JPS62246563A - Novel epoxy resin and production thereof - Google Patents
Novel epoxy resin and production thereofInfo
- Publication number
- JPS62246563A JPS62246563A JP8845686A JP8845686A JPS62246563A JP S62246563 A JPS62246563 A JP S62246563A JP 8845686 A JP8845686 A JP 8845686A JP 8845686 A JP8845686 A JP 8845686A JP S62246563 A JPS62246563 A JP S62246563A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- epoxy resin
- acid
- hydrogen atom
- group
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000003518 caustics Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 5
- -1 N,N-diglycidylamino group Chemical group 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical group [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003983 crown ethers Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 239000000126 substance Substances 0.000 claims 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 2
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 3
- 238000012690 ionic polymerization Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920006122 polyamide resin Polymers 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- AGIBHMPYXXPGAX-UHFFFAOYSA-N 2-(iodomethyl)oxirane Chemical compound ICC1CO1 AGIBHMPYXXPGAX-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- LHNICELDCMPPDE-UHFFFAOYSA-N anthracen-9-amine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=CC2=C1 LHNICELDCMPPDE-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 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 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- PPQRADLPLZYEKN-UHFFFAOYSA-N tritylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 PPQRADLPLZYEKN-UHFFFAOYSA-N 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は下記一般式Ｎ）
（式中、ＡｒはＮ、Ｎ−ジグリシジルアミノ基を少なく
とも１つ以上有すＣ１〜Ｃ＋ａの芳香族炭化水素を表し
、Ｒ２は水素原子又はメチル基でありｎは１〜３の整数
である）
で表される（メタ）アクリルアミド基とＮ、、Ｎ−ジグ
リシジル基を有する新規なエポキシ樹脂及びその製造方
法に関するものである。Detailed Description of the Invention The present invention relates to the following general formula N) (wherein, Ar represents a C1 to C+a aromatic hydrocarbon having at least one N,N-diglycidylamino group, and R2 is hydrogen The present invention relates to a novel epoxy resin having a (meth)acrylamide group represented by (atom or methyl group, and n is an integer of 1 to 3) and an N,,N-diglycidyl group, and a method for producing the same.
本発明者らは反応性の異なるエポキシ基とアクリロイル
基を同一分子内に含む新規な化合物について鋭意研究を
進めた結果、高い耐熱性を有する新規エポキシ樹脂を見
出し、本発明に到達した。The present inventors conducted intensive research on new compounds containing an epoxy group and an acryloyl group with different reactivities in the same molecule, and as a result, discovered a new epoxy resin with high heat resistance and arrived at the present invention.
即ち、本発明の第１は下記の一般式（Ｉ）（式中、Ａｒ
はＮ５Ｎ−ジグリシジルアミノ基を少なくとも１つ以上
有すＣ７〜Ｃ１４の芳香族炭化水素を表し、Ｒ，は水素
原子又はメチル基でありｎは１〜３の整数である）
で表される新規エポキシ樹脂を内容とし、本発明の第２
は下記の一般式（Ｉｆｌ）
（ＮＨａ下〒Ａｒ’ （ｍ）（式中、Ａｒ’
はＣｋ”Ｃ＋ａの芳香族炭化水素を表し、ｎ′は１〜３
の整数である）
で表される化合物とエピクロルヒドリンを付加せしめた
ものに下記一般式（ＩＶ）
ＣＨｔ＝Ｃ−ＣＮｌｌＣＨＪＲｚ （ＩＶ）（式
中、Ｒ１は水素原子又はメチル基を、Ｒ２は水素原子又
は０１〜Ｃ４の炭化水素基を表す）で示されるＮ−メチ
ロール（メタ）アクリルアミド又はＮ−アルコキシメチ
ル（メタ）アクリルアミドを縮合させた後、苛性アルカ
リで脱ハロゲン化水素反応を行うことを特徴とする新規
エポキシ樹脂の製造方法をそれぞれ内容とするものであ
る。That is, the first aspect of the present invention is the following general formula (I) (wherein, Ar
represents a C7 to C14 aromatic hydrocarbon having at least one N5N-diglycidylamino group, R is a hydrogen atom or a methyl group, and n is an integer from 1 to 3) The second embodiment of the present invention contains an epoxy resin.
