JPH03716A - New epoxy compound and preparation thereof - Google Patents
New epoxy compound and preparation thereofInfo
- Publication number
- JPH03716A JPH03716A JP13465089A JP13465089A JPH03716A JP H03716 A JPH03716 A JP H03716A JP 13465089 A JP13465089 A JP 13465089A JP 13465089 A JP13465089 A JP 13465089A JP H03716 A JPH03716 A JP H03716A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy compound
- alpha
- epoxy
- compd
- epihalohydrin
- 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
- 239000004593 Epoxy Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 title claims description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 8
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract description 4
- KSMBFKMHJGVFQO-UHFFFAOYSA-N 2-[2-(2-hydroxypropan-2-yl)phenyl]propan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1C(C)(C)O KSMBFKMHJGVFQO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- CTIZCUNJDUYUCR-UHFFFAOYSA-N 2-[2-[4-[2-(1-hydroxynaphthalen-2-yl)propan-2-yl]phenyl]propan-2-yl]naphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C(C)(C=3C=CC(=CC=3)C(C)(C)C=3C(=C4C=CC=CC4=CC=3)O)C)=CC=C21 CTIZCUNJDUYUCR-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- -1 α-hydroxy-2-naphthyl Chemical group 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000003944 halohydrins Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、耐熱性、耐湿性及び作業性に優れた新規な
エポキシ化合物及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel epoxy compound with excellent heat resistance, moisture resistance and workability, and a method for producing the same.
エポキシ樹脂は、電気絶縁材料、塗料、接着剤、各種複
合材料、土木建築材料等の分野で広く使用されており、
その用途に応じて耐熱性、耐水性、靭性等の性能が要求
されている。Epoxy resins are widely used in fields such as electrical insulation materials, paints, adhesives, various composite materials, and civil engineering and construction materials.
Depending on the application, properties such as heat resistance, water resistance, and toughness are required.
しかしながら、従来より知られているエポキシ樹脂にお
いては、これらの性能を同時にバランス良く満足するも
のは今のところ知られていない。However, among the conventionally known epoxy resins, there is currently no known one that simultaneously satisfies these performances in a well-balanced manner.
例えば、ビスフェノールＡのジグリシジルエーテルは、
常温で液状であり、作業性に優れていることや他の硬化
剤、添加剤等との混合が容易であることから、広く使用
されているが、このエポキシ樹脂には耐熱性や耐水性の
点で問題がある。For example, the diglycidyl ether of bisphenol A is
It is widely used because it is liquid at room temperature, has excellent workability, and is easy to mix with other hardening agents and additives. However, this epoxy resin has heat resistance and water resistance. There is a problem with this point.
また、耐熱性を改善したものとして、フェノール類ノボ
ラック型エポキシ樹脂が知られているが、このものは靭
性が低く、耐衝撃性や耐クラツク性に問題がある。Furthermore, phenolic novolac type epoxy resins are known as having improved heat resistance, but these have low toughness and have problems in impact resistance and crack resistance.
従って、本発明の目的は、耐熱性、耐湿性及び靭性のい
ずれにも優れた性能を発揮するエポキシ樹脂を製造する
ための新規なエポキシ化合物及びその製造方法を提供す
ることにある。Therefore, an object of the present invention is to provide a novel epoxy compound and a method for producing the same for producing an epoxy resin that exhibits excellent performance in all of heat resistance, moisture resistance, and toughness.
また、本発明の他の目的は、優れた力学的物性、特に高
い弾性率を有し、複合材マトリックス樹脂等において優
れた特性を有するエポキシ樹脂を製造することができる
新規なエポキシ化合物及びその製造方法を提供すること
にある。Another object of the present invention is to provide a novel epoxy compound capable of producing an epoxy resin having excellent mechanical properties, particularly a high modulus of elasticity, and having excellent properties in composite matrix resins, and the production thereof. The purpose is to provide a method.
