JPS6138732B2 - - Google Patents
Info
- Publication number
- JPS6138732B2 JPS6138732B2 JP2636679A JP2636679A JPS6138732B2 JP S6138732 B2 JPS6138732 B2 JP S6138732B2 JP 2636679 A JP2636679 A JP 2636679A JP 2636679 A JP2636679 A JP 2636679A JP S6138732 B2 JPS6138732 B2 JP S6138732B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- quinazolone
- groups
- reaction
- epoxy resin
- 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.)
- Expired
Links
- 239000004593 Epoxy Substances 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- -1 bisphenol compound Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 3
- 239000000047 product Substances 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
この発明はキナゾロン環含有エポキシ樹脂の製
造方法に関する。
本発明により得られるエポキシ樹脂は、エポキ
シ基と反応性のある基を有する硬化剤を用いて硬
化することができ、注形用、積層用、塗装用など
の用途に用いるのに適し、特に優れた耐熱性、機
械的、電気的性質を保持するという特長を有する
ものである。
一般に、ビスフエノールAなどの多価フエノー
ルとエピクロルヒドリンなどのエピハロゲンヒド
リンとの縮合によつて得られるエポキシ樹脂をア
ミノ基、カルボキシル基、カルボン酸無水物など
のエポキシ基と反応する官能基を有する硬化剤と
混合し、そのエポキシ基とこれらの官能基とを反
応させて樹脂状生成物(硬化物)を得ることは当
業界において広く行なわれている。しかし、これ
ら硬化物は電気的性質、寸法安定性、耐薬品性な
どにおいて優れた性能を有しているが、耐熱性に
おいては必ずしも十分であるといえない。
本発明によつて得られるエポキシ樹脂は熱安定
性に優れたものであり、しかも芳香族複素環の導
入にもかかわらず通常知られている硬化剤とよく
相溶し、容易に硬化性組成物を得るところに特長
を有するものである。一般に芳香族複素環のポリ
マー中への導入は高融点化、難溶化などによつて
反応性の低下が大きく、エポキシ化合物の製造に
は不適とされていた。しかるに、本発明者らは鋭
意検討の結果キナゾロン環含有誘導体を導入する
ことにより、芳香族複素環含有エポキシ樹脂を得
る方法を見出し、本発明を完成するに至つた。
すなわち、本発明は、一般式
(式中、OH基はo、m、p位のいずれかに置換
するものを表わし、Rはアルキレン基、アリーレ
ン基、アラルキレン基、などの2価の有機基を表
わす。)で示される1分子中に2個のキナゾロン
環を有するビスフエノール化合物と、1分子中に
少なくとも2個以上のエポキシ基を有するエポキ
シ化合物とを反応せしめることを特徴とするもの
で、かかる本発明の方法により得られるキナゾロ
ン環含有エポキシ樹脂は、アミノ基、カルボキシ
ル基、カルボン酸無水物などの硬化剤とよく相溶
し、混合して硬化する場合に特に優れた耐熱性を
有するものである。
一般にイミド環をはじめとして、その他芳香族
複素環を有する誘導体は難溶性であり、従来エポ
キシ樹脂への芳香族複素環の導入は困難とされて
いたが、上記一般式で示されるキナゾロン環含有
ビスフエノールはエポキシ化合物と反応性に富み
かつ、エポキシ化合物との相溶性にすぐれてお
り、本発明の製造方法により、耐熱性の優れた、
キナゾロン環含有エポキシ樹脂を容易に得ること
ができる。
本発明において使用される前記一般式で示され
るキナゾロン環含有ビスフエノール化合物は例え
ばアントラニル酸と、マロン酸クロライドまたは
テレフタル酸クロライド等とを反応させたのち、
脱水閉環を行なわせることにより容易に得られる
下記一般式で示されるビスオキサジノン
(式中Rは−CH2−、−C2H4−、−C3H6−などのア
ルキレン基、
This invention relates to a method for producing a quinazolone ring-containing epoxy resin. The epoxy resin obtained by the present invention can be cured using a curing agent having a group reactive with epoxy groups, and is suitable for use in applications such as casting, lamination, and painting, and is particularly excellent. It has the characteristics of maintaining high heat resistance, mechanical and electrical properties. Generally, epoxy resins obtained by condensation of polyhydric phenols such as bisphenol A and epihalogenhydrins such as epichlorohydrin are cured to have functional groups that react with epoxy groups such as amino groups, carboxyl groups, and carboxylic acid anhydrides. It is widely practiced in the art to obtain a resinous product (cured product) by mixing the epoxy group with a resin and reacting the epoxy group with these functional groups. However, although these cured products have excellent electrical properties, dimensional stability, chemical resistance, etc., they cannot necessarily be said to have