is the following general formula (Ifl) (NHa under 〒Ar' (m) (where Ar'
represents an aromatic hydrocarbon of Ck"C+a, and n' is 1 to 3
The following general formula (IV) CHt=C-CNllCHJRz (IV) (wherein, R1 is a hydrogen atom or a methyl group, and R2 is a hydrogen atom or It is characterized by condensing N-methylol (meth)acrylamide or N-alkoxymethyl (meth)acrylamide represented by (representing a hydrocarbon group of 01 to C4) and then performing a dehydrohalogenation reaction with a caustic alkali. Each content includes a method for producing a new epoxy resin.
本発明の新規エポキシ樹脂はエポキシ基側を通常用いら
れる酸無水物で硬化させ、アクリロイル基をラジカル重
合、イオン重合又は紫外線や電子線の照射により重合さ
せ硬化することにより、高い耐熱性を有する硬化物を得
ることができる。又、アミン類、ポリアミド樹脂、ポリ
スルフイツト樹脂、三フッ化ホウ素−アミンコンプレッ
クス、フェノール樹脂、ジシアンジアミド等でも硬化さ
せることができる。その用途は、コーティング材料、電
気絶縁材料、積層物構造材料、土木建築材料、接着材、
ポリオレフィンの改質剤等である。The new epoxy resin of the present invention is cured with high heat resistance by curing the epoxy group side with a commonly used acid anhydride and polymerizing and curing the acryloyl group by radical polymerization, ionic polymerization, or irradiation with ultraviolet rays or electron beams. can get things. It can also be cured with amines, polyamide resins, polysulfite resins, boron trifluoride-amine complexes, phenolic resins, dicyandiamide, and the like. Its uses include coating materials, electrical insulation materials, laminate structural materials, civil engineering and construction materials, adhesives,
Modifiers for polyolefins, etc.
本発明の新規エポキシ樹脂は一般式（Ｉ［［）％式％（
［）
（式中、Ａｒ’はＣ６〜Ｃ４４の芳香族炭化水素を表し
、ｎ′は１〜３の整数である）
で表される化合物とエピクロルヒドリンを付加せしめた
ものに、下記一般式（ＩＶ）
ＣＨｚ＝Ｃ−ＣＮＨＣＨｚＯＲｚ （ＩＶ ）ろ
（式中、Ｒ１は水素原子又はメチル基を、Ｒｔは水素原
子又はＣ，−Ｃ，の炭化水素基を表す）で示されるＮ−
メチロール（メタ）アクリルアミド又はＮ−アルコキシ
メチル（メタ）アクリルアミドを縮合させた後、苛性ア
ルカリで脱ハロゲン化水素反応を行うことにより製造で
きる。The novel epoxy resin of the present invention has the general formula (I[[)% formula%(
The following general formula (IV ) CHz=C-CNHCHzORz (IV) N- represented by (wherein, R1 represents a hydrogen atom or a methyl group, and Rt represents a hydrogen atom or a hydrocarbon group of C, -C,)
It can be produced by condensing methylol (meth)acrylamide or N-alkoxymethyl (meth)acrylamide and then performing a dehydrohalogenation reaction with a caustic alkali.
上記一般式（ＩＩ）で表されるアミノ基を１つ以上有す
る芳香族炭化水素としては任意のものが使用できるが、
例示すればアニリン、０−トルイジン、ｍ−トルイジン
、３．５−ジメチルアニリン等のアニリン性化合物、１
−ナフチルアミン、２−ナフチルアミン、９−アミノア
ントラセン等の多環状アミノ化合物等が挙げられる。こ
れらのもののうち、アニリン、トルイジンは特に安価な
工業原料であるので使用し易い。Any aromatic hydrocarbon having one or more amino groups represented by the above general formula (II) can be used, but
Examples include aniline compounds such as aniline, 0-toluidine, m-toluidine, 3,5-dimethylaniline, 1
Examples include polycyclic amino compounds such as -naphthylamine, 2-naphthylamine, and 9-aminoanthracene. Among these, aniline and toluidine are particularly inexpensive industrial raw materials and are therefore easy to use.