すなわち、本発明は、下記一般式（１）（但し、式中Ｒ
は水素原子又はメチル基を示し、ｎは０〜１０の整数を
示す）で表される新規なエポキシ化合物である。また、
本発明は、このような一般式（１）で表される化合物を
製造するために、下記一般式（２）
で表されるジヒドロキシ化合物と下記一般式（３）（但
し、式中Ｒは水素原子又はメチル基を示し、Ｘはハロゲ
ン原子を示す）で表されるエピハロヒドリンとを反応さ
せる新規なエポキシ化合物の製造方法である。That is, the present invention relates to the following general formula (1) (wherein R
represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10). Also,
The present invention uses a dihydroxy compound represented by the following general formula (2) and the following general formula (3) (wherein R is hydrogen) to produce a compound represented by the general formula (1). This is a method for producing a novel epoxy compound, which involves reacting an epihalohydrin represented by an atom or a methyl group, and X represents a halogen atom.
一般式（２）表されるジヒドロキシ化合物は、例えば、
α−ナフトールとビス（α−メチル−α−ヒドロキシエ
チル）ベンゼン類との縮合反応により容易に製造するこ
とができる。このジヒドロキシ化合物として、具体的に
は、１，４−ビス［（α−ヒドロキシ−２−ナフチル）
−α−メチルエチル１ベンゼンや１．３−ビス［（α−
ヒドロキシ−２−ナフチル）−α−メチルエチル１ベン
ゼン等が挙げられ、特に耐熱性の点から、１．４−ビス
［（α−ヒドロキシ−２−ナフチル）−α−メチルエチ
ル１ベンゼンが好ましい。The dihydroxy compound represented by general formula (2) is, for example,
It can be easily produced by a condensation reaction between α-naphthol and bis(α-methyl-α-hydroxyethyl)benzenes. Specifically, as this dihydroxy compound, 1,4-bis[(α-hydroxy-2-naphthyl)
-α-methylethyl 1benzene and 1,3-bis[(α-
Examples include hydroxy-2-naphthyl)-α-methylethyl 1-benzene, and 1,4-bis[(α-hydroxy-2-naphthyl)-α-methylethyl 1-benzene is particularly preferred from the viewpoint of heat resistance.
また、本発明で使用するエピハロヒドリンとしては、エ
ピクロルヒドリン、β−メチルエピクロルヒドリン、エ
ビブロモヒドリン、β−メチルエピブロモヒドリン等を
挙げることができるが、好ましくはエピクロルヒドリン
である。Further, examples of the epihalohydrin used in the present invention include epichlorohydrin, β-methylepichlorohydrin, shrimp bromohydrin, β-methylepibromohydrin, etc., but epichlorohydrin is preferable.
本発明のエポキシ化合物は、従来公知のエポキシ化合物
の合成法に従って製造することができる。The epoxy compound of the present invention can be produced according to conventionally known epoxy compound synthesis methods.
すなわち、ジヒドロキシ化合物とこのジヒドロキシ化合
物中の水酸基１モルに対して２〜１５倍モルのエピハロ
ヒドリンとの混合物に、水酸化ナトリウムや水酸化カリ
ウム等のアルカリ性化合物の固体又は濃厚水溶液を加え
、５０〜１５０°Ｃの温度で反応させることにより製造
する方法や、ジヒドロキシ化合物とこのジヒドロキシ化
合物中の水酸基１モルに対して２〜５倍モルのエピハロ
ヒドリンとの混合物に、テトラメチルアンモニウムクロ
ライドやテトラエチルアンモニウムクロライド等の四級
アンモニウム塩をジヒドロキシ化合物中の水酸基１モル
に対して０．００１〜０．１倍モル添加し、５０〜１５
０°Ｃの温度で反応させ、得られたハロヒドリンエーテ
ルに水酸化ナトリウムや水酸化カリウム等のアルカリ性
化合物の固体又は濃厚水溶液を加えて再度５０〜１５０
°Ｃの温度で反応させ、ハロヒドリンエーテルを閉環さ
せることにより製造する方法が挙げられる。That is, a solid or concentrated aqueous solution of an alkaline compound such as sodium hydroxide or potassium hydroxide is added to a mixture of a dihydroxy compound and epihalohydrin in an amount of 2 to 15 times the mole per mole of hydroxyl groups in the dihydroxy compound. There is a method in which tetramethylammonium chloride, tetraethylammonium chloride, etc. Add 0.001 to 0.1 mole of quaternary ammonium salt to 1 mole of hydroxyl group in the dihydroxy compound, and add 50 to 15 moles of quaternary ammonium salt.
