JPH0324042A - Aromatic allylamine compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (Ar is bivalent aromatic residue) R1 to R4 are allyl or H; at least one of R1 to R4 is allyl). EXAMPLE:1,3-Bis(4-aminophenoxy)benzene. USE:A raw material for thermosetting polyimide resin having excellent processability, heat resistance, mechanical properties and adhesivity. PREPARATION:The objective compound of formula can be produced by the dehydrohalogenation reaction of an aromatic diamine compound with an allyl halide compound. The aromatic allylamine compound is liquid at room temperature or thereabout and is easily miscible with polymaleimide compounds.

Description

Detailed Description of the Invention Industrial Field of Application The present invention relates to a novel aromatic allylamine compound, and more specifically to a novel thermosetting polyimide with excellent processability, heat resistance, mechanical properties, and adhesive properties. This invention relates to aromatic allylamine compounds used as raw materials for resins.

<Prior Art> Thermosetting resins are used as casting, impregnating, laminating, and molding materials for various electrical insulation materials, structural materials, and the like.

In recent years, the conditions for using materials in each of these applications have tended to become stricter, and in particular, the heat resistance of materials has become an important characteristic.

Conventionally, epoxy resins with improved heat resistance and thermosetting polyimide resins have been used for such purposes.

Problems to be Solved by the Invention Although heat-resistant epoxy resins have excellent molding processability, they are insufficient in high heat resistance such as mechanical properties at high temperatures, electrical properties, and long-term heat deterioration resistance. Bismaleimide resins have been proposed in order to improve these problems, but although their cured products alone exhibit high heat resistance, they have poor toughness and are of little practical use, and various copolymerization components have also been proposed.

A resin composition consisting of aromatic diamine and maleimide is both solid at room temperature, and the mixture melts only under high d conditions, and the viscosity of the melt is high, making casting and impregnation difficult. be. In addition, due to the low curing reactivity, high temperature and long molding conditions were required to obtain sufficient heat resistance, and furthermore, there were problems with the cured physical properties and heat deterioration resistance of the obtained cured product during high hoisting. .

Furthermore, resin mixtures consisting of alkenylphenol and/or alkenylphenol ether and maleimide have poor adhesive properties and have problems in use in impregnation, lamination, etc.

Means for Solving the Problems> Against this background, the present inventors have made extensive efforts to find compounds that can be copolymerized with polymaleimide resins that provide resin compositions with excellent heat resistance and adhesive properties, and excellent processability. As a result of investigation, it was discovered that a new allylamine compound having a specific structure satisfies the above-mentioned purpose, and the present invention was completed.

That is, the present invention provides the following general formula CI] [wherein Ar represents a divalent aromatic residue, R. , R
2R. ,R. each independently represents an allyl group or hydrogen; R. , R2, R. and at least one of R4 is an allyl group. ] This is an aromatic allylamine compound represented by:

The aromatic allylamine compound of the present invention can be easily synthesized by various methods. For example, there is a method using a dehydrohalogenation reaction between an aromatic diamine compound and an allyl halide compound.

As an example of an aromatic diamine used as a raw material for this reaction, in formula [I), R. , R2. R. and R,
The diamine compound has a structure in which all hydrogen atoms are present and the Ar moiety is, but is not limited to these. Note that there is no problem even if the aromatic nucleus has a substitution Go.

Particularly preferred is Ar, It is a thing.

Furthermore, R. , R2, R, and R4 are as described above, that is, the aromatic allylamine compound of the present invention is a compound having 1 to 4 allyl groups per molecule. Each may be used alone or as a mixture. When used for copolymerization with the above-mentioned polymaleimide compound, ■ an average of 1. Allylated aromatic allylamine compounds having 5 to 2.5 allyl groups are preferred. This is because in this case, the highest heat resistance can be obtained.

In the reaction between the aromatic diamine compound and the allyl halide compound described above, the number of allyl groups in one molecule can be appropriately selected by changing conditions such as the amount of allyl halide to be reacted and the reaction time.

The aromatic allylamine compound of the present invention thus obtained is liquid at around room temperature and can be easily combined with a polymaleimide compound.

