JPH05331116A - Diamine and its production - Google Patents

Abstract

PURPOSE:To obtain a new diamine, useful as a constituent monomer for polyamides, excellent in heat resistance and mechanical strength while having good processability and reactivity with low hygroscopicity and capable of producing curable polyimides at a low cost. CONSTITUTION:The diamine is expressed by formula I [X is reactive monovalent organic group, preferably formula II or III (R is H, CH2 CH2CH3, or aromatic group); Z is H, CH3 OCH3 phenyl, F or Cl], e.g. 1,3-diaminophenyl propargyl ether. This compound can be produced by (a) adding a compound of the formula Y-X (Y is halogen) into a solution containing a compound expressed by formula IV dissolved therein and providing an ether, (b) reducing a compound expressed by formula V or (c) deprotecting a compound expressed by formula VI (T is organic group which may have F). Furthermore, this compound has a thermally or optically reactive group and the resultant cured product has extremely high industrial value in wide uses such as laminated boards, heat-resistant coatings and molding materials.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diamine, more specifically, a diamine which is a constituent unit of a polymer or an oligomer and is suitable for synthesizing a resin having a low hygroscopicity and a thermosetting property, and its production. Regarding the method.

[0002]

2. Description of the Related Art Organic amines having a crosslinkable group are
It has been conventionally used as a constituent monomer of polyimide or polyamide having thermosetting property or photosensitivity. Recently, for example, a thermosetting polyimide in which 3-aminophenylacetylene is used as a primary amine and whose end is terminated is put on the market as "Thermid (trade name, manufactured by Kanebo NSC)" [Hughes Aircraft, JP 50-
5348]]. Several methods for the synthesis of 3-aminophenylacetylene used herein [eg,
USP 4,125,563] is known, but each has a problem that the synthetic route is long and the synthetic reagent is expensive. Further, a thermosetting polyimide in which the end is terminated by using propargylamine as a primary amine has also been proposed [Ube Industries, Ltd., JP-A-2-28492.
3, JP-A-3-174427]. However, it is known that the thermal reaction initiation temperature of a propargyl group is as high as 250 ° C., and an imide oligomer using this as a reactive group also has a high curing temperature and is inferior in terms of processability [Polymer Engineering Science ( Polym. Eng. Sc
i. ), 22 (1), 9-14 (1982)].

Further, it has been reported that a phenylacetylene group is introduced into the side chain of a divalent organic diamine.
[ACS Proceedings, 33 (1), 914 pages (199
2), Journal of Macromolecular Science Chemical Edition, A32 (8 & 9), 1
117 pages (1984)]. However, it has been a problem that they have a high processing temperature.

Various aromatic propargyl ethers have been proposed as a system utilizing a thermosetting reaction of a propargyl group [eg, Dow Chemical, JP-A 2-8].
5275, The European Polymer Journal (Eu
r. Polym. J. ), 27 (11), 1279-1
287 (1991)]. Aromatic propargyl ether is obtained by reacting with various phenols and halogenated propargyl halide in an aqueous caustic solution in the presence of a phase transfer catalyst. It is known that propargyl ether is polymerized via chromene by applying heat to produce a thermosetting polymer, and the cured product thereof has low hygroscopicity. However, these aromatic propargyl ethers are, for example, those obtained by converting both ends of bisphenol A into propargyl ether, and the polymer thereof has a relatively low molecular weight, so that the cured product is inferior in heat resistance and mechanical strength.

[0005]

An object of the present invention is to provide a novel diamine in which propargyl ether is introduced into the side chain of the diamine component. By using this diamine as a constituent monomer of an imide oligomer, for example, it is possible to provide a highly reactive polyimide having excellent heat resistance and mechanical strength while having good processability and low hygroscopicity. You can

[0006]

The inventors of the present invention have arrived at the present invention as a result of intensive investigations in order to solve these technical problems in view of such circumstances.

That is, the first aspect of the present invention is the general formula (1)

[0008]

[Chemical 9]

(Wherein X is a monovalent organic group having thermal crosslinking reactivity, Z is H, Me, OMe, Ph, F or Cl)
The second diamine of the present invention is a diamine represented by the following general formula (3):

[0010]

[Chemical 10]

(In the formula, Z is H, Me, OMe, Ph, F
Or Cl) in a solution of diaminophenol represented by the following general formula (4)

Y-X (4)

(Wherein Y is halogen and X is a monovalent organic group having reactivity), and an etherification is added to the above method for producing a diamine,

The third aspect of the present invention is to formula (5)

[0015]

[Chemical 11]

(In the formula, Z is H, Me, OMe, Ph, F
Alternatively, Cl and X are dinitrophenol derivatives represented by a monovalent organic group having a reactivity).