The reaction was carried out at a temperature of 0°C, and a solid or concentrated aqueous solution of an alkaline compound such as sodium hydroxide or potassium hydroxide was added to the obtained halohydrin ether to give a reaction temperature of 50 to 150 °C.
Examples include a method of manufacturing by reacting at a temperature of °C and ring-closing a halohydrin ether.
このエポキシ化合物を合成する反応には、必要により、
メタノール、エタノール、プロパツール、ブタノール等
の溶媒を用いることができ、また、その反応時間は、通
常１〜１０時間の範囲である。In the reaction to synthesize this epoxy compound, if necessary,
Solvents such as methanol, ethanol, propatool, butanol can be used, and the reaction time is usually in the range of 1 to 10 hours.
反応終了後、未反応のエピハロヒドリンや必要により使
用した溶媒を蒸留により除去し、また、生成した無機塩
は水による抽出あるいは濾別等の手段で分離除去し、目
的物のエポキシ化合物を得ることができる。After the reaction is complete, unreacted epihalohydrin and the solvent used if necessary are removed by distillation, and the produced inorganic salts are separated and removed by water extraction or filtration to obtain the target epoxy compound. can.
本発明のエポキシ化合物は、従来公知の硬化剤、例えば
、アミン類、酸無水物、フェノール類ノボラック樹脂、
ポリアミド樹脂、ポリスルフィド樹脂、ジシアンジアミ
ド等により硬化される。これらの硬化剤については、具
体的には、ジエチレントリアミン、ｍ−キシレンジアミ
ン等のような脂肪族アミン類や、ｍ−フェニレンジアミ
ン、４，４°−ジアミノジフェニルメタン、４，４′−
ジアミノジフェニルスルホン、４，４−ジアミノジフェ
ニルエーテル等のような芳香族アミン類や、無水フタル
酸、無水へキサヒドロフタル酸、無水メチルナジック酸
、無水ピロメリット酸、ベンゾフェノンテトラカルボン
酸無水物等の酸無水物や、フェノール、クレゾール等か
ら得られるノボラック樹脂等を挙げることができる。こ
れら硬化剤の使用量は、特に限定されるものではないが
、硬化剤中にアミノ基や水酸基等の活性水素を有するも
のについてはエポキシ化合物中のエポキシ基１モルに対
して硬化剤中の活性水素量が０．５−＝１．５倍モル量
であり、硬化剤が酸無水物である場合にはエポキシ化合
物中のエポキシ基１モルに対して０．５〜１゜０倍モル
であり、さらに、硬化剤がジシアンジアミドである場合
にはエポキシ化合物中のエポキシ基１モルに対して０．
１〜０．４倍モルである。The epoxy compound of the present invention can be prepared using conventionally known curing agents, such as amines, acid anhydrides, phenolic novolac resins,
Cured with polyamide resin, polysulfide resin, dicyandiamide, etc. Specifically, these curing agents include aliphatic amines such as diethylenetriamine, m-xylene diamine, etc., m-phenylene diamine, 4,4°-diaminodiphenylmethane, 4,4'-
Aromatic amines such as diaminodiphenylsulfone, 4,4-diaminodiphenyl ether, etc., acids such as phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. Examples include novolak resins obtained from anhydrides, phenols, cresols, and the like. The amount of these curing agents used is not particularly limited, but if the curing agent has active hydrogen such as an amino group or a hydroxyl group, the amount of active hydrogen in the curing agent per mole of epoxy group in the epoxy compound is The amount of hydrogen is 0.5-=1.5 times the molar amount, and when the curing agent is an acid anhydride, it is 0.5 to 1.0 times the molar amount per mole of the epoxy group in the epoxy compound. , and furthermore, when the curing agent is dicyandiamide, 0.0.
