WO2021049503A1 - Composé diamine et son procédé de production - Google Patents

Composé diamine et son procédé de production Download PDF

Info

Publication number
WO2021049503A1
WO2021049503A1 PCT/JP2020/034020 JP2020034020W WO2021049503A1 WO 2021049503 A1 WO2021049503 A1 WO 2021049503A1 JP 2020034020 W JP2020034020 W JP 2020034020W WO 2021049503 A1 WO2021049503 A1 WO 2021049503A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
diamine
resin
formula
epoxy resin
Prior art date
Application number
PCT/JP2020/034020
Other languages
English (en)
Japanese (ja)
Inventor
孔明 小山
佳太郎 子田
正幸 馬野
康之 山側
Original Assignee
岡村製油株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 岡村製油株式会社 filed Critical 岡村製油株式会社
Priority to KR1020227012227A priority Critical patent/KR20220062086A/ko
Priority to JP2021545554A priority patent/JP7357391B2/ja
Priority to CN202080064182.2A priority patent/CN114364656A/zh
Publication of WO2021049503A1 publication Critical patent/WO2021049503A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
    • C07C209/56—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions from carboxylic acids involving a Hofmann, Curtius, Schmidt, or Lossen-type rearrangement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds

Definitions

  • the present invention relates to a diamine compound and a method for producing the same. More specifically, the present invention is used in coexistence with a monomer or a curing agent capable of constituting a polymer material such as a thermosetting resin or a thermoplastic resin, or the polymer material.
  • the present invention relates to a diamine compound useful as an additive and a method for producing the same.
  • Resin materials composed of polymers are used in a wide range of applications such as paints, building materials, flooring materials, earth and wood, and electronic materials. Since the required properties differ depending on these uses, there are a wide variety of resin materials that satisfy the properties.
  • resin materials such as epoxy resin, polyimide, and polyamide-imide, which are polymers whose main chain is composed of aromatic rings, have excellent mechanical and electrical properties, but are hard and brittle, and are generally resistant. It has been pointed out that it lacks impact resistance and toughness. Therefore, it is necessary to alleviate the brittleness depending on the application, and various means have been proposed so far.
  • a method of modifying the polymer by introducing a flexible chain into the main chain of the polymer to impart flexibility is known.
  • a method for introducing such a flexible chain for example, in the case of producing a thermosetting resin, a compound having a flexible chain (for example, a polar group such as an ether group, an ester group, an amide group, or a urethane group) is used as a main agent or cured. It is known to be used as an agent.
  • a thermoplastic resin it is known to use a compound having such a flexible chain as a raw material monomer.
  • An object of the present invention is to solve the above problems, and an object of the present invention is to be flexible with respect to the resin without introducing a polar group into the constituent molecules of the resin such as an epoxy resin. It is an object of the present invention to provide a diamine compound which can be used as a resin additive and a method for producing the same, which can impart the above-mentioned substances and have little influence on other properties.
  • the present invention has the following formula (I):
  • R 1 is an alkylene or alkenylene group having a total carbon number of C 14 to C 28, which is linear or has one or more C 1 to C 4 alkyl and / or alkenyl groups.
  • An alkylene group or an alkenylene group having a branched chain of It is a diamine compound represented by.
  • the main chain portion of the alkylene group or alkenylene group constituting R 1 has C 2n carbon atoms (where n is 7 to 14).
  • the linear alkylene group or linear alkenylene group of C 14 to C 28 constituting R 1 has a branched chain composed of an ethyl group.
  • the diamine compound of the present invention is 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene.
  • the present invention is also a method for producing a diamine compound represented by the above formula (I).
  • R 1 is an alkylene or alkenylene group having a total carbon number of C 14 to C 28, which is linear or has one or more C 1 to C 4 alkyl and / or alkenyl groups.
  • An alkylene group or an alkenylene group having a branched chain of R 2 is a linear alkyl group of C 1 to C 4, The method.
  • the main chain portion of the alkylene group or alkenylene group constituting R 1 has C 2n carbon atoms (where n is 7 to 14).
  • the present invention is also a method for producing a diamine compound represented by the above formula (I).
  • R 1 is an alkylene or alkenylene group having a total carbon number of C 14 to C 28, which is linear or has one or more C 1 to C 4 alkyl and / or alkenyl groups.
  • the main chain portion of the alkylene group or alkenylene group constituting R 1 has C 2n carbon atoms (where n is 7 to 14).
  • the present invention is also a resin additive containing the above diamine compound.
  • the present invention is also a resin composition containing a resin and the above resin additive.
  • the present invention is also a resin composition containing one or more monomer compounds and a resin composed of the above resin additives.
  • the present invention is also a lubricating rust preventive for metal products containing the above diamine compound.
  • the diamine compound of the present invention can also be applied as an active ingredient such as a softener as a cationic surfactant and a rust preventive.
  • the diamine compound of the present invention has the following formula (I):
  • R 1 is an alkylene group or an alkylene group having a total carbon number of C 14 to C 28 , preferably C 16 to C 24 , and more preferably C 18 to C 22.
  • alkylene group or alkenylene group having a total carbon number of C 14 to C 28 is a linear or branched alkylene group having 14 to 28 carbon atoms and 14 carbon atoms. It includes a linear or branched alkenylene group having ⁇ 28.
  • Examples of an alkylene group or an alkenylene group having 14 to 28 carbon atoms are an alkylene group having a total carbon number of C 14 to C 28 and a linear structure; a total carbon number of C 14 to C 28 and 1 An alkylene group having a branched chain of one or more C 1 to C 4 alkyl groups and / or alkenyl groups; an alkenylene group having a total carbon number of C 14 to C 28 and being linear; a total carbon number of Alkenylene groups; which are C 14 to C 28 and have one or more branched chains of alkyl and / or alkenyl groups of C 1 to C 4;
  • Examples of the alkylene group having a total carbon number of C 14 to C 28 and being linear include an n-tetradecanylene group, an n-pentadecanylene group, an n-hexadecanylene group, an n-heptadecanelen group, and an n-octadecanylene group.
