JPS5857423B2 - Fuhouwa Polyester Imide Scale Materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel unsaturated polyesterimide compound having an N-allylimide group as an unsaturated group.

Examples of resins that have unsaturated bonds and can be cured radically include unsaturated polyesters that use maleic acid and diallyl phthalate resins (although these are known, they cannot be said to be sufficient in terms of heat resistance). .

Therefore, the inventor of the present invention has arrived at the present invention as a result of intensive research in order to obtain a compound that provides a cured resin with higher heat resistance.

That is, the present invention is based on (1) the following general formula [■] [wherein R2 is an m-valent aliphatic group, alicyclic group, or aromatic group having 16 or less carbon atoms, and m is 2 to 6 is an integer.

) Polyester cyclic acid anhydrides (including hydrated or alcoholic ring-opened products thereof).

same as below.

); The following general formula [■] [However, in the formula, R represents a hydrogen atom or a methyl group.

The following formula (III) is characterized by reacting with allylamine represented by the following formula (III) [wherein R, R2 and m are as defined above.

] A method for producing an unsaturated polyesterimide compound represented by the formula Contains ring-opened alcohol products.

same as below. ) in formula CI) to form a trinotimide bond; said allylamine reacts with at least one in formula CI) to form an allyltrimellitimide group; thus in formula CI) A method for producing an unsaturated polyesterimide compound that forms an imide bond with a polyamine or an allyl trimellitimide group with an allylamine.

It is.

According to the present invention, N having a tricarboxylic acid residue
-By introducing an allylimide group, an unsaturated polyesterimide compound that provides a cured resin with extremely excellent heat resistance can be obtained.

The polyester cyclic anhydride represented by the general formula CI) used in the present invention can be obtained by, for example, reacting a tricarboxylic acid anhydride or a functional derivative thereof with a polyhydroxyl compound or a functional derivative thereof according to a known method. It can be manufactured.

For example, a method in which a tricarboxylic anhydride monohalide and a polyhydroxyl compound are preferably used in the presence of an acid acceptor to preferentially react the hydroxyl group and an acid halide group, or a method in which a reaction between a hydroxyl group and an acid halide group is preferentially carried out using a tricarboxylic anhydride monohalide and a polyhydroxyl compound; Examples include a method of reacting with an esterified product such as a compound.

In the latter case, acetic acid etc. will be eliminated by the reaction.

In addition, in the various reactions described above, a polyester residue can also be introduced into R2 of the general formula [■] by, for example, adding and reacting polycarboxylic acid, hydroxycarboxylic acid, or a functional derivative thereof.

Furthermore, a corresponding residue can be introduced into R2 by adding and reacting other reaction reagents within a range suitable for the purpose of the present invention.

The polyhydroxyl residue remaining in the tricarboxylic acid constituting the general formula [I] may be any aliphatic, alicyclic, aromatic, etc. residue, and preferred examples include ethylene glycol, propylene glycol, and tetramethylene. Glycol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexandriolpentaerythritol, sorbitol, cyclohexane dimetatool, 2,2'-diphenylolpropane -bis-4・4'-(β-hydroxy: r-f/1/
), 2-7'', 4-diol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl ether, etc., and these are m-valent aliphatic compounds having 16 or less carbon atoms. group, alicyclic group, or aromatic group.

Examples of the residues of polyhydroxyl compounds include residues of polyesters with a low degree of condensation whose ends are mainly composed of hydroxyl groups, phenoxy resins, partially cured epoxy resins, and the like.

Among the above residues, the aromatic nucleus may have an inert substituent such as a nitro group, halogen, or lower alkyl group.

The present invention is carried out by reacting a polyester cyclic anhydride represented by the general formula [I] and/or its hydrated or alcoholic ring-opened product with an allylamine represented by the general formula (II, l). .

Generally, the formation of amic acids by addition of amines occurs even at relatively low temperatures, but in order to dehydrate them and convert them into imide groups, it is usually preferable to heat the amic acid to a temperature of 80 to 180°C.

A reaction time of 0.2 to 10 hours is generally suitable.

However, the general formula [■] [However, in the formula, R, R2 and m are as defined above.

] is obtained.

The above reaction can also be carried out in the presence of an inert organic medium, if necessary.

In addition, in place of a part of the above allylamine, aliphatic, alicyclic,
Aromatic polyamines and the like can be used.

Suitable examples include hexamethylene diamine, cyclohexane dimethylamine, diaminodiphenylmethane, m-
Examples include phenylenediamine.