It is 1 to 0.4 times the mole.
また、必要に応じて硬化促進剤を使用することができ、
この硬化促進剤としては、例えば、トリエチルアミン、
ジメチルベンジルアミン等第三級アミン類や、２−メチ
ルイミダゾール、２−エチル−４−メチルイミダゾール
等のイミダゾール類や、トリフェニルホスフィン等の有
機ホスフィン類や、１．８−ジアザビシクロ［５，４，
０］ウンデセン及びそのフェノール塩や蟻酸塩等を挙げ
ることができる。Additionally, a curing accelerator can be used if necessary.
Examples of the curing accelerator include triethylamine,
Tertiary amines such as dimethylbenzylamine, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and 1,8-diazabicyclo[5,4,
0] undecene and its phenol salts and formates.
本発明のエポキシ化合物は、上記硬化剤及び必要に応じ
て使用される硬化促進剤を加えてそのまま硬化させても
よいが、場合によりこれに充填剤を加えてもよい。この
充填剤としては、例えば、溶融シリカ粉、結晶シリカ粉
、石英ガラス粉、タルク、アルミナ、炭酸カルシウム、
ガラス繊維等が挙げられる。また、炭素繊維、アラミド
繊維等の高弾性繊維で補強を行ってもよい。The epoxy compound of the present invention may be cured as it is by adding the above-mentioned curing agent and a curing accelerator used if necessary, but a filler may be added thereto as occasion demands. Examples of the filler include fused silica powder, crystalline silica powder, quartz glass powder, talc, alumina, calcium carbonate,
Examples include glass fiber. Further, it may be reinforced with high elastic fibers such as carbon fibers and aramid fibers.
本発明のエポキシ化合物を硬化させて得られる硬化物は
、高い弾性率、低い線膨張係数及び低い吸水率を示すだ
けでなく、低い架橋密度にもかかわらず高いガラス点移
転を示し、また、この低い架橋密度により高靭性を発揮
する。The cured product obtained by curing the epoxy compound of the present invention not only exhibits a high modulus of elasticity, a low coefficient of linear expansion, and a low water absorption rate, but also exhibits a high glass point shift despite a low crosslink density. Demonstrates high toughness due to low crosslink density.
以下、実施例、比較例及び試験例に基づいて、本発明を
具体的に説明する。The present invention will be specifically described below based on Examples, Comparative Examples, and Test Examples.
実施例１
１．４−ビス［（α−ヒドロキシ−２−ナフチル）−α
−メチルエチル］ベンゼン９０重量部をエピクロルヒド
リン７４０重量部に溶解し、１１５°Ｃに加熱しながら
４８ｗｔＸ−水酸化ナトリウム水溶液３３．６重量部を
３．５時間かけて添加し、この間、水はエピクロルヒド
リンとの共沸により反応系外に除去し、エピクロルヒド
リンは反応系内に戻した。Example 1 1.4-bis[(α-hydroxy-2-naphthyl)-α
90 parts by weight of -methylethyl]benzene was dissolved in 740 parts by weight of epichlorohydrin, and 33.6 parts by weight of a 48wtX-sodium hydroxide aqueous solution was added over 3.5 hours while heating to 115°C. Epichlorohydrin was removed from the reaction system by azeotropy with the epichlorohydrin, and epichlorohydrin was returned to the reaction system.
この水酸化ナトリウム水溶液の滴下終了後、さらに同じ
温度で１５分間反応を継続した。After the dropwise addition of the sodium hydroxide aqueous solution was completed, the reaction was further continued at the same temperature for 15 minutes.