sufficient heat resistance. The epoxy resin obtained by the present invention has excellent thermal stability, and despite the introduction of an aromatic heterocycle, it is compatible with commonly known curing agents and can be easily formed into curable compositions. The feature is that it obtains the following. In general, the introduction of aromatic heterocycles into polymers causes a significant decrease in reactivity due to higher melting points, less solubility, etc., and has been considered unsuitable for the production of epoxy compounds. However, as a result of extensive studies, the present inventors have discovered a method for obtaining an aromatic heterocycle-containing epoxy resin by introducing a quinazolone ring-containing derivative, and have completed the present invention. That is, the present invention provides the general formula (In the formula, the OH group represents one substituted at the o, m, or p position, and R represents a divalent organic group such as an alkylene group, arylene group, or aralkylene group.) The quinazolone obtained by the method of the present invention is characterized by reacting a bisphenol compound having two quinazolone rings therein with an epoxy compound having at least two or more epoxy groups in one molecule. The ring-containing epoxy resin is well compatible with curing agents such as amino groups, carboxyl groups, and carboxylic acid anhydrides, and has particularly excellent heat resistance when mixed and cured. In general, derivatives containing imide rings and other aromatic heterocycles are poorly soluble, and conventionally it has been difficult to introduce aromatic heterocycles into epoxy resins. Phenol is highly reactive with epoxy compounds and has excellent compatibility with epoxy compounds, and the production method of the present invention can produce phenols with excellent heat resistance.
A quinazolone ring-containing epoxy resin can be easily obtained. The quinazolone ring-containing bisphenol compound represented by the general formula used in the present invention is obtained by reacting, for example, anthranilic acid with malonic acid chloride or terephthalic acid chloride, and then
Bisoxazinone represented by the following general formula that can be easily obtained by dehydration ring closure. (In the formula, R is an alkylene group such as -CH 2 -, -C 2 H 4 -, -C 3 H 6 -,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】などのアリーレン基、
及びアラルキレン基などから選ばれた2価の有機
基を示す)を出発原料とし、この1モルと例えば
p−アミノフエノール(o体、m体も同様であ
る)のごときアミノフエノールの2モルとを、m
−クレゾール、N−メチル2ピロリドン、N・N
−ジメチルアセトアミド等の有機溶媒と共に120
〜220℃で3〜10時間加熱させることにより容易
に得ることができる。尚、五酸化リンのごとき脱
水剤を反応触媒として用いると、副反応等を伴な
うことなく、反応をすみやかに完結させることが
できる。
本発明において用いられるエポキシ化合物は、
その分子中に環状エポキシ基、A divalent organic group selected from arylene groups such as [formula] and aralkylene groups is used as a starting material, and 1 mole of this and p-aminophenol (the same applies to o-form and m-form) are used as starting materials. 2 moles of aminophenol such as m
-Cresol, N-methyl 2-pyrrolidone, N・N
