molded body was obtained by holding at 200° C. for 1 hour under a pressure of f1G.
比較例１
実施例１の表−１で示した原料配合物を乳鉢で混合後ガ
ラス容器に入れ、ロータリーエバポレーターにセットし
た。ガラス容器を油浴に浸漬し、撹拌しながら常圧下で
１９時間加熱して熱硬化性樹脂を得た。Comparative Example 1 The raw material formulations shown in Table 1 of Example 1 were mixed in a mortar, placed in a glass container, and set in a rotary evaporator. The glass container was immersed in an oil bath and heated under normal pressure while stirring for 19 hours to obtain a thermosetting resin.
前記で得た樹脂の軟化点は８６℃であった。また前記の
反応においては、容器内部及び樹脂には水分があり、樹
脂を粉砕後「ふるい」にかけるにはその前処理として乾
燥工程が必要であった。The softening point of the resin obtained above was 86°C. In addition, in the above-mentioned reaction, there is moisture inside the container and in the resin, and a drying step is required as a pretreatment to "sieve" the resin after crushing.
出願人代理人 弁理士 池 浦 敏 明（ほか１名）Applicant's agent: Patent attorney Toshiaki Ikeura (and one other person)
Claims (1)
原料物質と、少くとも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主成分とする架橋剤
を、酸触媒の存在下に加熱反応させて熱硬化性樹脂を製
造するに当り、該反応混合物を減圧下に保持して反応さ
せた後、常圧ないし加圧下で、降温し、反応を停止する
ことを特徴とする熱硬化性樹脂の製造方法。(1) A raw material mainly composed of a fused polycyclic aromatic compound having three or more rings and a crosslinking agent mainly composed of an aromatic compound having at least two hydroxymethyl groups or halomethyl groups are combined with an acid catalyst. In producing a thermosetting resin by heating the reaction mixture in the presence of a thermosetting resin, the reaction mixture is kept under reduced pressure to react, and then the temperature is lowered under normal pressure or increased pressure to stop the reaction. A method for producing a thermosetting resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19602786A JPS6351419A (en) | 1986-08-21 | 1986-08-21 | Production of thermosetting hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19602786A JPS6351419A (en) | 1986-08-21 | 1986-08-21 | Production of thermosetting hydrocarbon resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6351419A true JPS6351419A (en) | 1988-03-04 |
Family
ID=16350997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19602786A Pending JPS6351419A (en) | 1986-08-21 | 1986-08-21 | Production of thermosetting hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6351419A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7932018B2 (en) | 2008-05-06 | 2011-04-26 | Az Electronic Materials Usa Corp. | Antireflective coating composition |
| US7989144B2 (en) | 2008-04-01 | 2011-08-02 | Az Electronic Materials Usa Corp | Antireflective coating composition |
| US8017296B2 (en) | 2007-05-22 | 2011-09-13 | Az Electronic Materials Usa Corp. | Antireflective coating composition comprising fused aromatic rings |
| US8486609B2 (en) | 2009-12-23 | 2013-07-16 | Az Electronic Materials Usa Corp. | Antireflective coating composition and process thereof |
-
1986
- 1986-08-21 JP JP19602786A patent/JPS6351419A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8017296B2 (en) | 2007-05-22 | 2011-09-13 | Az Electronic Materials Usa Corp. | Antireflective coating composition comprising fused aromatic rings |
| US7989144B2 (en) | 2008-04-01 | 2011-08-02 | Az Electronic Materials Usa Corp | Antireflective coating composition |
| US7932018B2 (en) | 2008-05-06 | 2011-04-26 | Az Electronic Materials Usa Corp. | Antireflective coating composition |
| US8486609B2 (en) | 2009-12-23 | 2013-07-16 | Az Electronic Materials Usa Corp. | Antireflective coating composition and process thereof |
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