反応終了後、エピクロルヒドリンを減圧下に留去し、メ
チルイソブチルケトンで抽出し、水洗後このメチルイソ
ブチルケトンを留去し、目的物のエポキシ化合物１０６
重量部を得た。After the reaction is completed, epichlorohydrin is distilled off under reduced pressure, extracted with methyl isobutyl ketone, and after washing with water, this methyl isobutyl ketone is distilled off to obtain the target epoxy compound 106.
Parts by weight were obtained.
このエポキシ化合物のエポキシ当量は３２４であり、軟
化点は１１４°Ｃであった。また、このエポキシ化合物
の赤外吸収スペクトルの結果を第１図に示す。The epoxy equivalent of this epoxy compound was 324, and the softening point was 114°C. Moreover, the results of the infrared absorption spectrum of this epoxy compound are shown in FIG.
実施例２
１．３−ビス［（α−ヒドロキシ−２−ナフチル）−α
−メチルエチル］ベンゼンを使用した以外は、実施例１
と同様に反応を行い、エポキシ化合物１１２重量部を得
た。Example 2 1.3-bis[(α-hydroxy-2-naphthyl)-α
Example 1 except that -methylethyl]benzene was used.
The reaction was carried out in the same manner as above to obtain 112 parts by weight of an epoxy compound.
このエポキシ化合物のエポキシ当量は３５０であり、軟
化点は９８．５℃であった。また、このエポキシ化合物
の赤外吸収スペクトルの結果を第２図に示す。The epoxy equivalent of this epoxy compound was 350, and the softening point was 98.5°C. Moreover, the results of the infrared absorption spectrum of this epoxy compound are shown in FIG.
試験例
上記実施例１及び２で得られたエポキシ化合物に、硬化
剤としてフェノールノボラック（軟化点６８°Ｃ）を化
学量論的割合で加え、トリフェニルホスフィンを硬化促
進剤として使用し、１８０℃で１６時間加熱硬化させて
成形片を得た。Test Example To the epoxy compounds obtained in Examples 1 and 2 above, phenol novolac (softening point 68°C) was added as a curing agent in a stoichiometric ratio, triphenylphosphine was used as a curing accelerator, and the temperature was heated at 180°C. The molded piece was obtained by heating and curing for 16 hours.
得られた成形片について、ガラス転移点、線膨張係数、
曲げ強度（ＪＩＳ Ｋ ６９１１） 、曲げ弾性率（Ｊ
ＩＳ Ｋ ６９１１） 、破壊靭性及び吸水率を測定し
た。Regarding the obtained molded piece, the glass transition point, linear expansion coefficient,
Bending strength (JIS K 6911), bending modulus (J
IS K 6911), fracture toughness and water absorption were measured.
結果を第１表に示す。The results are shown in Table 1.
また、比較のため、比較例１としてビスフェノールＡ型
エポキシ樹脂を使用し、また、比較例２として０−タレ
ゾールノボラック型エポキシ樹脂を使用し、実施例の場
合と同様に成形片を調製し、同様の物性を測定した。結
果を第１表に示す。For comparison, a bisphenol A type epoxy resin was used as Comparative Example 1, and an 0-talesol novolac type epoxy resin was used as Comparative Example 2, and molded pieces were prepared in the same manner as in the example. Similar physical properties were measured. The results are shown in Table 1.
なお、ガラス転移点及び線膨張係数は、熱機械分析装置
を用いて７℃／分の昇温速度で測定した。Note that the glass transition point and linear expansion coefficient were measured using a thermomechanical analyzer at a heating rate of 7° C./min.
また、破壊靭性は、ジャーナル・オブ・マテリアル・サ
イエンス第２１巻第２，４６２頁（１９８６）に記載さ
れた方法に準じて測定した。さらに、吸水率は、１３３
℃、３気圧の水蒸気中で１００時間吸湿させて求めた。Moreover, the fracture toughness was measured according to the method described in Journal of Materials Science, Vol. 21, p. 2, 462 (1986). Furthermore, the water absorption rate is 133
It was determined by absorbing moisture for 100 hours in water vapor at 3 atm.
