Diamine compound and method for producing the same

Abstract

The present invention discloses a diamine compound and a method for producing the same. The diamine compound of the present invention is the following formula (I): H2N—R 1 -NH2(I), (in formula (I), R 1 The total number of carbon atoms is C 14 ~C 28 The diamine compound of the present invention can impart appropriate flexibility to resins such as epoxy resins.

Description

Technical Field

[0001] The present invention relates to a diamine compound and a method for producing the same, and more particularly to a diamine compound useful as an additive used in combination with a monomer or curing agent that can constitute a polymer material such as a thermosetting resin or a thermoplastic resin, or the polymer material, and a method for producing the same. Background Art

[0002] Resin materials composed of polymers are used in a wide range of applications, such as coatings, building materials, flooring materials, civil engineering materials, electronic components, etc. The properties required for these applications are different, so there are many types of resin materials that meet the properties.

[0003] In particular, resin materials such as epoxy resin, polyimide, and polyamide-imide, whose main chains are composed of aromatic rings, have excellent mechanical and electrical properties, but on the other hand, they are hard and brittle, and generally, they are pointed out to lack impact resistance and toughness. Therefore, it is necessary to alleviate the brittleness according to the application, and various means have been proposed so far.

[0004] As one of such means, it is known that a flexible chain is introduced into the main chain of a polymer to impart flexibility, thereby modifying the polymer. As a method for introducing such a flexible chain, in the case of manufacturing, for example, a thermosetting resin, it is known to use a compound having a flexible chain (e.g., a polar group such as an ether group, an ester group, an amide group, an urethane group) as a main agent or a curing agent. Alternatively, in the case of manufacturing a thermoplastic resin, it is known that a compound having such a flexible chain can be used as a monomer of a raw material.

[0005] However, in these methods, compatibility and viscosity may be reduced, resulting in reduced curing properties, and the resulting cured product may have various properties other than flexibility changed, and other properties may be changed or reduced in an undesirable manner. This is believed to be caused by the polar groups introduced as flexible chains. Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention is an invention for solving the above-mentioned problems, and its object is to provide a diamine compound and a method for producing the same, wherein the diamine compound can be used as a resin additive that can impart flexibility to a resin such as an epoxy resin without introducing a polar group into the constituent molecules of the resin and has little effect on other properties.

[0008] Technical solutions to solve problems

[0009] The present invention is a diamine compound represented by the following formula (I):

[0010] H2N-R 1 -NH2 (I)

[0011] In formula (I),

[0012] R 1 The total number of carbon atoms is C 14 ~C 28 The alkylene or alkenylene group is a linear or branched alkylene or alkenylene group having one or more C1 to C4 alkyl and / or alkenyl groups.

[0013] In one embodiment, in formula (I), R 1 The main chain part of the alkylene or alkenylene group has C 2n (wherein n is 7 to 14) carbon atoms.

[0014] In one embodiment, in formula (I), R 1 The above C 14 ~C 28 The straight-chain alkylene group or the straight-chain alkenylene group has a branch consisting of an ethyl group.

[0015] In one embodiment, the diamine compound of the present invention is 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene.

[0016] The present invention also provides a method for producing the diamine compound represented by the above formula (I), the method comprising:

[0017] A step of reacting a dibasic acid ester represented by the following formula (II) with hydrazine to obtain a dihydrazide compound;

[0018] a step of reacting the dihydrazide compound with a nitrous acid compound to obtain an azide; and

[0019] a step of heating the azide to rearrange and hydrolyze it,

[0020]

[0021] In formula (II),

[0022] R 1 The total number of carbon atoms is C 14 ~C 28 and is a linear or branched alkylene or alkenylene group having one or more C1 to C4 alkyl and / or alkenyl groups,

[0023] R 2 It is a C1-C4 straight chain alkyl group.

[0024] In one embodiment, in formula (II), R 1 The main chain part of the alkylene or alkenylene group has C 2n (wherein n is 7 to 14) carbon atoms.

[0025] The present invention also provides a method for producing the diamine compound represented by the above formula (I), the method comprising:

[0026] A step of reacting a dibasic acid represented by the following formula (III) with ammonia to obtain a diamide compound; and

[0027] a step of subjecting the diamide compound to nitrilation and hydrogen reduction,

[0028]

[0029] In formula (III),

[0030] R 1 The total number of carbon atoms is C 14 ~C 28 The alkylene or alkenylene group is a linear or branched alkylene or alkenylene group having one or more C1 to C4 alkyl and / or alkenyl groups.

[0031] In one embodiment, in formula (III), R 1 The main chain part of the alkylene or alkenylene group has C 2n (wherein n is 7 to 14) carbon atoms.

[0032] The present invention also provides a resin additive containing the above diamine compound.

[0033] The present invention also provides a resin composition comprising a resin and the above resin additive.

[0034] The present invention also provides a resin composition comprising a resin composed of one or more monomer compounds and the above-mentioned resin additive.

[0035] The present invention also provides a lubricating rust preventive for metal products containing the diamine compound.

[0036] Effects of the Invention

[0037] According to the present invention, for example, flexibility can be provided to a resin such as epoxy resin. On the other hand, it is possible to avoid causing significant changes in other properties of the resin. The diamine compound of the present invention can be used as such a resin additive, and can also be used as an effective component of a cationic surfactant such as a softener and a rust inhibitor. DETAILED DESCRIPTION

[0038] The present invention is described in detail below.

[0039] (Diamine compound)

[0040] The diamine compound of the present invention is a compound represented by the following formula (I).

[0041] H2N-R 1 -NH2 (I)

[0042] Here, in formula (I), R 1 The total number of carbon atoms is C 14 ~C 28 , preferably C 16 ~C 24 , more preferably C 18 ~C 22 The alkylene or alkenylene group is a linear or branched alkylene or alkenylene group having one or more C1 to C4 alkyl and / or alkenyl groups.

[0043] The term "total number of carbon atoms is C 14 ~C 28 The term "alkylene or alkenylene" refers to a linear or branched alkylene group having 14 to 28 carbon atoms and a linear or branched alkenylene group having 14 to 28 carbon atoms.

[0044] Examples of the alkylene or alkenylene group having 14 to 28 carbon atoms include: 14 ~C 28 And it is a straight-chain alkylene group; the total number of carbon atoms is C 14 ~C 28 and having one or more C1-C4 alkyl and / or alkenyl branched alkylene groups; the total number of carbon atoms is C 14 ~C 28 And it is a straight-chain alkenylene group; the total number of carbon atoms is C 14 ~C 28 And it has a branched alkenylene group having one or more C1-C4 alkyl and / or alkenyl groups.

[0045] The total number of carbon atoms is C 14 ~C 28 The straight-chain alkylene group includes, for example, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecylene, n-eicosylene, n-heneicosylene, n-docosylene, n-tricosylene, n-tetracosylene, n-pentacosylene, n-hexacosylene, n-heptacosylene and n-octacosylene. 14 ~C 28Examples of the straight-chain alkenylene group include tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, nonadecenylene, eicosenylene, heneicosenylene, docosenylene, tricosenylene, tetracosenylene, pentacosenylene, hexacosenylene, heptacosenylene and octacosenylene.