  • N-nonadecanylene group n-icosanilen group, n-henicosanilen group, n-docosanilen group, n-tricosanilen group, n-tetracosanilen group, n-pentacosanilen group, n-hexacosanilen group, n-heptacosanilen group, and n-octacosanilen group.
  • the group is mentioned.
  • Examples of the alkenylene group having a total carbon number of C 14 to C 28 and being linear include a tetradecenelene group, a pentadeceneylene group, a hexadecenelene group, a heptadecenelene group, an octadecenelene group, a nonadekenylene group, an icosenylene group, a henicosenylene group, and a docosenylene group.
  • Tricosenylene group Tricosenylene group, tetracosenylene group, pentacosenylene group, hexacosenylene group, heptacosenylene group, and octacosenylene group.
  • Total carbon atoms having a branched-chain alkyl groups and / or alkenyl group C 14 is ⁇ C 28 and one or more of C 1 ⁇ C 4, alkylene group", C 1 ⁇ C 4 alkyl group and Refers to an alkylene group having a total carbon number of C 14 to C 28 , which comprises at least one group selected from the group consisting of C 1 to C 4 alkenyl groups as a branched chain.
  • Total carbon atoms having a branched-chain alkyl groups and / or alkenyl group C 14 is ⁇ C 28 and one or more of C 1 ⁇ C 4, alkenylene group", C 1 ⁇ C 4 alkyl group and Refers to an alkylene group having a total carbon number of C 14 to C 28 , which comprises at least one group selected from the group consisting of C 1 to C 4 alkenyl groups as a branched chain.
  • alkyl groups C 1 to C 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.
  • R 1 of the formula (I) can be imparted with appropriate flexibility to the obtained resin composition.
  • the diamine compound of the present invention can be easily produced using a commercially available dibasic acid or a derivative thereof as described later, and therefore, in the above formula (I), the alkylene group constituting R 1 or It is preferable that the main chain portion of the alkenylene group (that is, the chain hydrocarbon portion excluding the branched chain) has C 2n carbon atoms (where n is 7 to 14).
  • Linear saturated diamines such as tetradecane diamine, hexadecane diamine, octadecane diamine, eikosa diamine, docosa diamine, tetracosa diamine, octacosa diamine; Tetradecanediamine-7-ene, hexadecanediamine-6-ene, hexadecanediamine-8-ene, octadecanediamine-8-ene, octadecanediamine-10-ene, eikosadiamine-6-ene, eikosadiamine-8-ene , Eikosadiamine-12-ene, Eikosadiamine-8,12-diamine, Eikosadiamine-10,14-diamine, docosadiamine-7,11,15-triene, docosadiamine-8,12,16-triene, 1 , 24-Tetracosadiamine-8,12,16-
  • the diamine compound represented by the above formula (I) can be produced, for example, by the following first method or second method.
  • a dihydrazide compound is synthesized by reacting the dibasic acid esters represented by (1) with hydrazine.
  • R 1 is an alkylene group or an alkylene group having a total carbon number of C 14 to C 28 , preferably C 16 to C 24 , more preferably C 18 to C 22, and is linear. Or an alkylene or alkenylene group having a branched chain of one or more C 1 to C 4 alkyl groups and / or alkenyl groups, where R 2 is a C 1 to C 4 linear alkyl. It is a group.
  • R 1 is similar to that defined in formula (I) above.
  • R 1 when the diamine compound is used, for example, as a constituent component of a resin additive described later, R 1 can impart appropriate flexibility to the obtained resin composition.
  • compounds of the formula (II) are, for reasons of easy availability commercially as will be described later, in the above formula (II), the main chain portion of the alkylene group or alkenylene group constituting R 1 It is preferable that (that is, the chain hydrocarbon moiety excluding the branched chain) has C 2n carbon atoms (where n is 7 to 14).
  • examples of the linear alkyl groups C 1 to C 4 that can constitute R 2 include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
  • the dibasic acid esters represented by the above formula (II) are known and are commercially available, for example, by Okamura Oil Refinery Co., Ltd.
  • the reaction between the dibasic acid esters represented by the formula (II) and hydrazine is carried out, for example, by heating under reflux in an appropriate organic solvent.
  • organic solvents include alcohols such as methanol, ethanol, 1-propanol and 2-propanol.
  • the time required for heating and reflux can be appropriately selected by those skilled in the art depending on the dibasic acid esters used and the amount.
  • the dibasic acid esters of the formula (II) are hydrazideized, and a dihydrazide compound (carboxylic acid hydrazide) can be obtained.
  • this dihydrazide compound reacts with a nitrite compound to produce an azide.
  • the nitrite compound is a compound capable of producing an azide (carboxylic acid azide) from the above dihydrazide compound (carboxylic acid hydrazide).
  • examples of nitrite compounds include nitrites and nitrite esters.
  • reaction conditions can be appropriately selected by those skilled in the art.
  • the azide is heat-dislocated and hydrolyzed.
  • the azide is converted to isocyanate through the Curtius rearrangement by heating, and the subsequent hydrolysis produces the diamine compound represented by the above formula (I).
  • the conditions for the Curtius rearrangement and hydrolysis can also be appropriately selected by those skilled in the art.
  • a diamide compound is produced by reacting the dibasic acid represented by (1) with ammonia.
  • R 1 is an alkylene group or an alkenylene group having a total carbon number of C 14 to C 28 , preferably C 16 to C 24 , more preferably C 18 to C 22, and is linear. Or an alkylene or alkenylene group having a branched chain of one or more C 1 to C 4 alkyl and / or alkenyl groups.
  • R 1 is similar to that defined in formula (I) above.
  • R when the obtained diamine compound is used, for example, as a constituent component of a resin additive described later, R can be imparted to the obtained resin composition with appropriate flexibility.
  • Reference numeral 1 denotes an alkylene group having a total carbon number of C 14 to C 28, which is linear or has a branched chain of one or more C 1 to C 4 alkyl groups. It is more preferable that the alkylene group has a total carbon number of C 14 to C 28 , and the alkylene group has a branched chain of one C 1 to C 4 alkyl group, and the total carbon number is C.
  • the alkylene group is 14 to C 28 , and the alkylene group has a branched chain of one ethyl group.
  • the compound represented by the formula (III) has a main chain portion of an alkylene group or an alkenylene group constituting R 1 in the above formula (III) because it is easily available on the market as described later. It is preferable that (that is, the chain hydrocarbon moiety excluding the branched chain) has C 2n carbon atoms (where n is 7 to 14).
  • the dibasic acid represented by the above formula (III) is known and is commercially available, for example, by Okamura Oil Refinery Co., Ltd.
  • the reaction between the dibasic acid represented by the formula (III) and ammonia is preferably carried out under pressure and heating.