The polymaleimide compound to be combined with the aromatic allylamine compound of the present invention is a compound containing two or more maleimide groups represented by general formula (1) in the molecule.

(In the formula, R represents a hydrogen atom or a lower alkyl group.) Specific examples thereof include N,N'-diphenylmethane bismaleimide, N. N'-phenylene bismaleimide, N,N'-biphenylene bismaleimide, N,N'terphenylene bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-diphenylsulfone bismaleimide, N,N'- dicyclohexylmethane bismaleimide,
N,N'-xylene bismaleimide, N. N'-tolylene bismaleimide, N. N'-xylylene bismaleimide, N,N'-diphenyl hexane bismaleimide, NIN'-dichlorodiphenylmethane bismaleimide, N,N'-diphenyl hexane bismaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N'-diphenyl ether bismethylmaleimide, N,N'-diphenylsulfone bismethylmaleimide, N. N'-bis(aminophenoxybenzene) bismaleimide, N,N'-bis(aminophenoxy)bisphenol A bismaleimide (each includes isomers)
, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-hexamethylene bismethylmaleimide, and those obtained by adding these N,N'-bismaleimide compounds with diamines. The end is N
, a brepolymer having an N' bismaleimide skeleton, and maleimides or methylmaleimides of aniline/formalin polycondensates, aniline/aromatic aldehyde polycondensates, and the like. Particularly preferred are N,N'-diphenylmethane bismaleimide and N,N'-diphenyl ether bismaleimide.

Regarding thermal curing methods, curing is easily possible without catalysts, but organic peroxides, phosphine compounds,
It is also possible to carry out thermal curing using a polymerization initiator such as an azo compound. Examples of such polymerization initiators include penzoyl peroxide, dicumyl peroxide, triphenylphosphine, azobisisobutyronitrile, tertiary amines, quaternary ammonium salts, and imidazoles.

The resin composition comprising the aromatic allylamine compound and the polymaleimide compound of the present invention exhibits excellent heat-resistant mechanical properties when combined with a fiber base material. Examples include inorganic fiber base materials and organic fiber base materials such as aramid fibers.

Furthermore, the resin composition comprising the aromatic allylamine compound and the polymaleimide compound of the present invention may optionally contain an extender,
Can be combined with fillers, pigments, etc. for example,
Silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, pallite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, etc. are used for forming, laminating, adhesives, Used for composite materials, etc. Depending on the purpose, other known thermosetting resins such as alkenyl group-containing resins, triazine group-containing resins, unsaturated polyester resins, epoxy resins, silicone resins, phenol resins, etc. may be added.

Effects of the Invention> As explained above, the aromatic allylamine compound of the present invention can be used as a raw material for a resin composition that provides a shaped product with low viscosity, excellent workability, and excellent heat resistance and adhesive properties. can.

The resin composition is useful as a material for casting, impregnation, lamination, and molding.

<Examples> Next, Examples will be shown to explain the present invention in detail, but the present invention is not limited thereto.

Example 1 [Synthesis of compound of structural formula [■]] L1 equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
100 g (0.34 mol) of 1,3-bis(4-aminophenoxy)benzene and 334 g of dimethyl sulfoxide were placed in a 4-Turf flask, and after dissolving at room temperature,
87.2g of 8% sodium hydroxide aqueous solution (1.0mo
76.5g of allyl chloride (
1.0 mol) was added dropwise over 2 hours, and after dropping, the temperature was 50°C.
The mixture was kept warm for 4 hours and left overnight at room temperature. toluene 300
The organic layer was separated, washed twice with 500 g of 15% brine and twice with 500 g of water, and dehydrated using magnesium sulfate. The solvent was distilled off under reduced pressure to obtain the liquid allylated 1. 123 g of 3-bis(4-aminophenoxy)benzene was obtained.

The average allele number was determined by LC as follows: 1. per molecule of 3-bis(4-aminophenoxy)benzene, 2.
0, and the viscosity was 60 Stokes/25°C. Furthermore, the FD-MS spectrum and NMR spectrum of this compound are shown in Figure 1 and Figure 2, respectively.