[0046] The total number of carbon atoms is C 14 ~C 28 The term "alkylene group having one or more C1-C4 alkyl and / or alkenyl branched chains" means a group having a total carbon number of C1-C4 alkyl and C1-C4 alkenyl as a branched chain. 14 ~C 28 The total number of carbon atoms is C 14 ~C 28 The term "alkenylene group having one or more C1-C4 alkyl and / or alkenyl branches" means a group having a total carbon number of C1-C4 alkyl and C1-C4 alkenyl branches as branches. 14 ~C 28 Examples of C1 to C4 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Examples of C1 to C4 alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl and 3-butenyl.

[0047] When the diamine compound of the present invention is used as a constituent component of a resin additive described later, for example, R in formula (I) is preferably 1 Preferably, the total number of carbon atoms is C 14 ~C 28 The alkylene group is a linear or branched alkylene group having one or more C1 to C4 alkyl groups, and more preferably a alkylene group having a total carbon number of C 14 ~C 28 The alkylene group is preferably an alkylene group having a total carbon number of C1 to C4. 14 ~C 28 An alkylene group having an alkylene group and a branched alkylene group having one ethyl group.

[0048] Alternatively, the diamine compound of the present invention can be easily produced by using a commercially available dibasic acid or a derivative thereof as described below. In the above formula (I), R 1 The main chain portion of the alkylene or alkenylene group (i.e., the chain hydrocarbon portion excluding the branching chain) preferably has C 2n (wherein n is 7 to 14) carbon atoms.

[0049] More specific examples of such diamine compounds include:

[0050] Straight-chain saturated diamines such as tetradecanediamine, hexadecanediamine, octadecanediamine, eicosanediamine, docosanediamine, tetracosanediamine, and octacosanediamine;

[0051] Straight-chain unsaturated diamines such as tetradecanediamine-7-ene, hexadecandiamine-6-ene, hexadecandiamine-8-ene, octadecanediamine-8-ene, octadecanediamine-10-ene, eicosanediamine-6-ene, eicosanediamine-8-ene, eicosanediamine-12-ene, eicosanediamine-8,12-diene, eicosanediamine-10,14-diene, docosanediamine-7,11,15-triene, docosanediamine-8,12,16-triene, 1,24-tetradecanediamine-8,12,16-triene, and tetradecanediamine-10,14,18-triene;

[0052] Branched chain saturated diamines such as 6,8-dimethyltetradecanediamine, 7-ethyltetradecanediamine, 7-propyltetradecanediamine, 7-ethylhexadecanediamine, 7-butylhexadecanediamine, 7-isopropyl-10-methylhexadecanediamine, 8-ethyloctadecanediamine, 8-isopropyl-11-methyloctadecanediamine, 8,13-diethyloctadecanediamine, 8,13-dimethyleicosanediamine, 9,12-dimethyleicosanediamine, and 9,12-diethyleicosanediamine;

[0053] Branched unsaturated diamines such as 7-vinyltetradecanediamine, 7-vinylhexadecanediamine-8-ene, 7-isopropenyl-10-methylhexadecanediamine-9-ene, 8-vinyl-octadecanediamine-9-ene, 7,12-dimethyloctadecanediamine-7,11-diene, 7,12-diethyloctadecanediamine-7,11-diene, 8-isopropenyl-11-methyloctadecanediamine-10-ene, 8-ethyl-11-isopropenyloctadecanediamine-10-ene, 8,13-dimethyleicosanediamine-8,12-diene, and 9,12-dimethyleicosanediamine-8,12-diene; etc.

[0054] (Method for producing diamine compound)

[0055] The diamine compound represented by the above formula (I) can be produced by, for example, the following first method or second method.

[0056] The first method for producing the diamine compound represented by formula (I) will be described.

[0057] In the first method of the present invention, first, a dibasic acid ester represented by the following formula (II) is reacted with hydrazine to synthesize a dihydrazide compound.

[0058]

[0059] In formula (II), R 1 The total number of carbon atoms is C 14 ~C 28 , preferably C 16 ~C 24 , more preferably C 18 ~C 22 alkylene or alkenylene, and is a straight chain or branched chain alkylene or alkenylene having one or more C1 to C4 alkyl and / or alkenyl groups, R 2 It is a C1-C4 straight chain alkyl group.

[0060] In formula (II), R 1 The same as defined in the above formula (I).

[0061] In the formula (II), when the diamine compound is used as a constituent component of a resin additive described later, R 1 Preferably, the total number of carbon atoms is C 14 ~C 28 The alkylene group is a linear or branched alkylene group having one or more C1 to C4 alkyl groups, and more preferably a alkylene group having a total carbon number of C 14 ~C 28 The alkylene group is a branched alkylene group having one C1 to C4 alkyl group, and the total number of carbon atoms is more preferably C 14 ~C 28 Alternatively, the compound represented by formula (II) can be easily purchased as described below. In the above formula (II), R 1 The main chain portion of the alkylene or alkenylene group (i.e., the chain hydrocarbon portion excluding the branching chain) preferably has C 2n (wherein n is 7 to 14) carbon atoms.

[0062] On the other hand, in formula (II), as the compound that can constitute R 2 Examples of the C1-C4 straight-chain alkyl group include methyl, ethyl, n-propyl and n-butyl.

[0063] The dibasic acid esters represented by the above formula (II) are well known and are commercially available from, for example, Okamura Oil Manufacturing Co., Ltd.

[0064] The reaction of the dibasic acid ester represented by formula (II) and hydrazine can be carried out in a suitable organic solvent by, for example, heating under reflux. Examples of organic solvents that can be used include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol. The time required for heating under reflux can be appropriately selected by those skilled in the art according to the dibasic acid ester used and the amount.

[0065] In this way, the dibasic acid ester of formula (II) is hydrazide-converted to obtain a dihydrazide compound (carboxylic acid hydrazide).

[0066] Next, the dihydrazide compound is reacted with a nitrous acid compound to generate an azide.

[0067] In the present invention, the nitrite compound is a compound capable of generating an azide (carboxylic acid azide) from the above-mentioned dihydrazide compound (carboxylic acid hydrazide). Examples of the nitrite compound include nitrites and nitrite esters.

[0068] In the generation of the azide, the reaction conditions can be appropriately selected by those skilled in the art.

[0069] The azide is then heated to rearrange and hydrolyze.

[0070] Specifically, the azide is converted into an isocyanate by Curtius rearrangement under heating, and then hydrolyzed to generate the diamine compound represented by the above formula (I). It should be noted that the conditions for the Curtius rearrangement and hydrolysis can also be appropriately selected by those skilled in the art.

[0071] Next, the second method for producing the diamine compound represented by formula (I) will be described.

[0072] In the second method of the present invention, first, a dibasic acid represented by the following formula (III) is reacted with ammonia to produce a diamide compound.

[0073]

[0074] In formula (III), R 1 The total number of carbon atoms is C 14 ~C 28 , preferably C 16 ~C 24 , more preferably C 18 ~C 22 The alkylene or alkenylene group is a linear or branched alkylene or alkenylene group having one or more C1 to C4 alkyl and / or alkenyl groups.