-120 with organic solvents such as dimethylacetamide
It can be easily obtained by heating at ~220°C for 3 to 10 hours. Note that when a dehydrating agent such as phosphorus pentoxide is used as a reaction catalyst, the reaction can be completed quickly without side reactions. The epoxy compound used in the present invention is
Cyclic epoxy group in the molecule,
【式】 あるいは鎖状エポキシ基【formula】 Or linear epoxy group
【式】を少な
くとも2個有しているものである。すなわち、内
部に1・2−エポキシ基を含む化合物であつて、
エポキシド化したジオレフイン、ジエン、環状ジ
エン、ジオレフイン性不飽和カルボン酸エステル
などが含まれ、市販品として、チツソノツクス−
221、同−201、同−206、同−269(いずれもチツ
ソ社商品名)アラルダイトCY−179、同−178、
同−182、同−185、同−175(いずれもチバ社商
品名)などとして知られているものである。ま
た、鎖状エポキシド基を有する化合物としてはポ
リグリシジルエーテル、ポリグリシジルエステル
などが含まれ、前者の市販品としてエピコート
828(シエル社商品名)DER431、同−438(ダウ
社商品名)等があり、後者の商品名として、アラ
ルダイトCY−183(チバ社商品名)、エピコート
190、同−191(シエル社商品名)、レークサムX
−100(バイエル社商品名)、エピクロン400(大
日本インキ化学社商品名)等があるが、さらに多
くのものが知られている。
本発明において、目的とする上記キナゾロン環
含有エポキシ樹脂は、上記エポキシ化合物の任意
の一種以上のものと上記一般式で示されるキナゾ
ロン環含有ビスフエノールの任意の一種以上の化
合物との反応により製造することができる。ここ
で、キナゾロン環含有ビスフエノールの水酸基数
に対してエポキシ化合物のエポキシ基の数が2〜
30の範囲内(好ましくは4〜20の範囲内)に選択
して反応を行なうことにより、好結果が得られ
る。もし、キナゾロン環含有ビスフエノールの水
酸基数に対して、エポキシ化合物のエポキシ基数
が2以下で反応を行なうとき、反応系の粘度が上
昇しすぎ、さらに相溶性の低下も起り作業性が著
しく低下し、場合により反応途中でゲル化を引き
おこすこともある。一方、30以上で反応を行なえ
ば、相溶性は向上するが、得られたキナゾロン環
含有エポキシ樹脂の耐熱性向上はあまり認められ
ず、適当でない。
反応は80〜240℃の間で配合物を加熱すること
により有利に行なうことができるが、さらに好ま
しくは、130〜200℃の温度で行なうのが良い。反
応は無触媒下でも十分進行するが、反応をより容
易に開始させるために、活性水素を含まない少量
の脂肪族第3アミン、あるいは少量の炭酸カリウ
ム、炭酸ナトリウムなどを添加してもよく、これ
らを用いても本発明の効果はいささかも減じられ
ることはない。
また、適量のN・N−ジメチルアセトアミド、
N−メチル2ピロリドンのごとき有機極性溶媒
を、反応媒体として使用することも可能である。
以上の操作により得られるキナゾロン環含有エ
ポキシ樹脂は通常知られている硬化剤とよく相溶
し、硬化後の生成物は電気的性質、寸法安定性、
耐薬品性に優れ、しかも耐熱性が向上し、機械的
特性も向上したものであり、特にすぐれた耐熱性
機械的及び電気的性質を要求される材料として広
く用いることができる。
以下、実施例をあげて、本発明を具体的に説明
する。
実施例 1
で示されるビスキナゾロンフエノール244g(1.0
水酸基当量)とエポキシ当量190のエピコート828
760g(4.0エポキシ当量)とを混合し、180℃で
1時間反応させた。反応生成物は室温で固体状の
樹脂であり、60〜70℃に加熱すれば流動性を保持
していた。そのエポキシ当量は360であつた。
赤外吸収スペクトルの分析により、1660cm-1、
1590cm-1付近にキナゾロン環にもとずく吸収が認
められ、また、3200cm-1付近のフエノール性水酸
基の吸収が著しく減少していることが確認され
た。これによりキナゾロンエポキシ樹脂の生成が
認められた。
実施例 2
で示されるビスキナゾロンフエノール24.4(0.1
水酸基当量)とエポキシ当量180のノボラツク型
エポキシ樹脂であるDER−438の360g(2.0エポ
キシ当量)とを混合し、180℃1時間反応させ
た。反応生成物は室温で液状の樹脂でありエポキ
シ当量は210であつた。赤外吸収スペクトルの分
析により、実施例1と同様にしてキナゾロンエポ
キシ樹脂の生成が確認された。
実施例 3
で示されるピスキナゾロンフエノール275g(1.0
水酸基当量)とエポキシ当量160のCY−182、640
g(4.0エポキシ当量)とを混合し、180℃1時間
反応させた。反応生成物は室温で固体状の樹脂で
60〜80℃の加熱により流動性を保持していた。こ
の樹脂のエポキシ当量は310であつた。
赤外吸収スペクトルの分析により、実施例1と
同様にして、キナゾロンエポキシ樹脂の生成を確
認した。
実施例 4
で示されるビスキナゾロンフエノール32.1g
(0.1水酸基当量)とエポキシ当量180のエピコー
ト828、360g(2.0エポキシ当量)とを混合し、
180℃1時間加熱した。反応生成物は室温で液状
でありエポキシ当量は220であつた。赤外吸収ス
ペクトル分析により、実施例1と同様にして、キ
ナゾロンエポキシ樹脂の生成を確認した。
実施例 5〜8
実施例1〜4で得られたキナゾロンエポキシ樹
脂の1エポキシ当量に、メチルテトラヒドロフタ
ル酸無水物(MTHA)の150g(0.9酸無水物当
量)を加え、さらに硬化促進剤としてベンジルメ
チルアミン(BDMA)を0.5重量部加え、均一に
混合したのち、150℃8時間、ついで200℃8時間
加熱硬化させて、硬化物を得た。得られた硬化樹
脂について、Tg空気中での熱量減少(昇温速度
(10℃/分)を測定した。その結果を表1に挙げ
る。It has at least two formulas. That is, a compound containing a 1,2-epoxy group inside,
Contains epoxidized diolefins, dienes, cyclic dienes, diolefinic unsaturated carboxylic acid esters, and is commercially available as a commercially available product.