The fourth aspect of the present invention is to formula (6)

[0018]

[Chemical 12]

(In the formula, Z is H, Me, OMe, Ph, F
Alternatively, Cl and X may be a reactive organic group, and T may be an organic group having F. And a method for producing a diamine as described above, characterized in that the diaminophenol derivative represented by (4) is deprotected. In the present invention, Me, OMe, and Ph are CH ₃ ,
Represents OCH ₃ and phenyl.

The method for producing the diamine of the present invention will be described. Here, three kinds of methods are specifically described, but the diamine can be synthesized in good yield by any of the methods.

In the first method, the diaminophenol represented by the general formula (3) is dissolved in an alkaline aqueous solution in the presence of a phase transfer catalyst, and the organic halogen represented by the general formula (4) is added to the solution. Compound little by little,
A diaminophenol derivative is obtained. The reaction temperature at this time is preferably in the range of -15 to 120 ° C, more preferably 0 to 100 ° C, and further preferably 0 to 60 ° C. The reaction time is preferably 1 to 24 hours.

In the second method, the dinitrophenol derivative represented by the above general formula (5) is reduced to an amino group with an appropriate reducing agent in an aqueous solution and / or an organic solvent. There is no particular limitation on the reducing agent used here, and a general catalyst can be used. For example, 13 of “New Experimental Chemistry Course, Volume 14, Synthesis and Reaction of Organic Compounds (III)” edited by The Chemical Society of Japan is used.
Any one can be used as long as it can be used for the reduction reaction of the nitro group described on pages 33 to 1335. Here, the tin chloride / hydrochloric acid system is preferable from the viewpoint of cost and easy handling of the reaction. The temperature and the reaction time are not particularly limited, but in the above example, the reaction temperature is -15 to
The range of 120 ° C. is suitable, and more preferably 0 to 10
It is in the range of 0 ° C. The reaction time is preferably 1 to 24 hours.

The dinitro compound which is the precursor of the diamine of the present invention can be synthesized as follows. That is,
Dinitrophenol represented by the above general formula (7)

[0024]

[Chemical 13]

(Wherein Z is an alkyl residue such as H, Me and OMe, an aromatic residue such as Ph, or a halogen residue such as F and C1) is dissolved in an alkaline aqueous solution in the presence of a phase transfer catalyst. Then, the organic halide represented by the general formula (4) is added dropwise to the solution little by little to obtain the dinitrophenol derivative represented by the general formula (5). The reaction temperature at this time is preferably in the range of -15 to 120 ° C, more preferably 0 to 100 ° C, and further preferably 0.
-60 ° C is preferred. The reaction time is preferably 1 to 24 hours.

The third method is to convert the amide group into an amino group by deprotecting the amide compound represented by the general formula (6) in an aqueous solution and / or an organic solvent. As the deprotecting agent used here, a general catalyst can be used without any particular limitation. For example, pp. 398 of "Handbook of Organic Synthesis Experimental Method" edited by the Society of Organic Synthesis Chemistry, or "New Experimental Chemistry Course, Synthesis of Organic Compounds" edited by Maruzen And reaction (5) ”of 2555
Any material that can be used in the acetyl group elimination method described on page 2556 can be used. Here, the boiling treatment in hydrochloric acid is preferable from the viewpoint of cost and easy handling of the reaction. The temperature and the reaction time are not particularly limited, but in the above example, the reaction temperature is -15 to 15
The range of 0 ° C is suitable, and more preferably 0 to 130 ° C.
Is the range.

The amide compound which is the precursor of the diamine of the present invention can be synthesized as follows. That is, the general formula (8)

[0028]

[Chemical 14]

(In the formula, X is a reactive organic group, Z
Is an alkyl residue such as H, Me and OMe, an aromatic residue such as Ph, a halogen residue such as F and C1, and R is Me, Et and T
Is an organic group which may have F), and an amidephenol represented by the formula (4) is dissolved in an alkaline aqueous solution in the presence of a phase transfer catalyst, and the organic halide represented by the general formula (4) is added to the solution. Drop it little by little to obtain the above general formula (6).
An amide compound represented by The reaction temperature at this time is
The range of −15 to 120 ° C. is suitable, more preferably 0 to 100 ° C., and further preferably 0 to 60 ° C. The reaction time is preferably 1 to 24 hours.

The dinitrophenol used in the present invention is represented by the above formula (7), and more specifically, 3,5-dinitrophenol or 2,4-dinitrophenol is preferable from the viewpoint of the balance of various characteristics. is there. The diaminophenol used in the present invention is represented by the above formula (3). More specifically, from the viewpoint of the balance of various characteristics, 3,5
-Diaminophenol or 2,4-diaminophenol are preferred.