[0075] In formula (III), R 1 The same as defined in the above formula (I).

[0076] In the formula (III), when the diamine compound is used as a constituent component of a resin additive described later, R 1 Preferably, the total number of carbon atoms is C 14 ~C 28 The alkylene group is a linear or branched alkylene group having one or more C1 to C4 alkyl groups, and more preferably a alkylene group having a total carbon number of C 14 ~C 28 The alkylene group is preferably an alkylene group having a total carbon number of C1 to C4. 14 ~C 28 Alternatively, the compound represented by formula (III) can be easily purchased as described below. In the above formula (III), R 1 The main chain portion of the alkylene or alkenylene group (i.e., the chain hydrocarbon portion excluding the branching chain) preferably has C 2n (wherein n is 7 to 14) carbon atoms.

[0077] The dibasic acid represented by the above formula (III) is well known and is commercially available from, for example, Okamura Oil Manufacturing Co., Ltd.

[0078] The reaction of the dibasic acid represented by formula (III) and ammonia is preferably carried out under pressure and heating. The conditions of pressure and heating and the time required can be appropriately selected by those skilled in the art according to the dibasic acid used and the amount thereof.

[0079] In this way, a diamide compound can be obtained from the dibasic acid of formula (III).

[0080] Next, the diamide compound is nitrilated and reduced with hydrogen.

[0081] The conditions for nitrilation and hydrogen reduction are not particularly limited, and appropriate conditions can be appropriately selected by those skilled in the art.

[0082] In this manner, the diamine compound represented by the above formula (I) of the present invention can be produced.

[0083] (Resin additive and resin composition)

[0084] The resin additive of the present invention contains a diamine compound represented by the above formula (I).

[0085] Here, the term "resin additive" as used in this specification is used in a broad sense, including, for example, (1) substances that are added independently of the resin as a constituent component when constituting a resin composition, thereby improving the stability of the resulting resin composition and / or imparting functionality (for example, stabilizers, antioxidants, ultraviolet absorbers, etc. that can improve stability and / or plasticizers, flame retardants, nucleating agents, transparent agents, antistatic agents, lubricants, etc. that can impart prescribed functions); (2) substances that are physically or chemically linked or reacted with the resin as a constituent component when constituting a resin composition (for example, crosslinking agents, curing agents); and (3) substances that can constitute the resin itself through reaction (for example, raw material monomers).

[0086] In the resin additive of the present invention, in addition to the diamine compound represented by the above formula (I), other ingredients that can be added to a conventional resin composition may also be contained. Such other ingredients are not particularly limited, and examples thereof include antioxidants such as phenolic antioxidants, sulfur antioxidants and / or phosphorus antioxidants; antistatic agents such as anionic active agents, cationic active agents, nonionic active agents, and amphoteric active agents; lubricants such as hydrocarbon lubricants, fatty acid lubricants, higher alcohol lubricants, fatty acid amide lubricants, metal soap lubricants, and ester lubricants; flame retardants such as organic flame retardants and inorganic flame retardants; and combinations thereof. The content of the above other ingredients that can be contained in the resin additive of the present invention is not particularly limited, and any amount can be selected by a person skilled in the art.

[0087] In one embodiment, the resin composition of the present invention contains the above-mentioned resin additive and a resin (hereinafter, such a resin composition is referred to as a "first resin composition").

[0088] The resin that can constitute the first resin composition of the present invention can be a thermosetting resin or a thermoplastic resin, and various resins obtained by reaction with amino groups can be listed, for example. As such examples, epoxy resins, polyurethanes, polyimides, polyamide-imides, maleimide resins, polyamides, etc. can be listed. From the reason that appropriate flexibility can be given, the above-mentioned resin additive (that is, the diamine compound represented by formula (I)) is preferably able to be used as a curing agent or a resin constituent material of the above-mentioned resin, and more preferably can be used as a curing agent for epoxy resins.

[0089] In the first resin composition of the present invention, the contents of the resin and the resin additive are not particularly limited, and a person skilled in the art may select appropriate contents.

[0090] In one embodiment, the resin composition of the present invention contains a resin composed of one or more monomer compounds and the above-mentioned resin additive (hereinafter, such a resin composition is referred to as a "second resin composition").

[0091] 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 examples thereof include ε-caprolactam; undecane lactam; lauryl lactam; a combination of hexamethylenediamine and adipic acid; a combination of hexamethylenediamine and sebacic acid; a combination of hexamethylenediamine and terephthalic acid; a combination of hexamethylenediamine and isophthalic acid; a combination of nonanediamine and terephthalic acid; a combination of methylpentanediamine and terephthalic acid; a combination of ε-caprolactam and lauryl lactam; a combination of p-phenylenediamine and terephthalic acid; a combination of m-phenylenediamine and isophthalic acid; pyromellitic anhydride; a combination of trimellitic anhydride and diisocyanates; and a combination of trimellitic chloride and diamines.

[0092] In the second resin composition of the present invention, relative to one or more of the above-mentioned monomeric compounds, the above-mentioned resin additive (or the diamine compound represented by the above-mentioned formula (I)) can function as a monomer component for constituting a resin. The above-mentioned monomeric compound and the above-mentioned resin additive (or the diamine compound represented by the above-mentioned formula (I)) can be polymerized using, for example, a coupling reaction well known to those skilled in the art. The mixing ratio of the monomeric compound and the above-mentioned resin additive (or the diamine compound represented by the above-mentioned formula (I)) is not particularly limited, and a combination of various contents can be appropriately selected by those skilled in the art. Thus, a resin consisting of one or more monomeric compounds and the above-mentioned resin additive is produced.

[0093] The first resin composition and the second resin composition of the present invention may further contain any other resin additive. Examples of such other resin additives are not particularly limited, but other components that may be contained in the resin additive of the present invention may be cited. The amount of the other resin additive that may be contained in the resin additive of the present invention is not particularly limited, and any amount may be selected by a person skilled in the art.

[0094] The first resin composition and the second resin composition of the present invention can both impart appropriate flexibility to the resin of the constituent components by, for example, the resin additives (i.e., the diamine compounds represented by formula (I)) contained. At this time, the first resin composition and the second resin composition of the present invention are compared with the case of introducing a flexible chain of polar groups into the constituent molecules of the resin as described above, and other characteristics other than the preferred flexibility do not have a large change. In addition, the flexibility imparted by such resin additives can be easily modulated by adjusting, for example, the amount of the resin additive. It should be noted that, in the case where the resin contained in the second resin composition of the present invention is a polymer epoxy resin, polyimide, polyamide-imide, etc., whose main chain is composed of aromatic rings, such resins can have excellent physical properties in, for example, low dielectric constant, low dielectric loss tangent, low transmission loss, etc. Therefore, the second resin composition of the present invention is expected to be useful in, for example, the field of electronic materials.

[0095] (Other uses)

[0096] The diamine compound represented by formula (I) can also be used for other purposes other than the resin additives mentioned above. Examples of such other uses include surfactants (e.g., cationic surfactants) such as softeners, antistatic agents, and lubricating rust inhibitors that can prevent corrosion of metal products (e.g., various products of steel, stainless steel, and aluminum).

