JPS6163647A - Biscyanamide and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is S, O, SO2, or CO; Y is S or O; n is 0 or 1). EXAMPLE: 4,4'-Bis(4-cyanamidophenylthio)diphenyl sulfide. USE:Useful as a resin for laminated board, casting material, paint, varnish for glass-fiber reinforcement, etc. PREPARATION:The objective compound of formula I can be prepared by reacting the aromatic amine of formula II with cyanogen halide in the presence of a base (e.g. CaCO3, Na2CO3, etc.) in a solvent such as dimethylacetamide- water mixture, formamide-water mixture, etc. at -10-+20 deg.C. The amount of the cyanogen halide is 2.0-1.0mol per 1mol of the compound of formula II, and that of the base is 1-2mol per 1mol of the diamine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to biscyanamide useful as a resin used in laminates, casting materials, paints, glass fiber reinforcing panels, etc., and a method for producing the same.

[Conventional technology]

In recent years, as rotating electrical equipment, single-chip wiring circuit boards, etc. have become larger in capacitance, smaller and lighter, thermosetting resins with extremely high heat resistance are being used as insulating materials. It is requested. Also, conventionally,
Research is being conducted extensively on various heat-resistant polymer materials, but in the case of heat-resistant polymer materials for laminates, paints, and impregnations, it is important that no voids remain during the molding process. This is one of the requirements. Addition-curing heat-resistant polymer materials are known as materials that meet this requirement, and have been widely studied.

As such addition-curable heat-resistant polymer materials, addition-polymerizable polyimide resins such as bismaleimide resins as disclosed in Japanese Patent Publication No. 46-23250 have been proposed. This bismaleimide resin is cured by addition of diamines to double bonds and polymerization of double bonds, resulting in a cured resin that provides a high degree of heat resistance. However, bismaleimide resin has many points to be improved, such as slow curing speed and long curing time.

In addition, cyanamide group (-NH--C5i
N) is known (German patent 2,03
No. 3,696). That is, there is an aromatic biscyanamide compound obtained by reacting an aromatic diamine such as diaminodiphenylmethane with a cyanide halide. When these aromatic biscyanamide compounds are heated at 100 to 200° C., the cyanamide groups are easily tricyclized to give a cured product having an immelamine ring, and the obtained cured product has excellent heat resistance. However, the obtained cured product is inferior in mechanical properties such as flexibility. In addition, molding is difficult because the curing temperature and melting point are close to each other or opposite to each other.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a compound that can be heat-cured under mild conditions and has excellent heat resistance, flexibility, and moldability.

[Specific measures to solve the problem]

The above object is achieved by the general formula (1) [wherein xFis, o, SO- or CO; Y is S or O]. n is an integer from 0 to 1] This is achieved by using a biscyanamide represented by:

(Manufacture of biscyanamide) The biscyanamide represented by the above formula (1) can be obtained by reacting the aromatic diamine represented by the formula (1) with a cyanide halide in the presence of a base.

[xXy and n in the formula are the same as in formula (1)] (Aromatic diamine) Examples of the aromatic diamine compound represented by the above formula (1) include 4,4'-bis(4-aminophenyl) Thio)
diphenylsulfi)', 4.4'-his(4-aminophenylthio)diphenyl ether, 4.4'-bis(4-aminophenylthio)diphenylsulfone, 4.
4'-His(4-aminophenylthio)benzophenone, 414'-bis(4-aminophenoxy)diphenyl sulfide, 4.4'-bis(4-aminophenoxy)
Diphenyl ether, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 4,4'-bis(4-aminophenoxy)benzophenone, 1,4-bis(4-
Examples include aminophenylthio)benzene.

(cyanide halide) Halogenated cyanide, chloryanide, fu.

Larel using CffA Cyanka. The amount of cyanogen halide to be used is suitably in the range of 2.0 to 10 mol per 1 mol of the diamine compound represented by the above general formula 1. Preferably, the amount is 2.5 to 4.0% per mole of the diamine compound.
0 mol used.

(Base) As the base used as a deoxidizer, an alkali metal or alkaline earth metal carbonate, bicarbonate, or tertiary amine can be used. Preferably, alkali gold,
Metal or alkaline earth metal-charcoal salts are used. For example, CaCO3, Na2COa, K2COs, etc. The amount used is 1 to 2 moles per mole of diamine.

The solvent may be inert to cyanogen halides, and may be, for example, alcohols, ketones, ethers, aprotic dipolar solvents, or a mixed solvent system of these solvents and water. Preferably, a dimethylacetamide-water mixed solvent or a formamide-water mixed solvent is used.