Example 2 In the same manner as in Example 1, 100 g (0.34 +++ ol
), 48% sodium hydroxide aqueous solution 1 as a dehydrochlorination agent
28 g (1.5 mol), the dropping amount of allyl chloride was 26
By changing the amount to 0 g (1.7 mol) and reacting at 50° C. for 48 hours, 107 g of an allyl compound having an average number of allyl groups of 3.2 was obtained.

This allyl compound was a liquid with a viscosity of 23 Stokes and 725°C.

In addition, FD-MS spectrum and NMR of this compound
The spectra are shown in Figure 3 and Figure 4, respectively.

Example 3 [Synthesis of compound of structural formula [■]] IJ equipped with a stirrer, reflux condenser, thermometer, and dropping funnel
100 g (0.34 mol) of l,3-bis(3-aminophenoxy)benzene and 334 g of dimethylformamide were placed in a 4-tube flask, and after dissolving at room temperature,
Triethylamine 107g (1.06m
o I) and allyl chloride 161 at 30°C to 40°C.
g (2, Imol) was added dropwise over 2 hours, then 4
By reacting at 0° C. for 24 hours, 26 g of liquid allylated 1.3-bis(3-aminophenoxy)benzene was obtained.

The average number of allyl groups was 2.0 per molecule of 1.3-bis(3-aminophenoxy)benzene, and the viscosity was 70 Stokes at 725°C. Also, the FD-M of this compound
Figure 5 shows the S spectrum and NMR spectrum, respectively.
and shown in Figure-6.

Example 4 By reacting at 40°C for 48 hours in the same manner as in Example 3, the average number of allyl groups was 2.8, 18 Stokes/
137 g of an allyl compound having a viscosity of 25°C was obtained. Furthermore, the FD-MS spectrum and NMR spectrum of this compound are shown in Figures 7 and 8, respectively.

Example 5 [Synthesis of compound of structural formula [IV]] It was a liquid material with a viscosity of 20 Stokes/25°C. Further, the FD-MS spectrum and NMR spectrum of this compound are shown in Figure 9 and Figure IO, respectively.

Example 6 In the same manner as in Example 5, 100 g (0.34 mol) of 1,4-bis(4-aminophenoxy)benzene,
114g of 48% sodium hydroxide aqueous solution as a dehydrochlorination agent
(IJmol), the amount of allyl salt added was 104 g (
1. 3 mol) and reacted at 50°C for 48 hours to obtain 131 g of an allyl compound having an average number of allyl groups of 3.0 and a viscosity of 17 Stokes/25°C.

Example 7 [Synthesis of compound of structural formula [■]] 100 g (0.34 mol) of 1,4-bis(4-aminophenoxy)benzene was prepared in the same manner as in Example I.
, 57g of 48% sodium hydroxide aqueous solution as a dehydrochlorination agent
(0.68 mol), the amount of allyl salt added was 52
．． 3 g (0.68 mol) and reacted at 40° C. for 16 hours to obtain 122 g of an allyl compound having an average number of allyl groups of 2.0.

In the same manner as in Example 3, 82 g (0.2 mo
l), 81 g of triethylamine as a dehydrochlorination agent (0.
8 mol), and the amount of allyl chloride added was 55. 1 g (
0. 72 mol) and reacted at 40°C for 8 hours to obtain 97g of an allyl compound having an average number of allyl groups of 1.8 and a viscosity of 100 Stokes or more/25°C.

Example 8 In the same manner as in Example 7, the amount of allyl chloride dropped was reduced to 7.
3.5g (0.96mol) and 16% at 40°C.
By reacting for a period of time, 100 g of an allyl compound having an average number of allyl groups of 2.6 was obtained. This compound was a liquid substance with a temperature of 100 Stokes or more/25°C. Further, the FD-MS spectrum and NMR spectrum of this compound are shown in Figure 11 and Figure 12, respectively.