上記一般式（ＴＶ）で表される化合物としては、Ｎ−メ
チロールアクリルアミド、Ｎ−メチロールメタアクリル
アミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−メト
キシメチルアクリルアミド、Ｎ−ブトキシメチルアクリ
ルアミド、Ｎ−ブトキシメチルメタアクリルアミド等（
以下これらをＮ−メチロールアクリルアミド類という）
が使用できる。以下にその製造方法については詳しく説
明する。Examples of the compound represented by the above general formula (TV) include N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. (
These are hereinafter referred to as N-methylolacrylamides)
can be used. The manufacturing method will be explained in detail below.
第１段階の付加反応は一般式（ＩＩＩ）で表される化合
物とエピハロヒドリンを触媒量の水の存在下で反応させ
ることによって行う、エピハロヒドリンの使用量は化合
物（Ｉｌｌ）に対して２当量以上、より好ましくは２．
２〜５当量である。エピハロヒドリンとしては、エピク
ロルヒドリン、エピブロムヒドリン、エピヨードヒドリ
ン等が使用できる、又、触媒として木取外にもメタノー
ル、エタノール等のアルコール類、カルボン酸、フェー
ル等の酸類等を用いることができる０反応温度及び反応
時間は５０〜１２０℃、３０分以上で、より好ましくは
７０〜１００℃、２〜１０時間である。The first step addition reaction is carried out by reacting the compound represented by the general formula (III) with epihalohydrin in the presence of a catalytic amount of water, the amount of epihalohydrin used is 2 equivalents or more based on compound (Ill), More preferably 2.
It is 2 to 5 equivalents. As the epihalohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, etc. can be used, and as a catalyst, alcohols such as methanol, ethanol, etc., acids such as carboxylic acid, fer, etc. can be used in addition to Kitori. The reaction temperature and reaction time are 50 to 120°C for 30 minutes or more, more preferably 70 to 100°C for 2 to 10 hours.
第２段階の縮合反応は、ハロヒドリンとＮ−メチロール
アクリルアミド類とを酸触媒の存在下で反応させること
によって行う、酸触媒としては塩酸、硫酸、リン酸等の
無機酸、Ｐ−）ルエンスルホン酸、シェラ酸、酢酸等の
有機酸を使用できる、酸触媒の使用量は、化合物（ＩＩ
Ｉ）に対して０゜０１〜１０倍モル％の範囲で任意に選
択できる。The second stage condensation reaction is carried out by reacting halohydrin and N-methylolacrylamide in the presence of an acid catalyst. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and P-)luenesulfonic acid. The amount of the acid catalyst to be used can be an organic acid such as , Scherer's acid, or acetic acid.
It can be arbitrarily selected within the range of 0.01 to 10 times mole % relative to I).
より好ましくは０．１−１モル％の量を使用できる０反
応温度及び反応時間は２０〜８０℃、３０分以上で、よ
り好ましくは４〜１０時間である。More preferably, an amount of 0.1-1 mol% can be used.The reaction temperature and reaction time are 20-80°C, 30 minutes or more, and more preferably 4-10 hours.
第３段階は、第２段階で用いた酸を中和した後、相間移
動触媒の存在下で、苛性アルカリにより脱ハロゲン化水
素反応を行う、苛性アルカリとしては、尿酸化ナトリウ
ム、水酸化カリウム、水酸化リチウム等が使用できる。In the third step, after neutralizing the acid used in the second step, a dehydrohalogenation reaction is performed using a caustic alkali in the presence of a phase transfer catalyst.The caustic alkali includes sodium urinary oxide, potassium hydroxide, Lithium hydroxide etc. can be used.