The organic halide used in the present invention is represented by the above formula (4), and more specifically, propargyl halide or allyl halide is preferable from the viewpoint of balance of various characteristics. The propargyl halide is preferably propargyl chloride or propargyl bromide, and the allyl halide is preferably allyl chloride or allyl bromide.

The base catalyst used in the reaction for producing the procargyl ether of the present invention is not particularly limited and a general alkaline aqueous solution can be used, but potassium hydroxide, sodium hydroxide and carbonic acid are preferred. An aqueous solution of potassium or a mixture thereof is used.

In the propargyl ether formation reaction of the present invention, a phase transfer catalyst is used to obtain an ether product in high yield. As the phase transfer catalyst used here, a general phase transfer catalyst can be used, but tetraalkylated ammonium halide and tetraalkylated phosphonium halide are preferably used. The halide is iodide, bromide, chloride or a mixture thereof.

Further, an organic solvent can be used together with the aqueous solution in the reaction solution. The organic solvent used here together is preferably a general-purpose organic solvent such as toluene, benzene, chloroform or acetone. The solution concentration of the reaction solution is 5-50%
Is preferable, and more preferably in the range of 10 to 30%. If it exceeds this range, the reaction may not be sufficiently carried out or a reaction by-product may be easily produced.

[0035]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples, and the present invention is within the scope not departing from the gist thereof.
Various modifications, improvements, and changes can be made based on the knowledge of those skilled in the art.

Example 1 Synthesis of 1,3-diaminophenylpropargyl ether A 300 ml three-necked flask was equipped with a three-way cock, a Dimroth condenser, a dropping funnel and a searum cap. 15.41 g of 1,3-diaminophenol (0.
1 mol) and 4 g (0.1 mol) of sodium hydroxide to 10
An aqueous solution dissolved in 0 ml of water and 3.22 g (0.01 mol) of tetrabutylammonium bromide were charged and mixed. Next, 11.90 g (0.1 mol) of propargyl bromide
Was charged into a dropping funnel and added dropwise to the reaction system at room temperature over 10 minutes, and then reacted under reflux for 4 hours. After the reaction, the reaction solution was extracted with methylene chloride, the organic layer was washed with water, and then dehydrated and filtered with anhydrous sodium sulfate. When the solvent was distilled off with a rotary evaporator, 1
9.02 g (yield; 98%) of brown oil was obtained. This was heated at 180 ° C / 0.5 using a ball tube vacuum distillation device.
Distillation with Torr gave 18.2 g (yield; 90%) of 1,3-diaminophenylpropargyl ether as an orange oil.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3390, 3300, 28
60, 2720, 2620, 2120, 1600, 15
00, 1450, 1340, 1290, 1180, 11
60, 1100, 1040, 1000, 960, 93
0, 840, 770, 690 ¹ H-NMR (CDCl ₃ , TMS, ppm) δ = 2.19 (tr, J = 2.4 Hz, 1H), 3.8
2 (d, J = 2.4 Hz, 2H), 4.23 (bs, 4
H), 6.03 to 7.27 (m, 3H)

Reference Example 1 Synthesis of 2,4-diacetamide phenol A 300 ml three-necked flask was equipped with a 50 ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure.
The atmosphere was replaced with nitrogen. 200 ml of Tetrahydrofuran (TH
F) and 124.2 g (0.1 mol) of 2,4-diaminophenol were charged to the reaction system. 180 mol of acetic anhydride was added from the dropping funnel in about 1 hour while paying attention to reflux. The reaction was carried out under reflux for 4 hours, and the mixture was allowed to stand overnight, and the precipitated crystals were separated by filtration and dried to give 20.21 g (yield; 9
(5.2%) 2,4-diacetamide phenol was obtained.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3500, 3300, 29
60, 2880, 1880, 1650, 1610, 15
60, 1510, 1450, 1370, 1270, 12
40, 1180, 1030, 840, 810, 660,
630