[0097] Example

[0098] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0099] (Example 1: C 18 Synthesis of saturated branched diamine compounds

[0100] Into a 5L four-necked flask equipped with a thermometer and a stirrer, 1500g of a long-chain dibasic acid diester (SB-20MM manufactured by Okamura Oil Manufacturing Co., Ltd. / main component: dimethyl isoeicosanedioate, molecular weight 370) and 804g (16.1 mol) of hydrazine monohydrate and 1500mL of 2-propanol as a solvent were added and refluxed for 5 hours. After the reaction was completed, infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) confirmed a peak corresponding to the ester bond of dimethyl isoeicosanedioate (1731cm －1 ) and the peak corresponding to the hydrazide bond (1627 cm －1 and 1533cm －1) was generated. Furthermore, by high-speed liquid chromatography mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), it was confirmed that the peak of isoeicosanedioic acid dimethyl ester (molecular weight 370) as a raw material disappeared and a new peak corresponding to isoeicosanedioic acid dihydrazide (molecular weight 370) appeared. In this way, dihydrazide 1a corresponding to isoeicosanedioic acid dihydrazide was obtained.

[0101] Into a 5L four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, add the above-obtained dihydrazide 1a (450g), 2100mL of water, and 759g of 35% hydrochloric acid, and cool the temperature to below 10°C while stirring. Next, an aqueous solution of 170g (2.5mol) of sodium nitrite dissolved in 300mL of water is added dropwise, and the temperature is maintained below 10°C to generate azide in the solution. Thereafter, the obtained solution is heated under reflux to cause the generated azide to undergo Curtius rearrangement, and the generation of nitrogen and carbon dioxide is visually confirmed. After continuing to reflux for 3 hours, 714g (8.7mol) of 49% sodium hydroxide aqueous solution is added for hydrolysis, and the diamine is extracted with toluene and washed with water. Toluene is then distilled off under reduced pressure, and the amine value is measured in accordance with JISK7237. As a result, 221.3g of C with an amine value of 321 is obtained. 18 Saturated branched diamine 1b.

[0102] The obtained diamine 1b was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to have a peak (1627 cm －1 and 1533cm －1 ) disappeared, and a new peak corresponding to the amino group (1722 cm －1 and 1571cm －1 ). In addition, by high-speed liquid chromatography mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), it was confirmed that the peak confirmed in dihydrazide 1a (molecular weight 370) disappeared. And by gas chromatography mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation), it was confirmed that diamine 1b contained C as the main component. 18 7-Ethylhexadecanediamine and C 16 7-Ethyltetradecanediamine (molecular weight 256), a saturated branched diamine, has the following characteristic fragments.

[0103] (7-ethylhexadecanediamine)

[0104] m / z 284 (molecular ion peak), m / z 100 (reference peak)

[0105] (7-Ethyltetradecanediamine)

[0106] m / z 256 (molecular ion peak), m / z 100 (reference peak)

[0107] Next, the diamine 1b obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3 / 1 (volume ratio)) to separate the main components 7-ethylhexadecanediamine (91%) and 7-ethyltetradecanediamine (3%). 1 H NMR analysis (Mercury-300: manufactured by Varian). The δ values ​​are shown in Table 1 (CDCl3).

[0108] [Table 1]

[0109]

[0110] (Example 2: C 20 Synthesis of unsaturated branched diamine compounds

[0111] The same procedure as in Example 1 was carried out except that 1000 g of a long-chain dibasic acid diester (IPU-22MM manufactured by Okamura Oil Manufacturing Co., Ltd. / main component: dimethyl isodocosadienoate, molecular weight 394), 527 g (10.5 mol) of hydrazine monohydrate and 1000 mL of 2-propanol as a solvent were used to obtain 999 g of dihydrazide 2a (isodocosadienoic acid dihydrazide).

[0112] The obtained dihydrazide 2a was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to have a peak (1731 cm-1) corresponding to the ester bond of dimethyl isodocosadienoate. －1 ) and the peak corresponding to the hydrazide bond (1627 cm －1 and 1533cm －1 ) was generated. In addition, by high-performance liquid chromatography mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), it was confirmed that the peak of dimethyl isoeicosanedioate (molecular weight 394) as a raw material disappeared and a new peak corresponding to isoeicosanedioic acid dihydrazide (molecular weight 394) appeared.

[0113] The same method as in Example 1 was used except that 400 g (1.0 mol) of the above-obtained dihydrazide 2a was used instead of dihydrazide 1a, 582 g (6.1 mol) of methanesulfonic acid was used instead of hydrochloric acid, and the amount of sodium nitrite was changed to 167 g (2.4 mol). 100.7 g of C with an amine value of 339 was obtained. 20 Unsaturated branched diamine 2b.

[0114] The obtained diamine 2b was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to have a peak (1627 cm －1 and 1533cm －1 ) disappeared, and a new peak corresponding to the amino group (1722 cm －1 and 1572cm －1 ). In addition, by high-speed liquid chromatography mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), it was confirmed that the peak confirmed in dihydrazide 2a (molecular weight 394) disappeared. And by gas chromatography mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation), it was confirmed that diamine 2b contained C as the main component. 20 The unsaturated branched diamines are 7,12-dimethyloctadecanediamine-7,11-diene and 7-isopropenyl-10-methylhexadecanediamine-9-ene (molecular weight 308). The characteristic fragments are as follows.

[0115] (7,12-Dimethyloctadecanediamine-7,11-diene)

[0116] m / z 308 (molecular ion peak), m / z 181 (reference peak)

[0117] (7-isopropenyl-10-methylhexadecanediamine-9-ene)

[0118] m / z 308 (molecular ion peak), m / z 100 (reference peak)

[0119] Next, the diamine 2b obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3 / 1 (volume ratio)) to separate the main components of 7,12-dimethyl-7,11-eicosanediamine-7,11-diene (49%) and 7-isobutenyl-10-methylhexadecanediamine-9-ene (30%). 1 H NMR analysis (Mercury-300: manufactured by Varian). The δ values ​​are shown in Table 2 (CDCl3).

[0120] [Table 2]

[0121]

[0122] (Example 3: C 22 Synthesis of unsaturated branched diamine compounds

[0123] In a 5L autoclave equipped with a thermometer and a stirrer, 1661g of a long-chain dibasic acid (IPU-22 manufactured by Okamura Oil Co., Ltd. / main component: isodocosadienoic acid, molecular weight 366) and 50g of silica gel were added, and reacted with 300g (17.6mol) of ammonia at 300°C under pressure for 2 hours. Next, 650mL of methanol and 70g of activated carbon-immobilized nickel were added, and reacted with 130g (7.6mol) of ammonia and 420g (210mol) of hydrogen at 180°C under pressure for 2 hours. After cooling, the obtained reaction solution was filtered, and dilute sulfuric acid was added to remove the lower layer. The organic layer was washed with water, and after removing the water under reduced pressure, 1495g of diamine 3 with an amine value of 290 was obtained.