Further, although the reaction temperature and reaction time are not particularly limited, it is desirable to carry out the reaction at a temperature below the boiling point of the cyanogen halide.

Preferably, the reaction is carried out at a temperature range of -10°C to 20°C for 1 to 5 hours.

(Biscyanamide) Examples of the aromatic biscyanamide compound represented by formula (1) of the present invention include 4,4'-bis(4-cyanamidophenylthio)diphenyl sulfide, 4'4'-bis(4-cyanamide) phenylthio) diphenyl ether,
4e4'-bis(4-cyanamidophenylthio)diphenylsulfone, 4.4'-bis(4-cyanamidophenylthio)benzophenone, 4°4'-bis(4-cyanamidophenoxy)diphenylsulfide, 4*4'-bis (4-cyanamidophenoxy)diphenyl ether,
Examples include 4.4'-bis(4-cyanamidophenoxy)diphenylsulfone, 4.4'-bis(4-cyanamidophenoxy)benzophenone, and 1,4-bis(4-cyanamidophenylthio)benzene.

This aromatic biscyanamide compound is heated at a temperature of 100 to 200℃.
It can be easily cured by heating. The resulting cured product also provides an insoluble, infusible, heat-resistant polymeric material with excellent heat resistance, chemical resistance, mechanical properties, and the like.

The novel aromatic biscyanamide compound of the present invention is particularly useful as a varnish for impregnation, lamination, adhesives, films, and prepregs, as well as in organic solvent solutions (varnishes). Furthermore, it can also be made into a molding resin by adding inorganic brightening agents, flame retardants, deterioration inhibitors, pigments, and the like.

Next, the present invention will be illustrated in more detail with examples.

All parts in the text are by weight.

The examples do not limit the scope of the invention.

Example 1 Capacity 11 equipped with stirring device, dropping funnel and thermometer
32 parts (0.3 moles) of cyanogen bromide were added to 10 g of N,N'-dimethylacetothymide (DMAe) in a five-ring flask.
The pellets are dissolved in a mixed solvent of 0 parts and 40 parts of water, further added with 10 parts (o, t mol) of calcium carbonate, and kept at a temperature below 5°C.

Next, 4,4'-his(4-aminophenylthio)
Diphenylsulfide 43 parts (o, t mol) t-DMA
The resulting solution was added dropwise to the cyanogen bromide solution with stirring at a temperature of 5° C. or lower. After that, 5
The reaction was carried out for 2 hours at a temperature of ~10°C.

After the reaction was completed, the reaction solution was filtered, and the solution F was poured into 10 times the amount of water to precipitate the reaction product, which was filtered, washed, and dried under reduced pressure (day and night).

Product yield was 47 parts. When this product was analyzed by IR spectrum and NMR spectrum, it was found that 4+
It was confirmed to be 4'-bis(4-cyanamidophenylthio)diphenyl sulfide. The yield was 97%. The IR spectrum is shown in FIG. Further, the melting point measured by DSC was 145°C.

Example 2 Completely the same as Example 1 except that 47 parts of 4.4'-bis(4-aminophenylthio)diphenylsulfone was used instead of K4.4'-bis(4-aminophenylthio)diphenylsulfide. The reaction was carried out to obtain 49 parts of product.

When this product was analyzed by IR spectrum and NMR spectrum, it was confirmed that it was 4,4'-bis(4-cyanamido7elthio)diphenylsulfone. The yield was 95%. The IR spectrum is shown in FIG. Moreover, the melting point was 100°C.

Example 3 43 parts of ic4.4'-bis(4-aminophenylthio)benzophenone was used instead of 4.4'-bis(4-aminophenylthio)diphenyl sulfide, and 10.6 parts of sodium carbonate was used instead of calcium carbonate. The reaction was carried out in exactly the same manner as in Example 1 except that 46 parts of the product was obtained.

When this product was analyzed by IR spectrum and NMR spectrum, it was confirmed that it was 4,4'-bis(4-cyanamidophenylthio)benzophenone.

The yield was 95%. The IR spectrum is shown in Figure 'g3. Further, the melting point was approximately 150°C.

Example 4 Using 42 parts of 4.4'-bis(4-aminophenylthio)diphenyl ether instead of 4.4'-his(4-aminophenylthio)diphenyl sulfide, N.N.
A tail reaction was carried out in exactly the same manner as in Example 1, except that 100 parts of N,N'-dimethylformamide was used instead of '-dimethylacetamide, to obtain 546 parts of the product.