221, CY-201, CY-206, CY-269 (all Chitsuso product names) Araldite CY-179, CY-178,
These are known as -182, -185, and -175 (all product names of Ciba Corporation). In addition, compounds having a chain epoxide group include polyglycidyl ether, polyglycidyl ester, etc., and the commercially available product of the former is Epicoat.
There are 828 (product name of Ciel Corporation) DER431 and DER-438 (product name of Dow Corporation), and the latter's product names include Araldite CY-183 (product name of Ciba Corporation) and Epicote.
190, 191 (Ciel product name), Rexam X
-100 (trade name of Bayer Co., Ltd.), Epiclon 400 (trade name of Dainippon Ink Chemical Co., Ltd.), etc., but many more are known. In the present invention, the target quinazolone ring-containing epoxy resin is produced by reacting any one or more of the epoxy compounds with any one or more quinazolone ring-containing bisphenols represented by the general formula above. be able to. Here, the number of epoxy groups in the epoxy compound is 2 to 2 to the number of hydroxyl groups in the quinazolone ring-containing bisphenol.
Good results can be obtained by selecting the number within the range of 30 (preferably within the range of 4 to 20) and carrying out the reaction. If the reaction is carried out when the number of epoxy groups in the epoxy compound is less than 2 compared to the number of hydroxyl groups in the quinazolone ring-containing bisphenol, the viscosity of the reaction system will increase too much, and the compatibility will also decrease, resulting in a significant decrease in workability. In some cases, gelation may occur during the reaction. On the other hand, if the reaction is carried out at a temperature of 30 or more, the compatibility is improved, but the heat resistance of the obtained quinazolone ring-containing epoxy resin is not significantly improved and is not suitable. The reaction can advantageously be carried out by heating the formulation at a temperature between 80 and 240°C, more preferably at a temperature between 130 and 200°C. The reaction proceeds satisfactorily without a catalyst, but in order to start the reaction more easily, a small amount of aliphatic tertiary amine that does not contain active hydrogen, or a small amount of potassium carbonate, sodium carbonate, etc. may be added. Even if these are used, the effects of the present invention will not be diminished in the slightest. In addition, an appropriate amount of N・N-dimethylacetamide,
It is also possible to use organic polar solvents such as N-methyl 2-pyrrolidone as reaction medium. The quinazolone ring-containing epoxy resin obtained by the above procedure is well compatible with commonly known curing agents, and the cured product has good electrical properties, dimensional stability,
It has excellent chemical resistance, improved heat resistance, and improved mechanical properties, and can be widely used as a material that particularly requires excellent heat resistance, mechanical and electrical properties. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 Bisquinazolone phenol 244g (1.0
Epicote 828 with hydroxyl equivalent) and epoxy equivalent of 190
760g (4.0 epoxy equivalent) were mixed and reacted at 180°C for 1 hour. The reaction product was a solid resin at room temperature, and maintained fluidity when heated to 60-70°C. Its epoxy equivalent weight was 360. By analyzing the infrared absorption spectrum, 1660 cm -1 ,
Absorption based on the quinazolone ring was observed around 1590 cm -1 , and it was also confirmed that the absorption of phenolic hydroxyl groups around 3200 cm -1 was significantly reduced. This confirmed the formation of quinazolone epoxy resin. Example 2 Bisquinazolone phenol 24.4 (0.1
(hydroxyl group equivalent) and 360 g (2.0 epoxy equivalent) of DER-438, a novolak type epoxy resin with an epoxy equivalent of 180, were mixed and reacted at 180°C for 1 hour. The reaction product was a liquid resin at room temperature and had an epoxy equivalent weight of 210. Generation of quinazolone epoxy resin was confirmed in the same manner as in Example 1 by infrared absorption spectrum analysis. Example 3 Pisquinazolone phenol 275g (1.0
CY-182, 640 with hydroxyl equivalent) and epoxy equivalent of 160
g (4.0 epoxy equivalent) and reacted at 180°C for 1 hour. The reaction product is a solid resin at room temperature.