[0124] The obtained diamine 3 was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to have a peak (1711 cm-1) corresponding to the carboxyl group derived from isodocosadienic acid as a raw material. －1 ) disappeared, and a new peak corresponding to the amino group (1722 cm －1 and 1572cm －1 ). Furthermore, by gas chromatography mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation), it was confirmed that the peak corresponding to the raw material isodocosadienoic acid (molecular weight 366) disappeared. Furthermore, it was confirmed that diamine 2b contained C as the main component. 20 The unsaturated branched diamines are 8,13-dimethyl-8,12-docosahexadecadiene diamine and 8-isopropenyl-11-methyl-10-octadecadiene diamine (molecular weight 336). The characteristic fragments are as follows.

[0125] (8,13-Dimethyleicosanediamine-8,12-diene)

[0126] m / z 336 (molecular ion peak), m / z 195 (reference peak)

[0127] (8-isopropenyl-11-methyloctadecanediamine-10-ene)

[0128] m / z 336 (molecular ion peak), m / z 114 (reference peak)

[0129] Next, the diamine 3 obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3 / 1 (volume ratio)), and the main components 8,13-dimethyleicosanediamine-8,12-diene (50%) and 8-isopropenyl-11-methyloctadecanediamine-10-ene (28%) were separated. 1HNMR analysis (Mercury-300: manufactured by Varian). The δ values ​​are shown in Table 3 (CDCl3).

[0130] [Table 3]

[0131]

[0132] (Example 4: Preparation of Cured Epoxy Resin (E1))

[0133] An epoxy resin composition was prepared by mixing 10.0 g of bisphenol A epoxy resin (EPOMIC manufactured by Mitsui Chemicals, Inc., epoxy equivalent (hereinafter referred to as WPE) 188), 4.4 g of diamine 1b obtained in Example 1 as a curing agent (0.95 equivalent relative to WPE), and 0.1 g (1 phr) of N,N-dimethylbenzylamine as a curing accelerator. Next, 10 g of the resin composition was weighed in a heat-resistant container, heated at 70°C for 15 hours, and heated at 120°C for 1 hour to obtain an epoxy resin cured product (E1). For the obtained epoxy resin cured product (E1), a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to keep the sample at -50°C for 10 minutes, and then heated to 200°C at a heating rate of 10°C per minute, thereby measuring the glass transition temperature (Tg) from the heat change with respect to the heating. In order to measure the gelation rate of the epoxy resin cured product (E1), 5 g of the sample was subjected to Soxhlet extraction using acetone for 5 hours. 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 obtained results are shown in Table 4.

[0134] (Example 5: Preparation of Cured Epoxy Resin (E2))

[0135] The 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. The DSC analysis and gelation rate measurement of the obtained epoxy resin cured product (E2) were performed in the same manner as in Example 1. The obtained results are shown in Table 4.

[0136] (Example 6: Preparation of Cured Epoxy Resin (E3))

[0137] The epoxy resin cured product (E3) was prepared in the same manner as in Example 1 except that the diamine 3 (4.9 g) prepared in Example 3 was used instead of the diamine 1b as the curing agent. The DSC analysis and gelation rate measurement of the obtained epoxy resin cured product (E3) were performed in the same manner as in Example 1. The obtained results are shown in Table 4.

[0138] (Comparative Example 1: Preparation of Cured Epoxy Resin (CE1))

[0139] A cured epoxy resin (CE1) was prepared in the same manner as in Example 1 except that tetraethylenepentamine (1.4 g) was used instead of diamine 1b as the curing agent. DSC analysis and gelation rate measurement of the cured epoxy resin (CE1) were performed in the same manner as in Example 1. The results are shown in Table 4.

[0140] (Comparative Example 2: Preparation of Cured Epoxy Resin (CE2))

[0141] A cured epoxy resin (CE2) was prepared in the same manner as in Example 1 except that triethylenetetramine (1.2 g) was used instead of diamine 1b as the curing agent. DSC analysis and gelation rate measurement of the obtained cured epoxy resin (CE2) were performed in the same manner as in Example 1. The obtained results are shown in Table 4.

[0142] (Comparative Example 3: Preparation of Cured Epoxy Resin (CE3))

[0143] A cured epoxy resin (CE3) was prepared in the same manner as in Example 1 except that hexamethylenediamine (1.5 g) was used instead of diamine 1b as the curing agent. DSC analysis and gelation rate measurement of the cured epoxy resin (CE3) were performed in the same manner as in Example 1. The results are shown in Table 4.

[0144] (Comparative Example 4: Preparation of Cured Epoxy Resin (CE4))

[0145] A cured epoxy resin (CE4) was prepared in the same manner as in Example 1 except that 1,10-decanediamine (2.1 g) was used instead of diamine 1b as the curing agent. DSC analysis and gelation rate measurement of the obtained cured epoxy resin (CE4) were performed in the same manner as in Example 1. The obtained results are shown in Table 4.

[0146] (Comparative Example 5: Preparation of Cured Epoxy Resin (CE5))

[0147] A cured epoxy resin (CE5) was prepared in the same manner as in Example 1 except that a polyether diamine (Baxxodure EC302 manufactured by Mitsui Chemicals Fine Co., Ltd.; average molecular weight 400) (5.6 g) was used instead of diamine 1b as the curing agent. DSC analysis of the cured epoxy resin (CE5) and measurement of the gelation rate were performed in the same manner as in Example 1. The results are shown in Table 4.

[0148] [Table 4]

[0149]

[0150] As shown in Table 4, the epoxy resin cured products (E1) to (E3) prepared in Examples 4 to 6 have lower Tg than the epoxy resin cured products (CE1) and (CE2) of Comparative Examples 1 and 2 using conventional amine curing agents, and have a lower Tg than the epoxy resin cured product (CE3) of Comparative Example 3 using C6 diamine and the epoxy resin cured product (CE4) of Comparative Example 4 using C6 diamine. 10 The epoxy resin cured product (E1) to (E3) of Examples 1 to 3 using diamine 1b, 2b or 3 consisting only of amino groups and carbon chains and the epoxy resin cured product (CE5) of Comparative Example 5 using a curing agent containing a polyether chain have approximately the same Tg and gelation rate.

[0151] (Example 7: Evaluation of curability of epoxy resin composition (EC1))

[0152] Using the diamine 1b obtained in Example 1 as a curing agent, 50 g of an epoxy resin composition (EC1) was prepared in the same manner as in Example 4 and placed in a glass sample tube. It was immersed in an oil bath at 70°C, and the temperature of the resin was plotted at regular intervals (every 20 seconds) as a sign of exothermic curing. The gel point, gel time, maximum exothermic point, minimum curing time and pot life were obtained from the obtained exothermic curing curve. It should be noted that the pot life is calculated as a value 0.8 times (×0.8) the gel time. The obtained results are shown in Table 5.