  • the conditions of pressurization and heating and the time required for them can be appropriately selected by those skilled in the art depending on the dibasic acid and the amount used.
  • the diamide compound can be obtained from the dibasic acid of the formula (III).
  • this diamide compound is nitridated and hydrogenated.
  • the conditions for nitridation and hydrogen reduction are not particularly limited, and appropriate conditions can be appropriately selected by those skilled in the art.
  • the resin additive of the present invention contains a diamine compound represented by the above formula (I).
  • the term "resin additive" used in the present specification is used in a broad sense, and for example, (1) when constituting a resin composition, it is added independently of the resin which is a constituent component. Thereby, those caused by the improvement of the stability and / or the impartation of functionality of the obtained resin composition (for example, those capable of improving the stability of stabilizers, antioxidants, ultraviolet absorbers, etc.).
  • plasticizers flame retardants, nucleating agents, clearing agents, antistatic agents, lubricants, etc.
  • predetermined functions such as plasticizers, flame retardants, nucleating agents, clearing agents, antistatic agents, lubricants, etc.
  • It includes those that are physically or chemically linked or reacted with each other (for example, a cross-linking agent and a curing agent); and (3) those that can form the resin itself through the reaction (for example, a raw material monomer).
  • the resin additive of the present invention may contain other components that can be added in a normal resin composition, in addition to the diamine compound represented by the above formula (I).
  • Such other components are not particularly limited, but are, for example, antioxidants such as phenol-based antioxidants, sulfur-based antioxidants, and / or phosphorus-based antioxidants; anionic activators, cationic activities.
  • Antistatic agents such as agents, nonionic activators, amphoteric activators; lubricants such as hydrocarbon-based lubricants, fatty acid-based lubricants, higher alcohol-based lubricants, fatty acid amide-based lubricants, metallic soap-based lubricants, ester-based lubricants; organic Flame retardants such as flame retardants and inorganic flame retardants; and combinations thereof;
  • lubricants such as hydrocarbon-based lubricants, fatty acid-based lubricants, higher alcohol-based lubricants, fatty acid amide-based lubricants, metallic soap-based lubricants, ester-based lubricants; organic Flame retardants such as flame retardants and inorganic flame retardants; and combinations thereof;
  • organic Flame retardants such as flame retardants and inorganic flame retardants; and combinations thereof;
  • the content of the above other components that can be contained in the resin additive of the present invention is not particularly limited, and any amount can be selected by those skilled in the art.
  • the resin composition of the present invention contains the above resin additive and resin (hereinafter, such a resin composition is referred to as "first resin composition").
  • the resin that can constitute the first resin composition of the present invention is a thermosetting resin or a thermoplastic resin, and examples thereof include various resins obtained by reacting with an amino group. Examples of such examples include epoxy resins, polyurethanes, polyimides, polyamideimides, maleimide resins, and polyamides.
  • the resin additive (that is, the diamine compound represented by the formula (I)) is preferably a curing agent or resin constituent material of the resin, more preferably, because it can impart appropriate flexibility. Can be used as a curing agent for epoxy resins.
  • the contents of the resin and the resin additive are not particularly limited, and an appropriate content can be selected by those skilled in the art.
  • the resin composition of the present invention contains one or more monomer compounds and a resin composed of the above resin additives (hereinafter, such a resin composition is referred to as "second resin”. Composition ").
  • the monomer compound that can constitute the second resin composition of the present invention is one or more compounds that can constitute a thermoplastic resin or a thermosetting resin, and is, for example, ⁇ -caprolactam; undecanelamtam; Lauryl lactam; combination of hexamethylenediamine and adipic acid; combination of hexamethylenediamine and sebacic acid; combination of hexamethylenediamine and terephthalic acid; combination of hexamethylenediamine and isophthalic acid; combination of nonanediamine and terephthalic acid Combination of methylpentanediamine and terephthalic acid; combination of ⁇ -caprolactam and lauryllactam; combination of p-phenylenediamine and terephthalic acid; combination of m-phenylenediamine and isophthalic acid; pyromellitic acid anhydride; anhydrous Examples include a combination of trimellitic acid and diisocyanates; and a combination of trimelli
  • the resin additive (or the diamine compound represented by the above formula (I)) constitutes a resin with respect to one or more of the above monomer compounds. Can function as a monomer component.
  • the above-mentioned monomer compound and the above-mentioned resin additive (or the above-mentioned diamine compound represented by the formula (I)) can be polymerized by using, for example, a coupling reaction known to those skilled in the art.
  • the mixing ratio of the monomer compound and the resin additive (or the diamine compound represented by the above formula (I)) is not particularly limited, and combinations of various contents can be appropriately selected by those skilled in the art. As a result, a resin composed of one or more monomer compounds and the above resin additive is produced.
  • the first resin composition and the second resin composition of the present invention may also contain other resin additives.
  • other resin additives are not particularly limited, but include those included in other components that may be contained in the resin additive of the present invention.
  • the blending amount of the other resin additive that can be contained in the resin additive of the present invention is not particularly limited, and any amount can be selected by those skilled in the art.
  • Both the first resin composition and the second resin composition of the present invention are suitable for the constituent resin by, for example, the contained resin additive (that is, the diamine compound represented by the formula (I)). Flexibility can be imparted.
  • the first resin composition and the second resin composition of the present invention are preferably other than flexible as compared with the case where a flexible chain of a polar group is introduced into the constituent molecules of the resin as described above. There is no significant variation in other properties. Further, the flexibility imparted by such a resin additive can be easily adjusted by, for example, the blending amount of the resin additive.