Fluidity was maintained by heating at 60-80°C. The epoxy equivalent weight of this resin was 310. Generation of quinazolone epoxy resin was confirmed in the same manner as in Example 1 by infrared absorption spectrum analysis. Example 4 32.1g of bisquinazolone phenol represented by
(0.1 hydroxyl equivalent) and Epicote 828 with an epoxy equivalent of 180, 360 g (2.0 epoxy equivalent) were mixed,
Heated at 180°C for 1 hour. The reaction product was liquid at room temperature and had an epoxy equivalent weight of 220. Generation of quinazolone epoxy resin was confirmed by infrared absorption spectrum analysis in the same manner as in Example 1. Examples 5 to 8 150 g (0.9 acid anhydride equivalent) of methyltetrahydrophthalic anhydride (MTHA) was added to 1 epoxy equivalent of the quinazolone epoxy resin obtained in Examples 1 to 4, and further added as a curing accelerator. After adding 0.5 parts by weight of benzylmethylamine (BDMA) and mixing uniformly, the mixture was cured by heating at 150°C for 8 hours and then at 200°C for 8 hours to obtain a cured product. The resulting cured resin was measured for heat loss (heating rate (10° C./min) in Tg air. The results are listed in Table 1.
Claims (1)
いずれかに置換するものを表わし、Rは2価の有
機基を表わす。) で示される1分子中に2個のキナゾロン環を有す
るビスフエノール化合物と、1分子中に少なくと
も2個のエポキシ基を有するエポキシ化合物とを
反応させることを特徴とするキナゾロン環含有エ
ポキシ樹脂の製造方法。 2 ビスフエノール化合物の水酸基数に対し、エ
ポキシ化合物のエポキシ基数が2〜30の範囲内と
なるように反応させることを特徴とする特許請求
の範囲第1項記載のキナゾロン環含有エポキシ樹
脂の製造方法。[Claims] 1. General formula (In the formula, the OH group represents one substituted at any of the o-, m-, and p-positions, and R represents a divalent organic group.) Two quinazolone rings in one molecule represented by A method for producing a quinazolone ring-containing epoxy resin, which comprises reacting a bisphenol compound having the following with an epoxy compound having at least two epoxy groups in one molecule. 2. The method for producing a quinazolone ring-containing epoxy resin according to claim 1, characterized in that the reaction is carried out so that the number of epoxy groups in the epoxy compound is within the range of 2 to 30 with respect to the number of hydroxyl groups in the bisphenol compound. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2636679A JPS55118917A (en) | 1979-03-06 | 1979-03-06 | Production of quinazolone ring-containing epoxy resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2636679A JPS55118917A (en) | 1979-03-06 | 1979-03-06 | Production of quinazolone ring-containing epoxy resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS55118917A JPS55118917A (en) | 1980-09-12 |
JPS6138732B2 true JPS6138732B2 (en) | 1986-08-30 |
Family
ID=12191492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2636679A Granted JPS55118917A (en) | 1979-03-06 | 1979-03-06 | Production of quinazolone ring-containing epoxy resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS55118917A (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6667300B2 (en) | 2000-04-25 | 2003-12-23 | Icos Corporation | Inhibitors of human phosphatidylinositol 3-kinase delta |
ATE502941T1 (en) * | 2000-04-25 | 2011-04-15 | Icos Corp | HUMAN PHOSPHATIDYL-INOSITOL-3-KINASE DELTA INHIBITORS |
US7932260B2 (en) | 2004-05-13 | 2011-04-26 | Icos Corporation | Quinazolinones as inhibitors of human phosphatidylinositol 3-kinase delta |