相間移動触媒として一般に知られているもの、例えばテ
トラブチルアンモニウムブロマイド、トリオクチルメチ
ルアンモニウムクロライド、ベンジルトリエチルアンモ
ニウムクロライド、ベンジルトリメチルアンモニウムク
ロライド等の第４級アンモニウム塩；テトラフェニルホ
スホニウムクロライド、トリフェニルメチルホスホニウ
ムクロライド等の第４級ホスホニウム塩；第４級アルソ
ニウム塩、及びクラウンエーテル類が使用できる。相間
移動触媒は化合物（Ｉｌｌ）に対して０．１〜１００モ
ル％、より好ましくは１〜１０モル％の量を使用できる
。苛性アルカリの使用量は化合物（ＩＮ）に対して２倍
モル以上、より好ましくは２．２〜３倍モル使用できる
０反応温度及び反応時間は２０〜８０℃、１〜５時間、
より好ましくは４０〜６０℃、１〜３時間である。又、
反応は無溶媒もしくは、非反応性の水と混合しない溶剤
、例えばトルエン、キシレン、メチルイソブチルケトン
等中で行うことができる。Those generally known as phase transfer catalysts, such as quaternary ammonium salts such as tetrabutylammonium bromide, trioctylmethylammonium chloride, benzyltriethylammonium chloride, and benzyltrimethylammonium chloride; tetraphenylphosphonium chloride, triphenylmethylphosphonium chloride Quaternary phosphonium salts such as quaternary phosphonium salts; quaternary arsonium salts, and crown ethers can be used. The phase transfer catalyst can be used in an amount of 0.1 to 100 mol%, more preferably 1 to 10 mol%, based on compound (Ill). The amount of caustic alkali to be used is at least 2 times the mole of the compound (IN), more preferably 2.2 to 3 times the mole.The reaction temperature and reaction time are 20 to 80°C, 1 to 5 hours,
More preferably, the temperature is 40 to 60°C for 1 to 3 hours. or,
The reaction can be carried out without a solvent or in a non-reactive water-immiscible solvent such as toluene, xylene, methyl isobutyl ketone and the like.
反応終了後、生成する塩を水洗により除き、未反応エピ
ハロヒドリン、非反応性溶剤を留去することにより、一
般式（Ｉ）で示した化合物を主生成物とする混合物が得
られる。得られた混合物をカラムクロマトにより分離し
、一般式（Ｉ）の新規エポキシ樹脂が単離精製される。After the reaction is completed, the salt produced is removed by washing with water, and the unreacted epihalohydrin and non-reactive solvent are distilled off to obtain a mixture containing the compound represented by the general formula (I) as the main product. The resulting mixture is separated by column chromatography to isolate and purify the novel epoxy resin of general formula (I).
本発明のエポキシ樹脂の中でも、特に下記構造式（ｎ） Ｂ。Among the epoxy resins of the present invention, especially the following structural formula (n) B.
（式中、Ｒ１は水素原子又はメチル基であり、ｍは０〜
２の整数である）
で表されるエポキシ樹脂が原料入手が容易であることか
ら製造上有利である。この際用いられるで表される。具
体的な例としてはアニリン、０−１ｍ−１あるいはｐ−
）ルイジン等が挙げられる本発明のエポキシ樹脂は、エ
ポキシ基を酸無水物で硬化させ、アクリロイル基をラジ
カル重合、イオン重合、又は紫外線、電子線の照射によ
り重合させ硬化することにより、高い耐熱性を有する硬
化物を得ることができる。(In the formula, R1 is a hydrogen atom or a methyl group, and m is 0-
The epoxy resin represented by (2) is an integer of 2, and is advantageous in production because raw materials are easily available. In this case, it is expressed as: Specific examples include aniline, 0-1m-1 or p-
) The epoxy resin of the present invention, which includes luidine, has high heat resistance by curing the epoxy group with an acid anhydride and polymerizing and curing the acryloyl group by radical polymerization, ionic polymerization, or irradiation with ultraviolet rays or electron beams. A cured product having the following properties can be obtained.
以下に本発明を実施例により説明するが、本発明はこれ
ら実施例のみに限定されるものではない実施例１
エピクロルヒドリン３４６．５２ｇ （３，７４モル）
水３０．６ｇ （Ｉ，７モル）混合物攪拌中に７０℃で
アニリン１５８．２７ｇ （Ｉ，７モル）を９０分で滴
下した後８０℃に昇温し、攪拌を５時間行った。The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 346.52 g (3.74 mol) of epichlorohydrin
While stirring the mixture of 30.6 g (I, 7 mol) of water, 158.27 g (I, 7 mol) of aniline was added dropwise over 90 minutes at 70°C, and the mixture was heated to 80°C and stirred for 5 hours.