  • the resin contained in the second resin composition of the present invention is a resin such as an epoxy resin, a polyimide, or a polyamide-imide, which is a polymer whose main chain is composed of an aromatic ring
  • a resin such as an epoxy resin, a polyimide, or a polyamide-imide, which is a polymer whose main chain is composed of an aromatic ring
  • the second resin composition of the present invention is expected to be useful in the field of electronic materials, for example.
  • the diamine compound represented by the formula (I) can be applied to other uses other than the resin additives as described above.
  • Examples of such other applications are fabric softeners, antistatic agents, and surfactants such as lubricants and rust inhibitors that can prevent corrosion of metal products (eg steel, stainless steel, aluminum products).
  • a cationic surfactant for example, a cationic surfactant.
  • Example 1 Synthesis of C18 saturated branched diamine compound
  • SB-20MM manufactured by Okamura Oil Co., Ltd./main component: dimethyl isoeicosate, molecular weight 370
  • hydrazine monohydrate 804 g (16.1 mol) and 1500 mL of 2-propanol as a solvent were charged and refluxed for 5 hours.
  • Infrared spectroscopic analysis confirmed the disappearance of the peaks (1627 cm -1 and 1533 cm -1) corresponding to the hydrazide bond observed in the dihydrazide 1a. However, new appearances of peaks (1722 cm -1 and 1571 cm -1 ) corresponding to the amino group were confirmed.
  • high performance liquid chromatograph mass spectrometry confirmed the disappearance of the peak confirmed by dihydrazide 1a (molecular weight 370).
  • 1 1 H NMR analysis (Mercury-300: manufactured by Varian) was performed on each of the isolated diamines. The ⁇ values are shown in Table 1 (CDCl 3 ).
  • the obtained dihydrazide 2a was subjected to infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to eliminate the peak (1731 cm -1 ) corresponding to the ester bond of dimethyl isodocosaziendiate and the peak corresponding to the hydrazide bond (1731 cm -1). The formation of 1627 cm -1 and 1533 cm -1 ) was confirmed. At the same time, by high performance liquid chromatograph mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), the peak of dimethyl isoeicosate (molecular weight 394), which is a raw material, disappeared, and dihydrazide isodocosadiene diacid (molecular weight 394) was obtained. The appearance of the corresponding new peak was confirmed.
  • FT-IR infrared spectroscopic analysis
  • dihydrazide 1a 400 g (1.0 mol) of the dihydrazide 2a obtained above was used, and instead of hydrochloric acid, 582 g (6.1 mol) of methanesulfonic acid was used, and the amount of sodium nitrite was 167 g (2.4 mol). it was changed to), the same procedure as in example 1 to obtain 100.7g of C 20 unsaturated branched diamines 2b amine value 339.
  • Infrared spectroscopic analysis confirmed the disappearance of the peaks (1627 cm -1 and 1533 cm -1) corresponding to the hydrazide bond observed in the dihydrazide 2a. However, new appearances of peaks (1722 cm -1 and 1572 cm -1 ) corresponding to the amino group were confirmed.
  • high performance liquid chromatograph mass spectrometry LC-MS-20: manufactured by Shimadzu Corporation
  • Example 3 Synthesis of C 22 unsaturated diamine compound
  • 1661 g of long-chain dibasic acid IPU-22 manufactured by Okamura Oil Co., Ltd./main component: isodocosadiene diacid, molecular weight 366
  • 50 g of silica gel were charged into a 5 L autoclave equipped with a thermometer and a stirrer, and under pressurized conditions.
  • the reaction was carried out at 300 ° C. for 2 hours with 300 g (17.6 mol) of ammonia gas.
  • the obtained diamine 3 was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to confirm the disappearance of the peak (1711 cm -1) corresponding to the carboxyl group derived from the raw material isodocosadiene diacid. New appearances of peaks (1722 cm -1 and 1572 cm -1 ) corresponding to the amino group were confirmed. Furthermore, gas chromatograph mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation) confirmed the disappearance of the peak corresponding to the raw material isodocosadiene diacid (molecular weight 366).
  • FT-IR infrared spectroscopic analysis
  • FT-IR manufactured by JASCO Corporation
  • 1 1 H NMR analysis (Mercury-300: manufactured by Varian) was performed on each of the isolated diamines. The ⁇ values are shown in Table 3 (CDCl 3 ).
  • Example 4 Preparation of cured epoxy resin (E1)) 10.0 g of bisphenol A type epoxy resin (EPOMIC manufactured by Mitsui Chemicals, Inc., epoxy equivalent (hereinafter, WPE) 188) and 4.4 g of diamine 1b (0.95 equivalent with respect to WPE) obtained in Example 1 as a curing agent. And 0.1 g (1 phr) of N, N-dimethylbenzylamine as a curing accelerator was mixed to prepare an epoxy resin composition. Next, 10 g of this resin composition was weighed in a heat-resistant container, heated at 70 ° C. for 15 hours, and further heat-cured at 120 ° C. for 1 hour to obtain an epoxy resin cured product (E1).
  • EPOMIC bisphenol A type epoxy resin
  • WPE epoxy equivalent
  • a sample was held at ⁇ 50 ° C. for 10 minutes using a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation), and then at 10 ° C. per minute. By heating to 200 ° C. at a heating rate, the glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. Further, in order to measure the gelation rate of the cured epoxy resin (E1), a 5 g sample was extracted with acetone for 5 hours by Soxhlet extraction. The gelation rate of the resin was measured by the ratio of the mass of the raw material before extraction to the mass of the extract. The results obtained are shown in Table 4.
  • DSC differential scanning calorimeter
  • Example 5 Preparation of cured epoxy resin (E2)
  • An epoxy resin cured product (E2) was prepared in the same manner as in Example 1 except that the diamine 2b (4.2 g) prepared in Example 2 was used instead of the diamine 1b as the curing agent.
  • DSC analysis and gelation rate measurement of the cured product were performed in the same manner as in Example 1. The results obtained are shown in Table 4.
  • Example 6 Preparation of cured epoxy resin (E3)
  • E3 An epoxy resin cured product (E3) was prepared in the same manner as in Example 1 except that diamine 3 (4.9 g) prepared in Example 3 was used instead of diamine 1b as a curing agent.
  • diamine 3 4.9 g
  • diamine 1b diamine 1b
  • DSC analysis and gelation rate measurement of the cured product were performed in the same manner as in Example 1. The results obtained are shown in Table 4.
  • Example 2 Preparation of Epoxy Resin Cured Product (CE2)
  • An epoxy resin cured product (CE2) was prepared in the same manner as in Example 1 except that triethylenetetramine (1.2 g) was used as the curing agent instead of diamine 1b.
  • the obtained epoxy resin cured product (CE2) was subjected to DSC analysis and gelation rate measurement of the cured product in the same manner as in Example 1. The results obtained are shown in Table 4.