US9492449B2 (en) | 2008-11-13 | 2016-11-15 | Gilead Calistoga Llc | Therapies for hematologic malignancies |
EP2411391A1 (en) | 2009-03-24 | 2012-02-01 | Gilead Calistoga LLC | Atropisomers of2-purinyl-3-tolyl-quinazolinone derivatives and methods of use |
CN102458410A (en) | 2009-04-20 | 2012-05-16 | 吉联亚·卡利斯托加有限责任公司 | Methods of treatment for solid tumors |
CN102647987A (en) | 2009-07-21 | 2012-08-22 | 吉里德卡利斯托加公司 | Treatment of liver disorders with PI3K inhibitors |
AR090253A1 (en) | 2012-03-05 | 2014-10-29 | Gilead Calistoga Llc | Polymorphic forms of (S) -2- (1- (9H-PURIN-6-ILAMINO) PROPIL) -5-FLUOR-3-PHENYLQUINAZOLIN-4 (3H) -ONA |
MX2016008259A (en) | 2013-12-20 | 2016-10-13 | Gilead Calistoga Llc | Process methods for phosphatidylinositol 3-kinase inhibitors. |
US9708327B2 (en) | 2013-12-20 | 2017-07-18 | Gilead Calistoga Llc | Polymorphic forms of a hydrochloride salt of (S)-2-(1-(9H-purin-6-ylamino)propyl)-5-fluoro-3-phenylquinazolin-4(3H)-one |
SG11201609877XA (en) | 2014-06-13 | 2016-12-29 | Gilead Sciences Inc | Phosphatidylinositol 3-kinase inhibitors |
CN115044275B (en) * | 2022-07-22 | 2023-05-02 | 山东佰盛能源科技有限公司 | Pipeline protective coating and production process thereof |
-
1979
- 1979-03-06 JP JP2636679A patent/JPS55118917A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS55118917A (en) | 1980-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS6189219A (en) | Diethyltoluenediamine curing system and curable mixture containing the same | |
JPS6138732B2 (en) | ||
JPH01193317A (en) | Thermosetting liquid composition | |
US3679681A (en) | Diglycidyl ethers | |
CA1322619C (en) | Compostions containing epoxide flexibilizers | |
JPS60142973A (en) | Triglycidyl compound of aminophenol | |
US3644431A (en) | Diglycidyl esters of aliphatic dicarboxylic acids | |
US4190719A (en) | Imidazolidone polyamines as epoxy curing agents | |
US3798242A (en) | N,n'-diglycidyl-dicarboxylic acid dianilides | |
US4672101A (en) | Polyepoxy aromatic hydantoins | |
US3620983A (en) | {11 -methylglycidyl-isocyanurates | |
JPH04356523A (en) | Latent curing agent for epoxy resin | |
JPS5943048B2 (en) | Heat-resistant curable resin composition | |
US3931058A (en) | Polyglycidyl compounds, processes for their manufacture and use | |
EP0435497B1 (en) | Trifunctional polyoxyethylene diamine derivatives | |
JPH05214075A (en) | Addition product of diamino diphenyl sulfone compound as curing agent for epoxy resin | |
JPH05112551A (en) | Aromatic tris acid anhydride | |
JPS5923330B2 (en) | Heat-resistant epoxy resin composition | |
JPS5835500B2 (en) | Thermosetting ethynyl-terminated epoxy derivative compound and method for producing the same | |
JPS58136619A (en) | Novel epoxy resin composition | |
GB2037774A (en) | Adducts from a polyepoxide and bi-nuclear hydantoin compounds | |
JPH0198614A (en) | Epoxidized polycycloacetal and curable mixture containing the same | |
JPH08231683A (en) | Reactive resin system,production of fire-resistant casting resin molding material,and flame-resistant casting resin molding,covering or casing produced from the reactive resin system | |
US3943109A (en) | Diglycidylbenzimidiazolones | |
JP4565489B2 (en) | Curing agent for epoxy resin, epoxy resin composition, and cured product thereof |