反応混合物を３５℃に冷却し、９７．５％Ｎ−メチロー
ルアクリルアミド１９３．７ｇ （Ｉ，８７モル）を粉
末で添加し溶解した後、濃塩酸１７２．４ｇ （Ｉ，７
モル）を２０分で滴下した。５０℃に昇温し、７時間攪
拌を続けた。The reaction mixture was cooled to 35°C, and 193.7 g (I, 87 mol) of 97.5% N-methylolacrylamide was added as a powder and dissolved, followed by 172.4 g (I, 7 mol) of concentrated hydrochloric acid.
mol) was added dropwise over 20 minutes. The temperature was raised to 50°C and stirring was continued for 7 hours.
メチルイソブチルケトン４００ｍ１添加し、５Ｎ−苛性
ソーダ３４０ｍ１ （Ｉ，７モル）を３０分で滴下し
た後３０分撹拌を行い、静置し、デカンテーションによ
り水層を除去した。反応混合物［ｔ４’中にベンジルト
リエチルアンモニウムクロライド３．８６ｇ （０，０
１７モル）を添加し、４８．６％苛性ソーダ３４９．８
ｇ （４，２５モル）を９０分で滴下した後、２時間攪
拌を続けた。After adding 400 ml of methyl isobutyl ketone and dropping 340 ml of 5N caustic soda (I, 7 mol) over 30 minutes, the mixture was stirred for 30 minutes, allowed to stand, and the aqueous layer was removed by decantation. 3.86 g of benzyltriethylammonium chloride (0,0
17 mol), 48.6% caustic soda 349.8
g (4.25 mol) was added dropwise over 90 minutes, and stirring was continued for 2 hours.
静置し水層を除去し、水洗精製を行った後、未反応エピ
クロルヒドリン及びメチルイソブチルケトンを減圧によ
り除去し、淡黄色粘性液体４４５゜６６ｇを得た。一部
をシリカゲルを担体にしたカラムクロマト（展開溶媒：
酢酸エチル）により分離し、ｍ、ｐ、（ｉ３〜６６℃の
無色放射状結晶を単離・精製した。このものの赤外吸収
スペクトル（第１図）及び’ＨＮＭＲスペクトル（溶媒
二ＣＤＣｌ１３、ＴＭＳ基準） （第２図）°から、Ｎ
−（４−Ｎ’、Ｎ’−ジグリシジルアミノフェニルメチ
ル）アクリルアミドであることが判明した。こノモのは
上記一般式（■）において、ｐ−ｚ操体で且つｍ−０の
ものに相当する。又、塩酸−ピリジン法によるエポキシ
当量は１４１ （計算値１４４）であった。The mixture was allowed to stand, the aqueous layer was removed, and after washing and purification with water, unreacted epichlorohydrin and methyl isobutyl ketone were removed under reduced pressure to obtain 445.66 g of a pale yellow viscous liquid. Column chromatography using silica gel as a carrier (developing solvent:
Colorless radial crystals of m, p, (i3~66°C) were isolated and purified.The infrared absorption spectrum (Fig. 1) and 'HNMR spectrum (solvent 2 CDCl 13, TMS standard) of this (Figure 2) From ° to N
-(4-N',N'-diglycidylaminophenylmethyl)acrylamide. This item corresponds to the p-z body and m-0 in the above general formula (■). The epoxy equivalent determined by the hydrochloric acid-pyridine method was 141 (calculated value 144).
実施例２
エピクロルヒドリン２０．４ｇ （０，２２モル）、水
１．８ｇ （０，１モル）混合物撹拌中に７０℃でｍ−
）ルイジン１０．７ｇ （０，１モル）を１０分で滴下
した後、８０℃に昇温し攪拌を４時間行った。反応混合
物を３５℃に冷却し、９７．５％Ｎ−メチロールアクリ
ルアミド１１．４ｇ（０，１１モル）、濃塩酸１０．１
ｇ （０，１％ル）を添加し、５０℃に昇温し１０時間
攪拌を続けた。メチルイソブチルケトンを５０ｍ１添加
し、５Ｎ−苛性ソーダ２０ｍ１を添加した後、３０分攪
拌を行い、静置し、デカンテーションにより水層を除去
した０反応混合物攪拌中にベンジルトルエチルアンモニ
ウムクロライド０．２３ｇ （０，００１モル）を添加
し、４８．６％苛性ソーダ２０．６ｇ （０，２５モル
）を３０分で滴下した後３時間攪拌を続けた。Example 2 20.4 g (0.22 mol) of epichlorohydrin, 1.8 g (0.1 mol) of water were mixed at 70° C. while stirring.
