JP5858483B2 - 新規な硬化剤 - Google Patents
新規な硬化剤 Download PDFInfo
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- JP5858483B2 JP5858483B2 JP2012555494A JP2012555494A JP5858483B2 JP 5858483 B2 JP5858483 B2 JP 5858483B2 JP 2012555494 A JP2012555494 A JP 2012555494A JP 2012555494 A JP2012555494 A JP 2012555494A JP 5858483 B2 JP5858483 B2 JP 5858483B2
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- aniline
- curing agent
- epoxy resin
- component
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 27
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical compound C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 11
- 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 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001448 anilines Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- KZWGSWJFZCTEFR-UHFFFAOYSA-N aniline N,N'-diphenylmethanediamine Chemical compound C(NC1=CC=CC=C1)NC1=CC=CC=C1.NC1=CC=CC=C1 KZWGSWJFZCTEFR-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 37
- 239000011347 resin Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 13
- 230000009257 reactivity Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000004982 aromatic amines Chemical group 0.000 description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VIOMIGLBMQVNLY-UHFFFAOYSA-N 4-[(4-amino-2-chloro-3,5-diethylphenyl)methyl]-3-chloro-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C(=C(CC)C(N)=C(CC)C=2)Cl)=C1Cl VIOMIGLBMQVNLY-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- DDTKYVBFPULMGN-UHFFFAOYSA-N 2-methyl-6-propan-2-ylaniline Chemical compound CC(C)C1=CC=CC(C)=C1N DDTKYVBFPULMGN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 0 *c1cc(CNc(cc2*)cc(N)c2I)cnc1*=C Chemical compound *c1cc(CNc(cc2*)cc(N)c2I)cnc1*=C 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010944 pre-mature reactiony Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- NBMQGZICMNFIGL-UHFFFAOYSA-N 3,4-bis(oxiran-2-ylmethyl)naphthalene-1,2-diol Chemical compound C1OC1CC=1C(O)=C(O)C2=CC=CC=C2C=1CC1CO1 NBMQGZICMNFIGL-UHFFFAOYSA-N 0.000 description 1
- VDJBIPLKIGSVRG-UHFFFAOYSA-N 3-chloro-2,6-diethylaniline Chemical compound CCC1=CC=C(Cl)C(CC)=C1N VDJBIPLKIGSVRG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- -1 aromatic glycidyl amines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
ここで、R1〜R4はそれぞれ直線又は分岐C1〜C5アルキルから選択される。
35mlのプロパン−2−オールと65mlの水と15.4mlの濃硫酸を、機械式撹拌機を備えた500mlの反応フラスコ内で21.9グラムの2,6−ジエチルアニリン(DEA)と28.1グラムの2,6−ジイソプロピルアニリン(DIPA)に混ぜ加えた。得られた結晶のスラリーは撹拌により60℃に加熱し、13.3mlの35%w/wホルムアルデヒド水溶液が30分にわたって加えた。スラリーは徐々に粘度下がり、目に見えてより透明になった。5時間後、混合物は再び不透明になっており、35%アンモニア溶液で中和する前に混合物を室温まで冷却した。生成物をクロロホルムにより(混合物は完全に可溶性であった)抽出し、蒸留水で洗浄した。透明な有機相を硫酸ナトリウムで乾燥し、回転式膜蒸発(rotary film evaporation)により濾過し、溶媒を除去した。49グラムの透明な琥珀色の粘稠液が得られた。室温で14日後、この生成物中に結晶化を見ることができた。
アミン混合物が2−メチル−6−イソプロピルアニリン(MIPA)と2,6−ジエチルアニリン(DEA)であることを除いて、例1の条件が使用された。一連の反応が行われ、MIPAとDEAの比はホルムアルデヒド源としての14.71mlのホルマリン溶液を使用して変えられたた。使用した量を以下に示す。
25gのM−MIPAと20.3gのM−DEAを100℃で加熱することにより溶融した。次に、2つの液体硬化剤が混合し、室温まで冷却し粘着性の褐色の半固形物を形成した。結晶化は1日以内に発生した。