[0153] (Example 8: Evaluation of curability of epoxy resin composition (EC2))

[0154] An epoxy resin composition (EC2) was prepared in the same manner as in Example 4 except that diamine 2b (21.0 g) prepared in Example 2 was used instead of diamine 1b as a curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0155] (Example 9: Evaluation of curability of epoxy resin composition (EC3))

[0156] An epoxy resin composition (EC3) was prepared in the same manner as in Example 4 except that diamine 1b was used instead of diamine 3 (24.5 g) prepared in Example 3 as a curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0157] (Comparative Example 6: Evaluation of Curability of Epoxy Resin Composition (CC1))

[0158] The epoxy resin composition (CC1) was prepared in the same manner as in Example 4 except that tetraethylenepentamine (7.0 g) was used instead of diamine 1b as the curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0159] (Comparative Example 7: Evaluation of Curability of Epoxy Resin Composition (CC2))

[0160] The epoxy resin composition (CC2) was prepared in the same manner as in Example 4 except that triethylenetetramine (6.0 g) was used instead of diamine 1b as the curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0161] (Comparative Example 8: Evaluation of Curability of Epoxy Resin Composition (CC3))

[0162] The epoxy resin composition (CC3) was prepared in the same manner as in Example 4 except that hexamethylenediamine (7.5 g) was used instead of diamine 1b as the curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0163] (Comparative Example 9: Evaluation of Curability of Epoxy Resin Composition (CC4))

[0164] An epoxy resin composition (CC4) was prepared in the same manner as in Example 4 except that 1,10-decanediamine (10.5 g) was used instead of diamine 1b as the curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4. The obtained results are shown in Table 5.

[0165] (Comparative Example 10: Evaluation 1 of curability of epoxy resin composition (CC5))

[0166] An epoxy resin composition (CC5) was prepared in the same manner as in Example 4 except that polyether diamine (28.0 g) was used instead of diamine 1b as the curing agent, and an exothermic curing curve of the resin composition was attempted in the same manner as in Example 4. However, after the resin temperature reached 70°C, which was the same temperature as the oil bath temperature, no heat was generated even after 30 minutes had passed, indicating that the curability of the composition (CC5) was significantly low.

[0167] (Comparative Example 11: Evaluation 2 of curability of epoxy resin composition (CC5))

[0168] The epoxy resin composition (CC5) was prepared in the same manner as in Example 4 except that polyether diamine (28.0 g) was used instead of diamine 1b as the curing agent, and the gelling point, gelling time, maximum exothermic point, minimum curing time and pot life were obtained from the exothermic curing curve of the resin composition in the same manner as in Example 4 except that the oil bath temperature was set to 120°C. The obtained results are shown in Table 5.

[0169] [Table 5]

[0170]

[0171] As shown in Table 5, the epoxy resin compositions (EC1) to (EC3) prepared in Examples 7 to 9 have a longer gelling time and a longer minimum curing time, and therefore have a characteristic of curing more slowly than the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11. Regarding the pot life during curing, the epoxy resin compositions (EC1) to (EC3) prepared in Examples 7 to 9 are about 2 to 3 times longer than the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11. In addition, when focusing on the gelling temperature and the maximum exothermic point, the heat generation of the epoxy resin compositions (EC1) to (EC3) prepared in Examples 7 to 9 is similar to that of the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11. As can be seen from the results of Comparative Examples 10 and 11, the polyether diamine, which is a highly reactive flexibility-imparting agent, has a low reactivity and therefore has poor curability at low temperatures. That is, the diamines 1b, 2b and 3 used in the epoxy resin compositions (EC1) to (EC3) prepared in Examples 7 to 9 have a longer pot life than the curing agents of the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11, which are known as commercially available amine-based curing agents, and have better low-temperature curing properties than other flexibility-imparting agents.

[0172] (Example 10: Water resistance of cured epoxy resin (E1))

[0173] The epoxy resin cured product (E1) prepared in Example 4 (containing diamine 1b as a curing agent) was put into boiling water and boiled for 1 hour. The mass of the resin before the addition and the mass of the resin after boiling for 1 hour (it should be noted that the water attached to the surface was removed) were measured and the following formula was used:

[0174] Water absorption rate (%) = (mass of resin after boiling - mass of resin before addition) / (mass of resin before addition) × 100

[0175] The water absorption rate (%) of the epoxy resin cured material (E1) was calculated and evaluated as the water resistance of the epoxy resin cured material (E1).

[0176] (Example 11: Water resistance of cured epoxy resin (E2))

[0177] The cured epoxy resin (E2) prepared in Example 5 (containing diamine 2b as a curing agent) was used instead of the cured epoxy resin (E1). The cured epoxy resin (E2) was boiled in the same manner as in Example 10, and the water absorption (%) of the cured epoxy resin (E2) was calculated. The obtained results are shown in Table 6.

[0178] (Example 12: Water resistance of cured epoxy resin (E3))

[0179] The cured epoxy resin (E3) prepared in Example 6 (containing diamine 3 as a curing agent) was used instead of the cured epoxy resin (E1). The cured epoxy resin (E3) was boiled in the same manner as in Example 10, and the water absorption (%) of the cured epoxy resin (E3) was calculated. The obtained results are shown in Table 6.

[0180] (Comparative Example 12: Water resistance of cured epoxy resin (CE1))

[0181] The cured epoxy resin (CE1) prepared in Comparative Example 1 (containing tetraethylenepentamine as a curing agent) was used instead of the cured epoxy resin (E1). The cured epoxy resin (CE1) was boiled in the same manner as in Example 10, and the water absorption (%) of the cured epoxy resin (CE1) was calculated. The obtained results are shown in Table 6.

[0182] (Comparative Example 13: Water resistance of epoxy resin cured product (CE5))

[0183] The cured epoxy resin (CE5) prepared in Comparative Example 5 (containing polyether diamine as a curing agent) was used instead of the cured epoxy resin (E1). The cured epoxy resin (CE5) was boiled in the same manner as in Example 10, and the water absorption (%) of the cured epoxy resin (CE5) was calculated. The obtained results are shown in Table 6.

[0184] [Table 6]

[0185]

[0186] As shown in Table 6, the epoxy resin cured products (E1) to (E3) evaluated in Examples 10 to 12 (containing diamine 1b, 2b or 3 as a curing agent) and the epoxy resin cured product (CE1) (containing tetraethylenepentamine as a curing agent) equivalent to a conventional product evaluated in Comparative Example 12 all had a water absorption rate of 0%, and had sufficient water resistance. In contrast, the epoxy resin cured product (CE5) evaluated in Comparative Example 13, which contained a polyether diamine (molecular weight 400) known as a flexibility imparting agent as a curing agent, showed a water absorption rate of about 1%. That is, while polyether diamine imparts flexibility, it is accompanied by a decrease in water resistance in exchange, whereas the epoxy resin cured products (E1) to (E3) using diamine 1b, 2b or 3 (produced in Examples 4 to 6) can impart flexibility without impairing water resistance.

[0187] (Example 13: Preparation of bismaleimide prepolymer (EM1))

[0188] Into a 500 mL four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, 21.5 g (60.1 mmol) of 4,4'-bismaleimide diphenylmethane and 200 mL of THF were added, and the diamine 1b (5.2 g) obtained in Example 1 (30.0 mmol equivalent in terms of amino group) was added dropwise as a modifier. The temperature was raised to 50°C while stirring, and the mixture was stirred for another 1.5 hours. Next, 3.1 g (30.1 mmol) of acetic anhydride was added, and the mixture was stirred for another hour. THF was removed under reduced pressure to obtain 27.6 g of bismaleimide prepolymer (EM1).