  • the epoxy resin cured products (E1) to (E3) produced in Examples 4 to 6 are epoxy resin cured products (CE1) using the general-purpose amine-based curing agents of Comparative Examples 1 and 2. And (CE2) have a lower Tg, and moreover, Tg is higher than the epoxy resin cured product (CE3) using C 6 diamine of Comparative Example 3 and the epoxy resin cured product (CE 4) using C 10 diamine of Comparative Example 4. It was low and had an excellent flexibility-imparting effect.
  • the epoxy resin cured products (E1) to (E3) of Examples 1 to 3 using diamines 1b, 2b or 3 are the epoxy resin cured products (CE5) of Comparative Example 5 using a curing agent containing a polyether chain. It can be seen that they had substantially the same Tg and gelation rate.
  • Example 7 Evaluation of curability of epoxy resin composition (EC1)
  • 50 g of an epoxy resin composition (EC1) was prepared in the same manner as in Example 4, and this was charged into a glass sample tube. This was immersed in an oil bath at 70 ° C., and the temperature of the resin was plotted every hour (every 20 seconds) as a state of heat-generating curing. From the obtained heat-generating curve, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The pot life was calculated to be 0.8 times ( ⁇ 0.8) the gelation time. The results obtained are shown in Table 5.
  • Example 8 Evaluation of curability of epoxy resin composition (EC2)
  • An epoxy resin composition (EC2) was prepared in the same manner as in Example 4 except that the diamine 2b (21.0 g) prepared in Example 2 was used instead of the diamine 1b as a curing agent.
  • the gel point, gelation time, maximum heat generation point, minimum curing time, and pot life were determined from the heat curing curve of the resin composition. The results obtained are shown in Table 5.
  • Example 9 Evaluation of curability of epoxy resin composition (EC3)
  • An epoxy resin composition (EC3) was prepared in the same manner as in Example 4 except that diamine 3 (24.5 g) prepared in Example 3 was used instead of diamine 1b as a curing agent.
  • the gel point, gelation time, maximum heat generation point, minimum curing time, and pot life were determined from the heat curing curve of the resin composition. The results obtained are shown in Table 5.
  • the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 have a long gelation time and minimum curing time, and therefore the epoxy resin compositions of Comparative Examples 6 to 11 It had the characteristic of curing more slowly than those of (CC1) to (CC6).
  • the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 were compared with the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11. It is about 2 to 3 times longer. Focusing on the gelation temperature and the maximum heat generation point, the heat generation of the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 is the heat generation of the epoxy resin compositions (CC1) of Comparative Examples 6 to 11.
  • the polyether diamine which is a flexibility-imparting agent which is similar to that of (CC6) and shows high reactivity, has low reactivity, and therefore at a low temperature.
  • the diamines 1b, 2b and 3 used in the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 are Comparative Examples 6 to 11 which are also known as commercially available amine-based curing agents. It can be seen that the pot life is longer than that of the curing agents of the epoxy resin compositions (CC1) to (CC6) of No. 1 and the temperature curability is superior to that of other flexibility-imparting agents.
  • Example 10 Water resistance of the cured epoxy resin (E1)
  • Example 11 Water resistance of the cured epoxy resin (E2)
  • the water absorption rate (%) of the cured epoxy resin (E2) was calculated. The results obtained are shown in Table 6.
  • Example 12 Water resistance of the cured epoxy resin (E3)) Boil the cured product in the same manner as in Example 10 except that the epoxy resin cured product (E3) (containing diamine 3 as a curing agent) prepared in Example 6 was used instead of the epoxy resin cured product (E1). The water absorption rate (%) of the cured epoxy resin (E3) was calculated. The results obtained are shown in Table 6.
  • Comparative Example 12 Water resistance of cured epoxy resin (CE1)) Boil the cured product in the same manner as in Example 10 except that the epoxy resin cured product (CE1) (tetraethylenepentamine as a curing agent) prepared in Comparative Example 1 was used instead of the epoxy resin cured product (E1). The water absorption rate (%) of the cured epoxy resin (CE1) was calculated. The results obtained are shown in Table 6.
  • Comparative Example 13 Water resistance of hardened epoxy resin (CE5)
  • the cured product was boiled in the same manner as in Example 10 except that the epoxy resin cured product (CE5) (polyetherdiamine as a curing agent) prepared in Comparative Example 5 was used instead of the epoxy resin cured product (E1). Then, the water absorption rate (%) of the cured epoxy resin (CE5) was calculated. The results obtained are shown in Table 6.
  • the epoxy resin cured products (E1) to (E3) evaluated in Examples 10 to 12 (containing diamines 1b, 2b or 3 as a curing agent) and the general-purpose products evaluated in Comparative Example 12 In the corresponding epoxy resin cured product (CE1) (containing tetraethylenepentamine as a curing agent), the water absorption rate of the cured product was 0%, and the cured product had sufficient water resistance.
  • the epoxy resin cured product (CE5) evaluated in Comparative Example 13 containing a polyether diamine (molecular weight 400), which is also known as a flexibility-imparting agent, as a curing agent has a water absorption rate of about 1%. Was shown.
  • the polyether diamine is accompanied by a decrease in water resistance in exchange for imparting flexibility, whereas a cured epoxy resin (E1) using diamines 1b, 2b or 3 (produced in Examples 4 to 6) is used. It can be seen that in (E3), flexibility was imparted without impairing water resistance.
  • Example 13 Preparation of bismaleimide prepolymer (EM1)
  • EM1 bismaleimide prepolymer 1
  • Diamine 1b (5.2 g) (30.0 mmol equivalent as an amino group) was added dropwise. The temperature was raised to 50 ° C. with stirring, and the mixture was further stirred for 1.5 hours. Then, 3.1 g (30.1 mmol) of acetic anhydride was added, and the mixture was further stirred for 1 hour, and THF was removed under reduced pressure to obtain 27.6 g of bismaleimide prepolymer (EM1).
  • the obtained bismaleimide prepolymer (EM1) was subjected to infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) with a decrease in peaks (1606 cm -1) corresponding to ⁇ , ⁇ -unsaturated bonds and an imide. The peaks corresponding to the bonds (1705 cm -1 and 1510 cm -1 ) and the peaks corresponding to the amide bonds (1636 cm -1 ) were confirmed.
  • FT-IR infrared spectroscopic analysis
  • Example 14 Preparation of bismaleimide prepolymer (EM2)
  • EM2 bismaleimide prepolymer
  • Example 15 Preparation of bismaleimide prepolymer (EM3)
  • EM3 bismaleimide prepolymer (EM3) was obtained in the same manner as in Example 13 except that diamine 3 (5.8 g) prepared in Example 3 was used instead of diamine 1b as a modifier.