5リットルのフランジ付き反応容器中に、l37mlの硫酸と580mlの水と313mlのプロパン−2−オールの混合物を入れた。これに、250グラムの3−クロロ−2,6−ジエチルアニリンと203グラムの2−メチル−6−イソプロピルアニリンを加えた。フラスコに撹拌機と滴下漏斗と凝縮器とを備え、温度を60℃に上げた。
25gのM−MIPAと20.3gのM−CDEAが100℃に加熱して溶融した。次に、2つの液体硬化剤が混合し、室温まで冷却して、粘着性の褐色の半固形物を形成した。結晶化は1日以内に発生した。
100gのMY721エポキシ樹脂(Huntsman Advanced Materials,Switzerland)を例4で得られた76.3gのM−MIPACDEA硬化剤と80℃の温度で混合して、一様な混合物を形成した。
100gのMY721エポキシ樹脂(Huntsman Advanced Materials,Switzerland)を34.3gのM−MIPA及び41.9gのMCDEA硬化剤と80℃の温度で混合して、一様な混合物を形成した。M−MIPAとM−CDEAは完全に液体となるまで100℃で予め溶融された。
例6と比較例7の物質の性質を、以下の表内の商用樹脂トランスファ成形樹脂RTM6(Hexcelから入手可能)と比較した。反応性とTgはRTM6と類似しており、例6と比較例7の物質を航空宇宙用液体複合材成形として適したものにしている。
Claims (14)
- エポキシ樹脂用硬化剤組成物を作製する方法であって、前記エポキシ樹脂用硬化剤組成物は室温で液体であり、前記方法は、次の構造を有する2つのアニリンA及びBを、ホルムアルデヒドを又はホルムアルデヒドを形成する化合物を有する酸性媒質中でアニリンA対アニリンBの重量比4:1〜1:4で反応させて、少なくとも30重量パーセントのアニリンA及びアニリンBのハイブリッドメチレンビスアニリン、アニリンAのメチレンビスアニリン並びにアニリンBのメチレンビスアニリンを含有するエポキシ樹脂用硬化剤組成物を形成する工程を含み、
前記ハイブリッドメチレンビスアニリンは下記の式1で表され、
前記アニリンAのメチレンビスアニリンは下記の式2で表され、
前記アニリンBのメチレンビスアニリンは下記の式3で表され、
ここで、R1〜R4はそれぞれ直線又は分岐C1〜C5アルキルから個々に選択される、
方法。 - アニリンA対アニリンBの重量比が2:1〜1:2である、請求項1に記載の方法。
- エポキシ樹脂用硬化剤組成物であって、
室温で液体であり、
ホルムアルデヒドを又はホルムアルデヒドを形成する化合物を有する酸性媒質中での、重量比4:1〜1:4の次の構造を有するアニリンAとアニリンBとの反応生成物であり、
少なくとも30重量%のアニリンA及びアニリンBのハイブリッドメチレンビスアニリン、アニリンAのメチレンビスアニリン並びにアニリンBのメチレンビスアニリンを含有し、
前記ハイブリッドメチレンビスアニリンは下記の式1で表され、
前記アニリンAのメチレンビスアニリンは下記の式2で表され、
前記アニリンBのメチレンビスアニリンは下記の式3で表され、
ここで、R 1 〜R 4 はそれぞれ直線又は分岐C 1 〜C 5 アルキルから個々に選択される、
エポキシ樹脂用硬化剤組成物。 - 少なくとも50wt%の前記アニリンA及びアニリンBのハイブリッドメチレンビスアニリンを含む、請求項3に記載のエポキシ樹脂用硬化剤組成物。
- R1〜R4がそれぞれ直鎖又は分岐C1〜C3アルキル基である、請求項3に記載のエポキシ樹脂用硬化剤組成物。
- 請求項3に記載のエポキシ樹脂用硬化剤組成物を含む第1の液体成分と、硬化性エポキシ樹脂を含む第2の液体成分と、を含む二成分硬化性樹脂組成物。
- 前記第1の液体成分が63wt%の前記アニリンA及びアニリンBのハイブリッドメチレンビスアニリンを含む、請求項6に記載の二成分硬化性樹脂組成物。
- 前記第2の成分が少なくとも50wt%の前記硬化性エポキシ樹脂を含む、請求項6に記載の二成分硬化性樹脂組成物。
- 請求項6に記載の二成分硬化性樹脂組成物の硬化生成物である、硬化組成物。
- 繊維配列を含有する、請求項9に記載の硬化組成物。
- 前記繊維配列は構造繊維層を含む、請求項10に記載の硬化組成物。
- 二成分硬化性樹脂組成物を作製する方法であって、
請求項3に記載のエポキシ樹脂用硬化剤組成物を用意する工程、
硬化性エポキシ樹脂を用意する工程、及び
前記エポキシ樹脂用硬化剤組成物を前記硬化性エポキシ樹脂と混合して二成分硬化性樹脂組成物を形成する工程、
を含む方法。 - 請求項12に記載の方法であって、前記二成分硬化性樹脂組成物を構造繊維と組み合わせる追加工程をさらに含む、方法。
- 請求項12に記載の方法であって、前記二成分硬化性樹脂組成物を硬化する追加工程をさらに含む、方法。
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GB1003643A GB2478343A (en) | 2010-03-05 | 2010-03-05 | Asymmetric bis-aniline resin curing agent |
GB1003643.2 | 2010-03-05 | ||
PCT/GB2011/050412 WO2011107796A1 (en) | 2010-03-05 | 2011-03-01 | Novel curing agents |
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EP3102623B1 (en) * | 2014-02-06 | 2020-03-25 | Hexcel Composites Limited | Curing agents for epoxy resins |
GB201402052D0 (en) * | 2014-02-06 | 2014-03-26 | Hexcel Composites Ltd | 4,4' Methylene bis anilines as curing agents for epoxy resins |
RU2570434C1 (ru) * | 2014-06-11 | 2015-12-10 | Закрытое акционерное общество "Институт новых углеродных материалов и технологий" (ЗАО "ИНУМиТ") | Эпоксидная композиция и способ ее изготовления |
CN111491974A (zh) | 2017-12-22 | 2020-08-04 | 米其林集团总公司 | 环氧官能化的酚醛树脂组合物 |