) After 10.7 g (0.1 mol) of luidine was added dropwise over 10 minutes, the temperature was raised to 80° C. and stirring was performed for 4 hours. The reaction mixture was cooled to 35°C, and 11.4 g (0.11 mol) of 97.5% N-methylolacrylamide and 10.1 g of concentrated hydrochloric acid were added.
g (0.1%) was added, the temperature was raised to 50° C., and stirring was continued for 10 hours. After adding 50 ml of methyl isobutyl ketone and 20 ml of 5N caustic soda, the mixture was stirred for 30 minutes, allowed to stand, and the aqueous layer was removed by decantation. While stirring the reaction mixture, 0.23 g of benzyltoluethylammonium chloride ( After adding 20.6 g (0.25 mol) of 48.6% caustic soda dropwise over 30 minutes, stirring was continued for 3 hours.
静置し水層を除去し、水洗精製を行った後、未反応エピ
クロルヒドリン及びメチルイソブチルケトンを減圧によ
り除去し、淡黄色粘性液体２４゜６２ｇを得た。塩酸−
ピリジン法によるエポキシ当量は１６６であった。The mixture was allowed to stand, the aqueous layer was removed, and after washing and purification with water, unreacted epichlorohydrin and methyl isobutyl ketone were removed under reduced pressure to obtain 24.62 g of a pale yellow viscous liquid. Hydrochloric acid-
The epoxy equivalent by the pyridine method was 166.
得られた粘性液体をアルミナを担体にしたプレートクロ
マト（展開溶媒ニジエチルエーテル）により分離し、ｍ
、ｐ、１０２〜１０５℃の放射状結晶を単離精製した。The obtained viscous liquid was separated by plate chromatography using alumina as a carrier (developing solvent Nidiethyl ether).
, p, 102-105°C radial crystals were isolated and purified.
このものの赤外線吸収スペクトル（第３図）からＮ−（
３−メチル−４−Ｎ′、Ｎ′−ジグリシジルフェニルメ
チル）アクリルアミドであることが判明した。このもの
は上記一般式（ＩＩ）において、Ｐ−置換体で且つｍ＝
１のものに相当する。From the infrared absorption spectrum (Figure 3) of this material, N-(
It turned out to be 3-methyl-4-N', N'-diglycidylphenylmethyl)acrylamide. In the above general formula (II), this compound is a P-substituted product and m=
Corresponds to 1.
応用例１
実施例１で単離したＮ−（４−Ｎ’、Ｎ’−ジグリシジ
ルアミノフェニルメチル）アクリルアミド１００部、無
水メチルナジック酸１０７．３部、ベンジルメチルアミ
ン０．７部及びｔ−ブチルパーベンゾエート３部を混合
し、１００℃１５分、１４０℃１時間、１７０℃２時間
硬化した。硬化物のビカフト軟化点（荷重１ｋｇ重）は
２５０℃以上であった。Application Example 1 100 parts of N-(4-N', N'-diglycidylaminophenylmethyl)acrylamide isolated in Example 1, 107.3 parts of methylnadic anhydride, 0.7 part of benzylmethylamine, and t- 3 parts of butyl perbenzoate were mixed and cured at 100°C for 15 minutes, 140°C for 1 hour, and 170°C for 2 hours. The Vikaft softening point (load: 1 kg) of the cured product was 250°C or higher.