  • This bismaleimide prepolymer (EM3) was subjected to DSC analysis of the cured product in the same manner as in Example 13. The results obtained are shown in Table 7.
  • the cured products of the bismaleimide prepolymers (EM1) to (EM3) prepared in Examples 13 to 15 are all compared with the bismaleimide prepolymer (CM1) prepared in Comparative Example 14.
  • the Tg was significantly lower, and the two amino groups constituting diamines 1b, 2b and 3 used as the modifier were used. It can be seen that the longer the carbon chain arranged between them, the higher the flexibility can be imparted to the obtained cured product.
  • Example 16 Preparation of polyamides 18 and 6
  • 1b (3.8 g) of diamine obtained in Example 1 (21.8 mmol equivalent as an amino group)
  • triethylamine (2.2 g) (21.8 mmol) and 50 mL of hexane were charged and dissolved in 50 mL of hexane.
  • Adipoyl chloride (2.0 g) (10.9 mmol) was added with stirring, and solution polymerization was carried out. After stirring for 30 minutes, the mixture was filtered, the filtrate was washed with water and acetone, and dried to obtain 2.3 g of polyamides 18 and 6.
  • a differential scanning calorimeter (DSC-60 manufactured by Shimadzu Corporation) was used to hold the sample at 0 ° C. for 10 minutes, and then the temperature was raised at 5 ° C. per minute. By heating to 100 ° C., the glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. The results obtained are shown in Table 8.
  • Example 17 Preparation of polyamides 20 and 6
  • 2.5 g of polyamide 6.6 was obtained in the same manner as in Example 16 except that the diamine 2b (3.6 g) prepared in Example 2 was used instead of the diamine 1b.
  • the polyamide 20.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.
  • Example 18 Preparation of polyamides 2 and 6
  • Example 18 2.3 g of polyamide 6.6 was obtained in the same manner as in Example 16 except that diamine 3 (3.8 g) prepared in Example 3 was used instead of diamine 1b.
  • the polyamide 22.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.
  • the polyamides (polyamide 18.6, polyamide 20.6, polyamide 22.6) prepared in Examples 16 to 18 are all compared with the polyamide 2.6 prepared in Comparative Example 16.
  • Tg is significantly lower than that of Polyamide 6.6 in Example 17.
  • the longer the carbon chain arranged between the two amino groups constituting the diamines 1b, 2b and 3 used in the polyamide the higher the flexibility of the obtained cured product. You can see that it was possible.
  • Example 19 Fabrication of polyimide (ED1)
  • ED1 polyimide
  • a reactor equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube was charged with pyromellitic anhydride (50.0 g) and cyclohexanone (200 ml) and heated to 60 ° C.
  • pyromellitic anhydride 50.0 g
  • cyclohexanone 200 ml
  • 40.0 g of the diamine 1b obtained in Example 1 dissolved in toluene (100 ml) was added, imidized at 140 ° C. for 3 hours, the solvent was removed under reduced pressure, and 80.1 g of polyimide (ED1) was obtained. It was.
  • Example 20 Fabrication of polyimide (ED2)
  • ED2 polyimide
  • 78.9 g of polyimide (ED2) was obtained in the same manner as in Example 19 except that the diamine 2b (37.9 g) prepared in Example 2 was used instead of the diamine 1b.
  • the polyimide (ED2) was subjected to DSC analysis of the resin in the same manner as in Example 19. The results obtained are shown in Table 9.
  • Example 21 Fabrication of polyimide (ED3) 81.3 g of polyimide (ED3) was obtained in the same manner as in Example 19 except that the diamine 3 (44.3 g) prepared in Example 3 was used instead of the diamine 1b.
  • ED3 DSC analysis of the resin was carried out in the same manner as in Example 19. The results obtained are shown in Table 9.
  • diamine compound of the present invention (diamine 1b, 2b and 3) having a long carbon chain between two amino groups is used as a resin additive, flexibility is imparted to the resin.
  • these diamine compounds have slower reactivity than commercially available amine curing agents as epoxy resin curing agents as used in Comparative Examples 6 to 11, but gels from Table 1 show. The conversion rate is high, and it can be seen that the curing reaction is sufficiently progressing. Therefore, it is the most suitable material for adjusting the pot life.
  • the polyether diamine (molecular weight 400), which had a flexibility-imparting effect, had a flexibility-imparting effect corresponding to the molecular weight (Table 1), but the reactivity was remarkably low (70 ° C.). At worst, the curing reaction proceeds at 120 ° C. (Table 2). Further, from Table 3, the cured product using a polyether diamine is inferior in water resistance, while the cured product using a long-chain diamine has the same water resistance as a general-purpose amine curing agent without impairing the water resistance. Be done. For this reason, the diamine compound of the present invention is more useful than the current flexibility-imparting agent, polyether diamine.
  • Example 22 Corrosion prevention effect on metal products
  • a glass sample tube was charged with 50 mL of an aqueous solution containing the diamine 1b obtained in Example 1 as a corrosion inhibitor in a proportion of 0.05% by mass in 10% hydrochloric acid.
  • a standard test plate JIS G 3141; manufactured by Nippon Test Panel Co., Ltd.
  • the test plate after corrosion was washed with water and dried, and the corrosion rate (%) was calculated according to the following formula from the mass difference before and after immersion.
  • Corrosion rate (%) (mass of test plate before immersion-mass of test plate after immersion) / (mass of test plate before immersion) x 100
  • the diamine 1b (isooctadecanediamine) used in Example 22 has the lowest corrosion rate of the steel sheet and has a high anticorrosive effect against an acidic aqueous solution.
  • Such corrosion inhibitors are useful during cleaning treatments such as pickling, acid immersion, and etching of metals.
  • the diamine compound of the present invention it is possible to provide a resin composition having excellent flexibility by using various resins.
  • the resin composition is used as a material composed of resins such as epoxy, polyurethane, polyimide, polyamideimide, maleimide, and polyamide, for example, in earth and wood, building materials, repair materials for flooring materials, various paints, various adhesives, and electronic materials.
  • resins such as epoxy, polyurethane, polyimide, polyamideimide, maleimide, and polyamide
  • resins such as epoxy, polyurethane, polyimide, polyamideimide, maleimide, and polyamide
  • sealants underfills
  • insulating members such as insulating members, mold resins, resist materials, resin-reinforced solder solder paste materials, flexible printed substrate materials, various films, plastic molded products in thermoplastic resins, nylon fibers, etc. Is.
  • the diamine compound of the present invention when used as a cationic surfactant in a lubricating rust preventive, it can exert a high corrosion prevention effect on metal products. Therefore, it is also useful in the fields of metal processing, machinery, and the like.