第 １ 表
途に有利に使用できるものである。また、本発明の方法
によれば、このように優れた性能を有する硬化物を与え
るエポキシ化合物を有利に製造することができる。1. It can be used advantageously in public. Further, according to the method of the present invention, it is possible to advantageously produce an epoxy compound that provides a cured product having such excellent performance.
第１図及び第２図は、実施例１及び２によって得られた
エポキシ化合物の赤外吸収スペクトルを示すグラフ図で
ある。
特許出願人 新日鐵化学株式会社1 and 2 are graphs showing infrared absorption spectra of epoxy compounds obtained in Examples 1 and 2. Patent applicant: Nippon Steel Chemical Co., Ltd.
Claims (2)
〜１０の整数を示す）で表される新規なエポキシ化合物
。(1) The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, in the formula, R represents a hydrogen atom or a methyl group, and n is 0
A novel epoxy compound represented by (representing an integer of ~10).
式、化学式、表等があります▼（３） （但し、式中Ｒは水素原子又はメチル基を示し、Ｘはハ
ロゲン原子を示す）で表されるエピハロヒドリンとを反
応させ、下記一般式（１） ▲数式、化学式、表等があります▼（１） （但し、式中Ｒは水素原子又はメチル基を示し、ｎは０
〜１０の整数を示す）で表されるエポキシ化合物を製造
することを特徴とする新規なエポキシ化合物の製造方法
。(2) The dihydroxy compound represented by the following general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) and the following general formula (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) (However, , in which R represents a hydrogen atom or a methyl group, and X represents a halogen atom) is reacted with epihalohydrin represented by the following general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) ( However, in the formula, R represents a hydrogen atom or a methyl group, and n is 0
A novel method for producing an epoxy compound, characterized by producing an epoxy compound represented by (representing an integer from 10 to 10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13465089A JPH03716A (en) | 1989-05-30 | 1989-05-30 | New epoxy compound and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13465089A JPH03716A (en) | 1989-05-30 | 1989-05-30 | New epoxy compound and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03716A true JPH03716A (en) | 1991-01-07 |
Family
ID=15133332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13465089A Pending JPH03716A (en) | 1989-05-30 | 1989-05-30 | New epoxy compound and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03716A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171869A (en) * | 1991-01-25 | 1992-12-15 | Shin-Etsu Chemical Company Limited | Allyl or propenyl group-containing naphthalene derivatives |
| JPH0597970A (en) * | 1991-10-07 | 1993-04-20 | Shin Etsu Chem Co Ltd | Thermosetting resin composition and semiconductor device |
| JP2005226004A (en) * | 2004-02-13 | 2005-08-25 | Nippon Steel Chem Co Ltd | Method for producing epoxy resin, epoxy resin composition and cured product |
| AU2008291797B2 (en) * | 2007-08-31 | 2013-05-09 | Kimberly-Clark Worldwide, Inc. | Refillable dispensing carton system |
| DE102016214430B4 (en) | 2015-08-04 | 2021-11-18 | Yazaki Corporation | Harness winding device |
-
1989
- 1989-05-30 JP JP13465089A patent/JPH03716A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171869A (en) * | 1991-01-25 | 1992-12-15 | Shin-Etsu Chemical Company Limited | Allyl or propenyl group-containing naphthalene derivatives |
| JPH0597970A (en) * | 1991-10-07 | 1993-04-20 | Shin Etsu Chem Co Ltd | Thermosetting resin composition and semiconductor device |
| JP2005226004A (en) * | 2004-02-13 | 2005-08-25 | Nippon Steel Chem Co Ltd | Method for producing epoxy resin, epoxy resin composition and cured product |
| JP4667753B2 (en) * | 2004-02-13 | 2011-04-13 | 新日鐵化学株式会社 | Epoxy resin production method, epoxy resin composition and cured product |
| AU2008291797B2 (en) * | 2007-08-31 | 2013-05-09 | Kimberly-Clark Worldwide, Inc. | Refillable dispensing carton system |
| DE102016214430B4 (en) | 2015-08-04 | 2021-11-18 | Yazaki Corporation | Harness winding device |
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