When this product was analyzed by IR spectrum and NMR spectrum, it was confirmed that it was 4.4'-bis(4-cyanamidophenylthio)diphenyl ether. The yield was 98%. The IR spectrum is shown in FIG. Moreover, the melting point was 125°C.

Example 5 32.4 parts of 4,4'-di(4-aminophenylthio)benzene was used in place of 4.4'-bis(4-aminophenylthio)diphenyl sulfide, and cyanogen chloride was used in place of cyanogen bromide. The reaction was carried out in exactly the same manner as in Example 1, except that 19 parts were used. The product was 36 parts.

When the product was analyzed using IR spectrum and NMR spectrum, it was confirmed that it was 4,4'-di(4-cyanadophenylthio)benzene. Yield is 97%
Met. Moreover, the melting point was about 130°C.

Example 6 40 parts of 4.4'-bis(4-aminophenoxy)benzophenone was used instead of 4.4'-bis(4-aminophenylthio)diphenyl sulfide, and 2 parts of DM Ac was used.
The reaction was carried out in exactly the same manner as in Example 1 except that 44 parts of the product was obtained.

When the obtained product was analyzed by IR spectrum and NMR spectrum, it was confirmed to be 4,4'-bis(4-cyanamidophenoxy)benzophenone. The yield was 99%. FIG. 5 shows the IR spectrum. Moreover, the melting point was 145°C.

Application Example 1 When each of the novel aromatic biscyanamide compounds obtained in Examples 1 to 6 was heated at 180 to 200°C for 2 hours, an insoluble and infusible cured product was obtained.

In addition, when differential thermal analysis (DSC) was performed on these new biscyanamide compounds, all of the compounds showed 120
A sharp exothermic peak was observed around ~180°C. At this point, a cyclization and trimerization reaction of the cyanamide group occurs, and the novel aromatic biscyanamide compound of the present invention is considered to form a crosslinked network. In the IR spectra before and after heating, 2 20 (1
The absorption of m almost disappeared by heating, and a new absorption believed to be derived from the chemitine structure of the inomelamine ring was observed at 1620.

Application Example 2 The novel aromatic biscyanamide compounds obtained in Examples 1 to 6 were treated with a mixed solvent of methyl ethyl ketone and cellosolve (Example 1.2.4.5) or an N,N'-dimethylacetamide solvent ( Example 3.6) was dissolved to prepare a festival with a solid content of 50%.

These fests were applied on a glass plate and heated to 50°C and 70°C.
, 1 hour each at 90°C, then dried at 120°C and 150°C.
The mixture was heated at 200°C and 200°C for 2 hours each. In both cases, films with good flexibility were obtained.

The heating loss characteristics (T GA) of the six types of films listed in b were measured in air at a heating rate of 10°C/min. It was found that the temperature drop was 480° C. or higher, and that the material had extremely excellent heat resistance. .

Application Example 3 The electrical properties of the film of the novel aromatic biscyanamide compound obtained in Example 4 were measured. Silver electrodes with a diameter of 1 ctn were attached to both sides of the film by vapor deposition to prepare a measurement sample, and the dielectric constant, dielectric loss, and resistivity were measured at a frequency of 100 KHz.

Dielectric constant 3.96 Dielectric loss 0.0044 Resistivity z x io”Ω・α Application example 4 The novel aromatic biscyanamide compound obtained in Example 4 was dissolved in a 1:1 mixed solvent of acetone and cellosolve, Furthermore,
A preliminary reaction was carried out at 60° C. for about 2 hours to prepare a 50% solid content festival.

The above cloth was impregnated with aminosilane-treated glass cloth and dried at 80°C for 10 minutes until the amount of resin impregnated was about 45%.
% prepreg was created.

Next, 8 sheets of each prepreg were stacked and a pressure of 20 to 40 Kf was applied.
/i, laminated and bonded at a temperature of 100 to 120°C, and then cured for 2 hours each at 150°C and 180°C to a thickness of about 1.6 w
A laminate of m was prepared. The obtained laminate had no internal bubbles or peeling, and had excellent surface smoothness.

[Brief explanation of drawings]

1, 2, 3, 4 and 5 are IR spectra of biscyanamide obtained in practical examples of the present invention.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is S, O, SO_2 or CO; Y is S or O. n is an integer of 0 or 1] A biscyanamide represented by: 2) A method for producing biscyanamide represented by the following formula by reacting a diamine represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ with cyanogen halide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is S, O, SO_2 or CO; Y is S or O. n is an integer of 0 or 1. ]