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)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un composé diamine et son procédé de production. Ce composé diamine est un composé représenté par la formule (I) : H2N-R1-NH2 (dans la formule (I), R1 représente un groupe alkylène ou un groupe alcénylène ayant un nombre total de carbone de C14-C28, le groupe alkylène ou le groupe alcénylène étant soit linéaire, soit ayant une chaîne ramifiée d'un ou de plusieurs groupes alkyle et/ou alcényle en C1-C4. Ce composé diamine peut conférer une flexibilité appropriée à une résine telle qu'une résine époxy.
PCT/JP2020/034020 2019-09-13 2020-09-08 Composé diamine et son procédé de production WO2021049503A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020227012227A KR20220062086A (ko) 2019-09-13 2020-09-08 디아민 화합물 및 이의 제조 방법
JP2021545554A JP7357391B2 (ja) 2019-09-13 2020-09-08 ジアミン化合物およびその製造方法
CN202080064182.2A CN114364656A (zh) 2019-09-13 2020-09-08 二胺化合物和其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019167694 2019-09-13
JP2019-167694 2019-09-13

Publications (1)

Publication Number Publication Date
WO2021049503A1 true WO2021049503A1 (fr) 2021-03-18

Family

ID=74866170

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/034020 WO2021049503A1 (fr) 2019-09-13 2020-09-08 Composé diamine et son procédé de production

Country Status (4)

Country Link
JP (1) JP7357391B2 (fr)
KR (1) KR20220062086A (fr)
CN (1) CN114364656A (fr)
WO (1) WO2021049503A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090348A1 (fr) * 2021-11-22 2023-05-25 日本化薬株式会社 Résine polyimide, composition de résine contenant ladite résine polyimide et produit durci associé
WO2023112849A1 (fr) * 2021-12-13 2023-06-22 日本化薬株式会社 Résine polyimide modifiée par isocyanate, et composition de résine contenant ladite résine polyimide modifiée par isocyanate et produit durci de celle-ci