Reference Example 1 The allyl compound obtained in Example I was mixed with N,N'-diphenylmethane bismaleimide (Bestlex BH-130 manufactured by Sumitomo Chemical (II)) in the proportions shown in Table 1.
After blending, the mixture was heated and melted at 1600C-170C, defoamed, poured into a mold set in advance in an oven, held at 150oC for 1 hour, gelled, held at 200C for 5 hours, and removed from the mold. A cured product with a thickness of 2 m was prepared. For comparison, N,N'-diphenylmethane bismaleimide and 1,3-bis(4-aminophenoxy)benzene (Comparative Reference Example 1), 1,3-bis(3-aminophenoxy)benzene (Comparative Reference Example 2), 1 .4-bis(4-
Aminophenoxy)benzene (Comparative Reference Example 3), 2,2
-Bis(4-aminophenoxyphenyl)propane (Comparative Reference Example 4) was heated and mixed at a molar ratio of 1:0.4, and after pressing at 200°C for 1 hour at 50 kg/crl, at 200°C. 2 mm by curing for 4 hours
A thick cured product was obtained. Table 1 shows the physical properties of each cured product.

Umbrella 1: By TMA method *2: Based on JIS K6911 The composition consisting of an allylated aromatic diamine compound and a polymaleimide compound of the present invention is easy to process, and can be used as a raw material for Examples 1 to 8. It can be seen that the composition has excellent heat resistance and toughness compared to the composition composed of the aromatic diamine compound and the polymaleimide compound used.

Reference Examples 2 to 9, Comparative Reference Examples 1 to 4 Allylated aromatic diamines obtained in Examples 1 to 8 and N,N'-diphenylmethane bismaleimide (Best Iex @ BH-130 manufactured by Sumitomo Chemical ■) Table -
Blend in the ratio shown in 2, heat and melt mix at 150°C-160°C, and keep warm for 20 minutes with stirring to 150°C.
A prepolymer having a viscosity of 6 to 7 poise at °C was obtained. 60 parts of this prepolymer was mixed with 4 parts of N,N-dimethylformamide.
Dissolved in 0 parts N. A resin varnish in which N'-diphenylmethane bismaleimide does not precipitate was obtained. The varnish was coated with glass cloth (Kanebo (Kiyuki KS-1600, aminosilane treated))
A prepreg was obtained by impregnating the prepreg with water and heat-treating it in an oven at 160°C for 20 minutes.

6 sheets of prepreg and copper foil (Furukawa Circuit Foil (1@T)
TA I treatment, 35μ thickness) stacked at 200℃, 50kg/
Press molding was carried out at a pressure of CD for 2 hours to obtain a copper-clad laminate having a thickness of 1 mm. The physical properties of this laminate were determined according to JIS-C-64.
81, and the results shown in Table 2 were obtained.

For measuring the bending strength at 240° C., a 1.6 mm thick laminate made of eight sheets of the above prepreg formed under the same conditions was used.

Comparative Reference Example 5 60 parts of Kerimide@-601 (manufactured by O-Ne Poulenc) was mixed with N. A glass cloth was impregnated with a varnish obtained by dissolving it in 40 parts of N-dimethylformamide in the same manner as in Reference Example 1, heat treated to form a prepreg, and heated at 200°C and 50k.
A copper-clad laminate was obtained by pressing at g/crl for 2 hours. Table 2 shows the physical properties of each cured product.

From the measurement results in Table 2, it can be seen that the thermosetting resin copper-clad laminate produced using the aromatic allylamine compound of the present invention has excellent heat resistance and adhesiveness.

[Brief explanation of the drawing]

Figures 1, 3, 5, 7, 9 and 11 show FD-MS spectra of allylamine compounds obtained in Examples. Figures 2, 4, 6, 8, IO and 12 represent NMR spectra of allylamine compounds obtained in Examples. RO 0 C4 0 0 FU 0 C4 RO NO RO N 0 0 RO N 0 RO 0 C4 0 0 FU 0 04 RO N

Claims (1)

[Claims] 1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, Ar represents a divalent aromatic residue, R_1R_
2, R_3, and R_4 each independently represent an allyl group or hydrogen, and at least one of R_1, R_2, R_3, and R_4 is an allyl group. ] An aromatic allylamine compound represented by 2) The divalent aromatic residue in formula [I] is ▲formula,
The aromatic allylamine compound according to claim 1, which has a chemical formula, table, etc. ▼ or ▲ has a numerical formula, chemical formula, table, etc. ▼.