Reference Example 2 Synthesis of 2,4-diacetamide phenyl-1-propargyl ether A 300 ml three-necked flask was equipped with a 50 ml dropping funnel, a three-way cock, and a seam cap, and dried under reduced pressure.
The atmosphere was replaced with nitrogen. 20.82 g (0.1 mol) of Reference Example 1
3.24-g with 2,4-diacetamide phenol obtained in
After charging (0.01 mol) of tetra-n-butylammonium bromide into the reactor, 4 g (0.1 mol)
A solution of sodium hydroxide in 130 ml of water was added. After raising the reaction temperature to 50 ° C. to dissolve 2,4-diacetamide phenol, 13.0 from a dropping funnel.
About 3 g of 9 g (0.11 mol) of propargyl bromide
Added over 0 minutes. After reacting at 50 ° C for 4 hours,
The mixture was stirred overnight at room temperature. The precipitated crystals were filtered out and recrystallized from ethanol. 24.1 g (95.5%) of 2,
4-Diacetamidophenyl-1-propargyl ether was obtained.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3500, 3300, 29
60, 2880, 1880, 1650, 1610, 15
60, 1510, 1450, 1370, 1270, 12
40, 1180, 1030, 840, 810, 660,
630 ¹ H-NMR (CDCl ₃ , ppm) δ = 2.12 (s., 6H), 2.48 (tr., 1)
H), 4.61 (d., J = 2.4 Hz, 2H), 6.
77-7.6 (m., 3H), 7.85 (br.s.,
2H)

Example 2 Synthesis of 2,4-diaminophenyl-1-propargyl ether A 50 ml dropping funnel, a three-way cock, and a seam cap were attached to a 300 ml three-necked flask and dried under reduced pressure.
The atmosphere was replaced with nitrogen. 7.38 g (0.03 mol) of Reference Example 2
The 2,4-diacetamide phenyl-1-propargyl ether obtained in 1. and 150 g of 3N hydrochloric acid were charged into the reaction system,
The reaction was carried out under reflux for 4 hours. After the reaction, the reaction solution was poured into a saturated sodium carbonate solution and extracted from methylene chloride. The organic layer was dehydrated and filtered, and the solvent was distilled off. By recrystallizing the precipitated crystal from ethanol, 6.58
g (yield; 94.7%) of 2,4-diaminophenyl-
1-Propargyl ether was obtained.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60, 990, 905, 860, 780, 735, 69
0 ¹ H-NMR (CDCl ₃ , ppm) δ = 2.5 (tr., 1H), 3.5 (br.s., 4)
H), 4.75 (d., J = 1.2 Hz, 1H), 6.
7 (m., 3H)

Reference Example 3 Synthesis of 2,4-dinitrophenyl-1-allyl ether A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock and a seal cap, dried under a reduced pressure and replaced with argon. 8.0 g (0.2 mol) of sodium hydroxide was dissolved in 200 ml of water and charged into the reactor. After adding 27.82 g (0.2 mol) 2.4-dinitrophenol and 6.45 g (0.2 mol) tetra-n-butylammonium bromide, 24.79 g (17.1 ml, 0.2 mol) was added from the dropping funnel. Allyl bromide was added over about 30 minutes, the reaction was carried out at 80 ° C. for 4 hours, and then stirring was continued overnight at room temperature. The precipitated crystal was filtered and recrystallized from toluene. 30.9 g
(Yield; 94.2%) of 2,4-dinitrophenyl-1
-Allyl ether was obtained.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60, 990, 905, 860, 780, 735, 69
0 ¹ H-NMR (chloroform-d, ppm) δ = 3.8 (d., J = 2.0 Hz, 2H), 5.1
(M., 2H), 5.9 (m., 1H), 7.9
(M., 3H)

Example 3 Synthesis of 2,4-diaminophenyl-1-allyl ether A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock and a seal cap, dried under reduced pressure and replaced with argon. 23.67 g (0.14 mol)
2,4-dinitrophenyl-1-allyl ether obtained in Reference Example 3 and 270 ml of dioxane were charged into a reaction vessel. 260.49 g (1.16 mol) of tin chloride and 27
0 ml of concentrated hydrochloric acid was added dropwise over 2 hours under ice cooling. The reaction solution was stirred under ice cooling for 1 hour and then 1 liter of 10
It was dropped into a wt% sodium hydroxide aqueous solution. After filtering the precipitated aqueous tin, the filtrate was extracted from methylene chloride. After dehydration and filtration, the solvent was distilled off and the precipitated crystals were separated by filtration and recrystallized from toluene. 21.62 g (yield; 93.2%) of 2,4-diaminophenyl-1-allyl ether was obtained.