[0189] The obtained bismaleimide prepolymer (EM1) was analyzed by infrared spectroscopy (FT-IR: manufactured by JASCO Corporation), and a peak corresponding to an α,β-unsaturated bond (1606 cm －1 ) decreased, and a peak corresponding to the imide bond (1705 cm －1 and 1510cm －1 ), the peak corresponding to the amide bond (1636 cm －1 ).

[0190] In addition, 10 g of the bismaleimide prepolymer (EM1) was weighed in a heat-resistant container and heated at 170° C. for 2 hours to cure. The obtained cured product was kept at 0° C. for 10 minutes using a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation), and then heated to 400° C. at a heating rate of 10° C. per minute, thereby measuring the glass transition temperature (Tg) from the heat change for the heating. The obtained results are shown in Table 7.

[0191] (Example 14: Preparation of bismaleimide prepolymer (EM2))

[0192] The same method as in Example 13 was used except that the diamine 2b (5.0 g) prepared in Example 2 was used instead of the diamine 1b as the modifier to obtain 27.8 g of a bismaleimide prepolymer (EM2). The DSC analysis of the cured product of the bismaleimide prepolymer (EM2) was performed in the same manner as in Example 13. The obtained results are shown in Table 7.

[0193] (Example 15: Preparation of bismaleimide prepolymer (EM3))

[0194] The same method as in Example 13 was used except that the diamine 3 (5.8 g) prepared in Example 3 was used instead of the diamine 1b as the modifier, to obtain 58.0 g of a bismaleimide prepolymer (EM3). The DSC analysis of the cured product of the bismaleimide prepolymer (EM3) was performed in the same manner as in Example 13. The obtained results are shown in Table 7.

[0195] (Comparative Example 14: Preparation of Bismaleimide Prepolymer (CM1))

[0196] The same method as in Example 13 was used except that hexamethylenediamine (1.8 g) was used instead of diamine 1b as the modifier to obtain 22.5 g of a bismaleimide prepolymer (CM1). The DSC analysis of the cured product of the bismaleimide prepolymer (CM1) was performed in the same manner as in Example 13. The obtained results are shown in Table 7.

[0197] (Comparative Example 15: DSC Analysis of 4,4'-Bismaleimidodiphenylmethane)

[0198] For comparison, 10 g of 4,4′-bismaleimidodiphenylmethane was cured alone without adding diamine 1b, and the cured product was analyzed by DSC in the same manner as in Example 13. The obtained results are shown in Table 7.

[0199] [Table 7]

[0200]

[0201] 1) Only 4,4-bismaleimide diphenylmethane was used

[0202] As shown in Table 7, the cured products of the bismaleimide prepolymers (EM1) to (EM3) prepared in Examples 13 to 15 have significantly lower Tg than the cured products of the bismaleimide prepolymer (CM1) prepared in Comparative Example 14 and 4,4'-bismaleimide diphenylmethane (modifier not added) of Comparative Example 15. The longer the carbon chain disposed between the two amino groups constituting the diamines 1b, 2b and 3 used as the modifier, the higher the flexibility can be imparted to the obtained cured product.

[0203] (Example 16: Preparation of polyamide 18,6)

[0204] In a 200 ml measuring cup, diamine 1b (3.8 g) (21.8 mmol equivalent in terms of amino groups), triethylamine (2.2 g) (21.8 mmol), and 50 mL of hexane were placed, and adipic acid dichloride (2.0 g) (10.9 mmol) dissolved in 50 mL of hexane was added while stirring to carry out solution polymerization. After continuous stirring for 30 minutes, the mixture was filtered, and the filtrate was washed with water and acetone and dried to obtain 2.3 g of polyamide 18,6.

[0205] The obtained polyamide 18,6 was analyzed by infrared spectroscopy (FT-IR: manufactured by JASCO Corporation), and a peak corresponding to an amide bond (1635 cm －1 、1542cm －1 ).

[0206] In addition, for this polyamide 18,6, a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to measure the glass transition temperature (Tg) from the heat change with respect to the temperature increase by heating the sample to 100°C at a temperature increase rate of 5°C per minute after the sample was kept at 0°C for 10 minutes. The obtained results are shown in Table 8.

[0207] (Example 17: Preparation of polyamide 20,6)

[0208] 2.5 g of polyamide 6.6 was obtained in the same manner as in Example 16 except that diamine 2b (3.6 g) prepared in Example 2 was used instead of diamine 1b. DSC analysis of the cured product of polyamide 20.6 was performed in the same manner as in Example 16. The obtained results are shown in Table 8.

[0209] (Example 18: Preparation of polyamide 22,6)

[0210] The same procedure as in Example 16 was repeated except that diamine 3 (3.8 g) prepared in Example 3 was used instead of diamine 1b to obtain 2.3 g of polyamide 6.6. The cured product of polyamide 22.6 was subjected to DSC analysis in the same manner as in Example 16. The results are shown in Table 8.

[0211] (Comparative Example 16: Preparation of Polyamide 2,6)

[0212] In a 200 ml measuring cup, ethylenediamine (0.7 g) (10.9 mmol), 49% sodium hydroxide (0.9 g) (10.9 mmol), and 50 mL of water were added, and adipic acid dichloride (2.0 g) (10.9 mmol) dissolved in 50 mL of hexane was added while stirring to perform interfacial polymerization. After continuous stirring for 30 minutes, the mixture was filtered, and the filtrate was washed with water and acetone and dried to obtain 0.9 g of polyamide 2,6. For this polyamide 2.6, DSC analysis of the cured product was performed in the same manner as in Example 16. The results obtained are shown in Table 8.

[0213] (Comparative Example 17: Preparation of Polyamide 6,6)

[0214] The same procedure as in Comparative Example 16 was followed except that hexamethylenediamine (1.3 g) was used instead of ethylenediamine to obtain 0.7 g of polyamide 6.6. The DSC analysis of the cured product of polyamide 6.6 was performed in the same manner as in Example 16. The obtained results are shown in Table 8.

[0215] [Table 8]

[0216]

[0217] As shown in Table 8, the polyamides (polyamide 18.6, polyamide 20.6, polyamide 22.6) prepared in Examples 16 to 18 all have significantly lower Tg than polyamide 2.6 prepared in Comparative Example 16 and polyamide 6.6 of Comparative Example 17. As in other Examples, the longer the carbon chain between the two amino groups of diamines 1b, 2b, and 3 used to constitute the polyamide, the higher the flexibility can be imparted to the obtained cured product.

[0218] (Example 19: Preparation of polyimide (ED1))

[0219] Pyromellitic anhydride (50.0 g) and cyclohexanone (200 ml) were placed in a reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, and heated to 60° C. Then, 40.0 g of the diamine 1b obtained in Example 1 dissolved in toluene (100 ml) was added, and imidization was carried out at 140° C. for 3 hours. The solvent was removed under reduced pressure to obtain 80.1 g of a polyimide (ED1).

[0220] The polyimide (ED1) obtained above was confirmed to have a peak corresponding to an imide bond (1769 cm-1) by infrared spectroscopy (FT-IR: manufactured by JASCO Corporation). －1 ).