EP4296297A1 (en) * | 2021-02-18 | 2023-12-27 | Toray Industries, Inc. | Epoxy resin composition for fiber-reinforced composite material, fiber-reinforced composite material, and method for producing fiber-reinforced composite material |
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GB120377A (en) | 1917-09-04 | Ansgarius Betulander Gotthilf | Improvements in Electrical Relay Mechanism. | |
SU115541A1 (ru) * | 1958-01-29 | 1958-11-30 | М.С. Акутин | Способ отверждени эпоксидных смол |
FR1549769A (ja) * | 1966-12-20 | 1968-12-13 | ||
JPS509839B2 (ja) * | 1972-02-18 | 1975-04-16 | ||
DE2339237A1 (de) * | 1973-08-02 | 1975-02-20 | Nippon Kayaku Kk | 4,4'-diaminodiphenylmethane, verfahren zu ihrer herstellung und ihre verwendung als haerter fuer epoxyharze |
CH660358A5 (de) | 1984-07-06 | 1987-04-15 | Lonza Ag | Substituierte p,p'-methylen-bisaniline. |
CH666260A5 (de) * | 1985-10-23 | 1988-07-15 | Lonza Ag | Substituierte p,p'-methylen-bis-aniline und deren verwendung als kettenverlaengerungsmittel oder vernetzungsmittel fuer polyurethane. |
EP0356392A3 (de) * | 1988-08-24 | 1991-09-18 | Ciba-Geigy Ag | Härtbares Epoxidharzgemisch |
JPH05132540A (ja) * | 1991-04-18 | 1993-05-28 | Nippon Kayaku Co Ltd | エポキシ樹脂用硬化剤及びそれを用いるエポキシ樹脂の硬化法 |
JPH05239238A (ja) * | 1991-08-26 | 1993-09-17 | Matsushita Electric Works Ltd | プリプレグの製造法及び該プリプレグを用いた積層板 |
JP3312872B2 (ja) * | 1998-04-30 | 2002-08-12 | 大塚化学株式会社 | エポキシ樹脂用硬化剤 |
CN1082504C (zh) * | 1999-02-01 | 2002-04-10 | 华东理工大学 | 一种芳香二胺扩链剂及其制备方法和应用 |
US7144969B2 (en) * | 2001-11-16 | 2006-12-05 | Ppg Industries Ohio, Inc. | Impact resistant polyureaurethane and polyureaurethane prepolymer having low NCO/OH ratio |
JP2004359672A (ja) * | 2003-05-09 | 2004-12-24 | Nippon Kayaku Co Ltd | アニリン系化合物、およびその製造方法 |
DE10344379B4 (de) * | 2003-09-23 | 2008-09-11 | Mankiewicz Gebr. & Co (Gmbh & Co Kg) | Verwendung einer Zweikomponenten-Zusammensetzung zur Herstellung von flexiblen Polyurethan-Gelcoats für Kunstharz-Verbundwerkstoffe, Verfahren zur Herstellung der Verbundwerkstoffe und Verbundwerkstoffe |
JP4459612B2 (ja) * | 2003-12-25 | 2010-04-28 | イハラケミカル工業株式会社 | メチレンビスアニリン化合物の変色防止方法 |
TWI465473B (zh) * | 2009-12-17 | 2014-12-21 | Albemarle Corp | 塗料組合物 |
EP2638088B1 (en) * | 2010-09-02 | 2015-11-18 | Lonza Ltd | Halogenation of 4,4'-methylene-bis-anilines |
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JP2013521370A (ja) | 2013-06-10 |
WO2011107796A1 (en) | 2011-09-09 |
AU2011222728A1 (en) | 2012-08-23 |
RU2576615C2 (ru) | 2016-03-10 |
EP2542610A1 (en) | 2013-01-09 |
EP2542610B1 (en) | 2015-06-24 |
CA2791424A1 (en) | 2011-09-09 |
BR112012021944A2 (pt) | 2016-05-31 |
GB201003643D0 (en) | 2010-04-21 |
CN102782003A (zh) | 2012-11-14 |
RU2012142322A (ru) | 2014-04-10 |
GB2478343A (en) | 2011-09-07 |
US20120316262A1 (en) | 2012-12-13 |
US8986825B2 (en) | 2015-03-24 |
BR112012021944B1 (pt) | 2019-10-08 |
ES2546418T3 (es) | 2015-09-23 |
AU2011222728B2 (en) | 2013-11-21 |
CN106893079A (zh) | 2017-06-27 |
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