第１図、第２図は、それぞれ実施例１で得られた本発明
のエポキシ樹脂の赤外吸収スペクトル及び’ＨＮＭＲス
ペクトルであり、第３図は実施例２で得られた本発明の
エポキシ樹脂の赤外吸収スペクトルである。Figures 1 and 2 are the infrared absorption spectrum and 'HNMR spectrum of the epoxy resin of the present invention obtained in Example 1, respectively, and Figure 3 is the epoxy resin of the present invention obtained in Example 2. This is the infrared absorption spectrum of
Claims (1)
とも１つ以上有すＣ＿６〜Ｃ＿１＿４の芳香族炭化水素
を表し、Ｒ＿１は水素原子又はメチル基であり、ｎは１
〜３の整数である） で表される新規エポキシ樹脂。 ２、エポキシ樹脂が下記構造式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１は水素原子又はメチル基であり、ｍは０
〜２の整数である） で表される化合物である特許請求の範囲第１項記載のエ
ポキシ樹脂。 ３、下記一般式（III） （ＮＨ＿２）−＿ｎ＿′Ａｒ′（III） （式中、Ａｒ′はＣ＿６〜Ｃ＿１＿４の芳香族炭化水素
を表し、ｎ′は１〜３の整数である） で表される化合物とエピクロルヒドリンを付加せしめた
ものに下記一般式（IV） ▲数式、化学式、表等があります▼（IV） （式中、Ｒ＿１は水素原子又はメチル基を、Ｒ＿２は水
素原子又はＣ＿１〜Ｃ＿４の炭化水素基を表す）で示さ
れるＮ−メチロール（メタ）アクリルアミド又はＮ−ア
ルコキシメチル（メタ）アクリルアミドを縮合させた後
、苛性アルカリで脱ハロゲン化水素反応を行うことを特
徴とする新規エポキシ樹脂の製造方法。 ４、一般式（III）で表される化合物とエピハロヒドリ
ンを付加せしめたものと一般式（IV）で表される化合物
との縮合反応の触媒として、塩酸、硫酸、リン酸、シュ
ウ酸、酢酸及びＰ−トルエンスルホン酸から選択される
少なくとも１種を用いる特許請求の範囲第３項記載の製
造方法。 ５、苛性アルカリによる脱ハロゲン化水素反応時の相間
移動触媒として、第４級アンモニウム塩、第４級ホスホ
ニウム塩、第４級アルソニウム塩及びクラウンエーテル
類から選択される少なくとも１種を用いる特許請求の範
囲第３項記載の製造方法。[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar is C_6~ having at least one N,N-diglycidylamino group C_1_4 represents an aromatic hydrocarbon, R_1 is a hydrogen atom or a methyl group, and n is 1
An integer of ~3) A novel epoxy resin represented by: 2. The epoxy resin has the following structural formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 is a hydrogen atom or a methyl group, and m is 0
The epoxy resin according to claim 1, which is a compound represented by: 3. Expressed by the following general formula (III) (NH_2)-_n_'Ar'(III) (wherein, Ar' represents an aromatic hydrocarbon of C_6 to C_1_4, and n' is an integer from 1 to 3) The following general formula (IV) is added to the compound and epichlorohydrin. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is a hydrogen atom or C_1 ~ A novel epoxy characterized by condensing N-methylol (meth)acrylamide or N-alkoxymethyl (meth)acrylamide represented by C_4 (representing a hydrocarbon group) and then performing a dehydrohalogenation reaction with a caustic alkali. Method of manufacturing resin. 4. Hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, acetic acid and The manufacturing method according to claim 3, using at least one selected from P-toluenesulfonic acid. 5. A patent claim in which at least one selected from quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, and crown ethers is used as a phase transfer catalyst during the dehydrohalogenation reaction using a caustic alkali. The manufacturing method according to scope 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8845686A JPS62246563A (en) | 1986-04-17 | 1986-04-17 | Novel epoxy resin and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8845686A JPS62246563A (en) | 1986-04-17 | 1986-04-17 | Novel epoxy resin and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62246563A true JPS62246563A (en) | 1987-10-27 |
Family
ID=13943294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8845686A Pending JPS62246563A (en) | 1986-04-17 | 1986-04-17 | Novel epoxy resin and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62246563A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013089006A1 (en) * | 2011-12-15 | 2013-06-20 | 東レ・ファインケミカル株式会社 | Method for producing glycidylamine epoxy compound |
-
1986
- 1986-04-17 JP JP8845686A patent/JPS62246563A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013089006A1 (en) * | 2011-12-15 | 2013-06-20 | 東レ・ファインケミカル株式会社 | Method for producing glycidylamine epoxy compound |
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