[0221] In addition, for this polyimide (ED1), a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to measure the glass transition temperature (Tg) of the sample from the heat change with respect to the temperature increase by heating the sample to 400°C at a temperature increase rate of 10°C per minute after the sample was kept at 0°C for 10 minutes. The obtained results are shown in Table 8.

[0222] (Example 20: Preparation of polyimide (ED2))

[0223] 78.9 g of polyimide (ED2) was obtained in the same manner as in Example 19 except that diamine 2b (37.9 g) prepared in Example 2 was used instead of diamine 1b. DSC analysis of the resin of this polyimide (ED2) was performed in the same manner as in Example 19. The obtained results are shown in Table 9.

[0224] (Example 21: Preparation of polyimide (ED3))

[0225] 81.3 g of polyimide (ED3) was obtained in the same manner as in Example 19 except that diamine 3 (44.3 g) prepared in Example 3 was used instead of diamine 1b. DSC analysis of the polyimide (ED3) was performed in the same manner as in Example 19. The obtained results are shown in Table 9.

[0226] (Comparative Example 18: Preparation of polyimide (CD1))

[0227] 69.7 g of polyimide (CD1) was obtained in the same manner as in Example 19 except that p-phenylenediamine (24.8 g) was used instead of diamine 1b. DSC analysis of the polyimide (CD1) was performed in the same manner as in Example 19. The obtained results are shown in Table 9.

[0228] (Comparative Example 19: Preparation of polyimide (CD2))

[0229] 70.9 g of a polyimide (CD2) was obtained in the same manner as in Example 19 except that hexamethylenediamine (26.6 g) was used instead of diamine 1b. DSC analysis of the polyimide (CD2) was performed in the same manner as in Example 19. The obtained results are shown in Table 9.

[0230] [Table 9]

[0231]

[0232] As shown in Table 9, although both Comparative Examples 18 and 19 use diamines having 6 carbon atoms, Comparative Example 19 using an aliphatic diamine has a lower Tg. In contrast, the diamines used in Examples 19 to 20 are aliphatic diamines having a larger number of carbon atoms, and have lower Tg than Comparative Example 19. Therefore, as in other Examples, the longer the carbon chain disposed between the two amino groups of diamines 1b, 2b, and 3 used to constitute the polyimide, the higher the flexibility can be imparted to the obtained polymer.

[0233] (summary)

[0234] To summarize the above-mentioned embodiments, it can be said that when the diamine compounds of the present invention (diamines 1b, 2b and 3) having a long carbon chain between two amino groups are used as resin additives, flexibility can be imparted to the resin (see, for example, Table 4, Table 7, Table 8 and Table 9). In addition, as can be seen from Table 2, although these diamine compounds are slightly slower in reactivity when used as epoxy resin curing agents compared to the commercially available amine curing agents used in Comparative Examples 6 to 11, it can be seen from Table 1 that their gelation rate is high and the curing reaction is fully carried out. Therefore, it is the most suitable material for adjusting the pot life. On the other hand, it can be seen that the polyether diamine (molecular weight 400) that can impart flexibility has obtained a flexibility imparting effect corresponding to the molecular weight (Table 1), but the reactivity is significantly deteriorated at low temperature (70°C), and the curing reaction can be carried out at 120°C (Table 2). In addition, it can be seen from Table 3 that the water resistance of the cured product using polyether diamine is poor, while the cured product using long-chain diamine can obtain water resistance equivalent to that of conventional amine curing agents without sacrificing water resistance. It can be seen from this that the diamine compound of the present invention is more useful than the polyether diamine of the current flexibility imparting agent.

[0235] (Example 22: Anticorrosion effect on metal products)

[0236] 50 mL of an aqueous solution containing 0.05 mass % of the diamine 1b obtained in Example 1 added to 10% hydrochloric acid as an anticorrosive agent was placed in a glass sample tube. A standard test plate (JIS G3141; manufactured by Japan Test Panel Co., Ltd.) that had been subjected to three times of grinding and toluene washing was immersed in the aqueous solution, and the test plate was heated at 60° C. for 1 hour to be corroded. The corroded test plate was washed with water and dried, and the corrosion rate (%) was calculated from the mass difference before and after immersion according to the following formula.

[0237] Corrosion rate (%) = (mass of the test plate before immersion - mass of the test plate after immersion) / (mass of the test plate before immersion) × 100

[0238] The obtained results are shown in Table 10.

[0239] (Comparative Example 20: Anticorrosion Effect on Metal Products)

[0240] The corrosion rate of the standard test plate was measured in the same manner as in Example 22 except that the anticorrosive agent (diamine 1b in Example 1) was not added. The obtained results are shown in Table 10.

[0241] (Comparative Example 21: Anticorrosion Effect on Metal Products)

[0242] The corrosion rate of the standard test plate was measured in the same manner as in Example 22, except that 0.05 mass % of dodecylamine was used instead of diamine 1b as the anticorrosive agent.

[0243] (Comparative Example 22: Anticorrosion Effect on Metal Products)

[0244] The corrosion rate of the standard test plate was measured in the same manner as in Example 22, except that 0.05 mass % of hexamethylenediamine was used instead of diamine 1b as the anticorrosive agent.

[0245] [Table 10]

[0246]

[0247] As shown in Table 10, the corrosion rate of the steel plate was the lowest when diamine 1b (isooctadecanediamine) of Example 22 was used, and the corrosion protection effect was high against the acidic aqueous solution. Such an anticorrosive agent is useful when performing cleaning treatments such as pickling, acid immersion, and etching of metals.

[0248] Industrial Applicability

[0249] According to the diamine compound of the present invention, various resins can be used to provide a resin combination with excellent flexibility. The resin combination is a material composed of resins such as epoxy, polyurethane, polyimide, polyamide-imide, maleimide, polyamide, etc., and is useful in various technical fields such as sealants (bottom filling glue) in repair materials, various coatings, various adhesives, electronic materials, insulating components, mold resins, photoresist materials, resin-reinforced solder paste materials, flexible printed circuit board materials, various films, thermoplastic resins, and nylon fibers. And, when the diamine compound of the present invention is used as a cationic surfactant for lubricating rust preventives, high anticorrosion effects can be exerted for metal products. It can be seen from this that it is useful in metal processing fields, mechanical fields, etc.

Claims

1. A resin additive comprising a diamine compound, wherein: The diamine compound is represented by the following formula (I): H2N—R1—NH2 (Ⅰ) In formula (I), R 1 The total number of carbon atoms is C 14 ~C 28 The alkylene group is a branched alkylene group having one methyl group or ethyl group.

2. The resin additive according to claim 1, characterized in that: In formula (I), R 1 The main chain of the alkylene group has C 2n carbon atoms, wherein n is 7 to 14.

3. The resin additive according to claim 1, characterized in that: The diamine compound is 7-ethyltetradecanediamine or 8-ethyloctadecanediamine.

4. A resin composition, characterized in that: Containing a resin and the resin additive according to claim 1.

5. A resin composition, characterized in that: A resin comprising one or more monomer compounds and the resin additive according to any one of claims 1 to 3.

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