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60, 990, 905, 860, 780, 735, 69
0 ¹ H-NMR (chloroform-d, ppm) δ = 3.5 (tr., 1H), 4.2 (br.s., 4)
H), 5.15 (d., J = 1.2 Hz, 1H), 6.
7 (m., 3H)

Application Example A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, dried under reduced pressure, and replaced with argon. After charging 5.77 g (0.01 mol) of bisphenol A bis (trimellilate) dianhydride and 6.44 g (0.02 mol) of benzophenone tetracarboxylic dianhydride into the reactor, 200 ml
Distilled DMF (dried over calcium hydride) was added. From the dropping funnel, dissolved in 50 ml of DMF 1
6.39 g (0.031 mol) of 2,4-diaminophenyl-1-propargyl ether obtained in Example 2 was added dropwise. The mixture was stirred at 80 ° C for 2 hours. After the reaction temperature was returned to room temperature, the obtained polyamic acid was chemically dehydrated and cyclized by adding 11 ml of acetic anhydride and 10 ml of pyridine. After the reaction, the reaction solution was poured into 1 liter of methanol to precipitate the polyimide. It was filtered under reduced pressure with an aspirator and dried in vacuum at 80 ° C. for 48 hours to obtain a polyimide as a pale yellow powder in a yield of 25.2 (yield: 86.3%). Reduced viscosity is 1.05dl / g
(0.495 g / dl, 23 ° C, m-cresol).

[Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 17
80, 1750, 1700, 1620, 1600, 15
80, 1495, 1450, 1350, 1295, 12
20, 1160, 990, 905, 860, 780, 7
35,690

220 ° C. using 8.3 g of polyimide
・ 20 minutes, 250 ° C. ・ 30 minutes, 270 ° C. ・ 1 hour, pressed under contact pressure to have a density of 1.39 g / cm ³ 12
A casting plate of mm (width) × 12 cm (length) × 3.4 mm (thickness) was obtained. This casting plate has a bending strength of 58.8 Kg / mm ² and 3
It had a flexural modulus of 15 kg / mm ² and an impact strength of 35 kg · cm / cm ² . From the measurement of dynamic viscoelasticity, the glass transition temperature (Tg) was 256 ° C. Also, 250 ℃, 2
After 4 hours of after cure, Tg was 2
The temperature was 95 ° C., and the heat resistance was improved by post-curing of the reactive group. Moisture absorption rate is 0.27% (C-96 / 2
0/65).

Comparative Application Example Using 9.2 g of a commercially available imide type thermosetting oligomer, 220 ° C. for 20 minutes, 250 ° C. for 30 minutes, 270 ° C.
Pressed under contact pressure for 1 hour, density 1.35g / cm ³
12mm (width) × 12cm (length) × 3.5mm (thickness)
To obtain a casting plate. The casting plate, 38.2Kg / flexural strength of mm ² and 261 kg / mm ² in bending elastic modulus and 18 Kg · cm / cm
It was a resin having an impact strength of ² and a glass transition temperature (Tg) of 212 ° C. The moisture absorption rate is 0.75% (C-96 /
20/65).

[0052]

INDUSTRIAL APPLICABILITY The diamine having a reactive group due to heat or light according to the present invention has a high heat resistance and a curable polyimide having a low hygroscopic property at low cost by using, for example, as a constituent monomer of polyimide. Can be provided. Further, the obtained cured product can provide a material having an extremely high industrial value in a wide range of applications such as a laminated plate, a heat-resistant paint and a molding material, and its utility is great.

Claims (8)

[Claims] 1. A compound represented by the general formula (1): (In the formula, X is a monovalent organic group having reactivity, Z is H, M
e, OMe, Ph, F or Cl). 2. X is a compound represented by the general formula (2): The diamine according to claim 1, wherein R is H, CH ₃ , CH ₂ CH ₃ or an aromatic group. 3. A compound represented by the following general formula (3): (In the formula, Z is H, Me, OMe, Ph, F or Cl)
An organic halide represented by the following general formula (4) Y-X (4) (wherein Y is halogen and X is a monovalent organic group having reactivity) in a solution in which diaminophenol represented by The method for producing a diamine according to claim 1, further comprising adding ether. 4. X is a compound represented by the general formula (2): The method according to claim 3, wherein R is H, CH ₃ , CH ₂ CH ₃ or an aromatic group. 5. The following general formula (5): (In the formula, X is a monovalent organic group having reactivity, Z is H,
The method for producing a diamine according to claim 1, wherein a ditonilophenol derivative represented by Me, OMe, Ph, F or Cl) is reduced. 6. X is a compound represented by the general formula (2): The method according to claim 5, wherein R is H, CH ₃ , CH ₂ CH ₃ or an aromatic group. 7. The following general formula (6): (In the formula, Z is H, Me, OMe, Ph, F or Cl,
X is an organic group having reactivity, T is an organic group and may have F. The method for producing a diamine according to claim 1, wherein the diaminophenol derivative represented by (4) is deprotected. 8. X is a compound represented by the general formula (2): (Wherein R is H, CH ₃ , CH ₂ CH ₃ or an aromatic group).