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647146A (en) * 1949-07-01 1953-07-28 Du Pont Process for the preparation of diprimary diamines
US3382186A (en) * 1965-09-22 1968-05-07 Betz Laboratories Aliphatic hydrocarbon amine corrosion inhibitors
JPS5112674B1 (fr) * 1970-07-09 1976-04-21
JPS51125500A (en) * 1974-11-07 1976-11-01 Ciba Geigy Ag Setting composite and process for producing same
JPS5471189A (en) * 1977-10-28 1979-06-07 Ciba Geigy Ag Crystalline polyamide
JPS5555127A (en) * 1978-10-18 1980-04-22 Ciba Geigy Ag Substituted 1*111diaminoundecane*its manufacture and its use
JPS5883656A (ja) * 1981-10-12 1983-05-19 チバ−ガイギ−・アクチエンゲゼルシヤフト 置換１，１１−ジアミノウンデカンの製造方法
JP2006143759A (ja) * 2004-11-16 2006-06-08 Yokohama Rubber Co Ltd:The 二液型常温硬化性エポキシ樹脂組成物および金属接着剤組成物
US20150183724A1 (en) * 2012-07-06 2015-07-02 Monash University Process for producing amine compounds
JP2018070699A (ja) * 2016-10-26 2018-05-10 三菱ケミカル株式会社 ポリイミド樹脂組成物
CN108671746A (zh) * 2018-05-05 2018-10-19 安徽乐金环境科技有限公司 一种复合空气净化滤芯及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307218B (zh) * 2008-06-20 2011-06-22 上海天洋热熔胶有限公司 服装用耐高温水洗聚酰胺热熔胶及其制备方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647146A (en) * 1949-07-01 1953-07-28 Du Pont Process for the preparation of diprimary diamines
US3382186A (en) * 1965-09-22 1968-05-07 Betz Laboratories Aliphatic hydrocarbon amine corrosion inhibitors
JPS5112674B1 (fr) * 1970-07-09 1976-04-21
JPS51125500A (en) * 1974-11-07 1976-11-01 Ciba Geigy Ag Setting composite and process for producing same
JPS5471189A (en) * 1977-10-28 1979-06-07 Ciba Geigy Ag Crystalline polyamide
JPS5555127A (en) * 1978-10-18 1980-04-22 Ciba Geigy Ag Substituted 1*111diaminoundecane*its manufacture and its use
JPS5883656A (ja) * 1981-10-12 1983-05-19 チバ−ガイギ−・アクチエンゲゼルシヤフト 置換１，１１−ジアミノウンデカンの製造方法
JP2006143759A (ja) * 2004-11-16 2006-06-08 Yokohama Rubber Co Ltd:The 二液型常温硬化性エポキシ樹脂組成物および金属接着剤組成物
US20150183724A1 (en) * 2012-07-06 2015-07-02 Monash University Process for producing amine compounds
JP2018070699A (ja) * 2016-10-26 2018-05-10 三菱ケミカル株式会社 ポリイミド樹脂組成物
CN108671746A (zh) * 2018-05-05 2018-10-19 安徽乐金环境科技有限公司 一种复合空气净化滤芯及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Synthesis and Reaction of Organic Compounds III", THE CHEMICAL SOCIETY OF JAPAN, NEW EXPERIMENTAL CHEMISTRY LECTURE 14, vol. 14, no. III, 1978, pages 1391 - 1393 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090348A1 (fr) * 2021-11-22 2023-05-25 日本化薬株式会社 Résine polyimide, composition de résine contenant ladite résine polyimide et produit durci associé
WO2023112849A1 (fr) * 2021-12-13 2023-06-22 日本化薬株式会社 Résine polyimide modifiée par isocyanate, et composition de résine contenant ladite résine polyimide modifiée par isocyanate et produit durci de celle-ci

Also Published As

Publication number Publication date
JP7357391B2 (ja) 2023-10-06
JPWO2021049503A1 (fr) 2021-03-18
CN114364656A (zh) 2022-04-15
KR20220062086A (ko) 2022-05-13

Similar Documents

Publication Publication Date Title
US4179551A (en) Low temperature curable compliant bismaleimide compositions
JP7357391B2 (ja) ジアミン化合物およびその製造方法
US20220169791A1 (en) Polyamic Acid Resin, Polyimide Resin, and Resin Composition Including These
US4269961A (en) Low temperature curable compliant bismaleimide compositions
CN113396173B (zh) 环氧树脂溶液
WO2011125888A1 (fr) Composition d'agent durcissant les polyamides
TW202219116A (zh) 異氰酸酯改質聚醯亞胺樹脂、樹脂組成物及其硬化物
US10619008B2 (en) Aliphatic polyimides from unsaturated monoanhydride or unsaturated diacid reacted with both monoamine and diamine
JP2022517851A (ja) バイオ由来の化合物を含む弾性接着剤
US4541958A (en) Hardening agent for epoxy resins comprising an amideamine compound
JP2009263570A (ja) 末端変性イミドオリゴマーおよびワニス並びにその高弾性率硬化物
US20170044320A1 (en) Aliphatic polyimides from a 1:1 molar ratio of diamine and unsaturated monoanhydride or unsaturated diacid
US9221849B2 (en) Silane coupling agent, making method, primer composition, and coating composition
Shah et al. Synthesis and characterisation of cycloaliphatic and aromatic amines based cardanol benzoxazines: A comparative study
KR101803753B1 (ko) 중방식 에폭시 도료용 폴리아마이드 경화제의 제조방법 및 이에 의해 제조된 폴리아마이드 경화제를 포함하는 중방식 에폭시 도료
Mirmohseni et al. Polyamidoamines based on castor oil‐styrene co‐oligomer/triethylenetetramine as curing agents in high‐performance epoxy coatings
TW201518285A (zh) 苯并呋喃衍生物組成物、聚醯亞胺前驅物組成物、聚醯亞胺樹脂以及其製造方法
JP7432331B2 (ja) エポキシ樹脂組成物の硬化方法
EP1999184A1 (fr) Polyamides
JP2022162256A (ja) 複合体、及び複合体の製造方法
JP2021134236A (ja) ポリアミドイミド
WO2019189542A1 (fr) Corps stratifié de résine polyimide modifiée par de la silicone-caoutchouc de silicone
JP5477327B2 (ja) ポリイミド樹脂の製造方法
JP7322837B2 (ja) シリコーン変性ポリイミド樹脂組成物
WO2018158877A1 (fr) Résine polyamide-imide et son utilisation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20862962

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021545554

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20227012227

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 20862962

Country of ref document: EP

Kind code of ref document: A1