Thus, the above polyamine reacts with at least one of m in formula [■] to form a trimellitimide bond; the allylamine reacts with at least one of m in formula [I]; An unsaturated polyesterimide compound is obtained which reacts to form an allyl I.limellitimide group; however, it forms an imide bond with a polyamine or an allyl trimellitimide group with an allylamine.

If the product is a single product, it can be purified by known means such as recrystallization.

Even if it has a statistical structure, it can be purified by means such as reprecipitation.

The unsaturated polyesterimide compound obtained by the method of the present invention can be converted into a polyesterimide resin with excellent heat resistance by radical curing as described above, and can be used in a wide range of applications as molded products.

The structure of the product of the present invention can be confirmed by infrared absorption spectrum, nuclear magnetic resonance absorption spectrum, elemental analysis, etc.

The present invention will be described in detail with reference to Examples below, but the Examples are for illustrative purposes only and are not intended to be limiting.

Example 1 2,2-isopropyritine-bis(P-phenylene trime')-1,2- in a 200cc three-bottle flask.
28.81 (0.05 mol) of anhydride) and 50 g of N-methylpyrrolidone were added, and allylamine (7 mol) was added with stirring.
? (0.12 mol) is added slowly.

10 rul of xylene is added to raise the bath temperature to 170-180°C, and the water produced is distilled off by azeotropy with xylene.

After the reaction was completed, the reaction system was poured into a large amount of water to obtain 30.4P of white product (yield: 93%).

The melting point of this product was 168.0 to 169.0°C, and when an infrared absorption spectrum was measured, absorption of imide groups, ester groups, and vinyl-type unsaturated bonds was clearly observed.

Furthermore, elemental analysis revealed that the theoretical value was 71.56% carbon and 4% hydrogen.
．． 59%, nitrogen 4.28%, carbon 71.35%, hydrogen 4.62%, nitrogen 418%, showing good agreement.

From the above results, it was confirmed that 2,2-isopropyritinpis (P-phenylenetrimethic acid-4-ester-1,2-N-7 lylimide) was obtained.

Next, this compound 2'? dicumyl baroxide 5
It was confirmed that a yellow cured polymer was obtained by adding 0 m9 and continuing heating at 170° C. to 180° C. for 3 hours.

Example 2 Ethylene bis(trimery r-1□) dianhydride 20.5 ? (0.05 mol)
, and 30 g of N-methylpyrrolidone.

Separately diaminodiphenylmethane 4-. 0? (0,0
2 mol), allylamine 3.42 (0.06 mol), N
- A solution consisting of 30 g of methylpyrrolidone is prepared and slowly added to the previous reaction vessel under stirring.

Add 10 rnl of xylene, raise the bath temperature to 170-180°C, and distill off the water produced by azeotroping with the xylene. After the reaction is complete, the reaction system is poured into a large amount of water, and a yellow unsaturated polyesterimide compound of 22.8 cm is produced. was gotten.

When the infrared absorption spectrum was measured, absorption of imide groups, ester groups, and vinyl-type unsaturated bonds was clearly observed.

The softening temperature of this product was 161-168°C.

Example 3 Terephthalic acid dichloride t6.2P (0.08 mol)
, 4-chloroformylphthalic anhydride 50.51 (0,
24 mol) and ethylene glycol 12.4P (0,2
Polyester 5 having an acid anhydride group at the terminal from
Obtained 4.4P.

50.0P of this polyester was placed in a 200cc three-bottle flask, 70g of N-methylpyrrolidone was added thereto, and 15% of allylamine was added thereto with stirring. (0.25 mol) is added slowly.

20 ml of xylene is added and the bath temperature is raised to 170-180°C, and the water produced is distilled off by azeotropy with xylene.

After the reaction was completed, the reaction system was poured into a large amount of water to obtain 53.9P of a yellow unsaturated polyesterimide compound.

When an infrared absorption spectrum was measured, absorption of imide groups, ester groups, and vinyl-type unsaturated bonds was clearly observed.

The softening temperature of this material was 128-135°C.

Example 4 28.81 (0.05 mol) of 2,2-isopropyritine-bis(P-phenylene trimellitate = 1,2 anhydride) and 50 g of N-methylpyrrolidone were placed in a 200 cc three-bottle flask, Hexamethylenediamine 2.3P
(0.02 mol) and methallylamine 4.31 (0.06 mol)
mol).

Add 10rui of xylene and raise the bath temperature to 170°C to 180°C.
The water produced is removed by azeotrope with xylene.

When the reaction system is poured into a large amount of water after the reaction is completed, a yellowish-white unsaturated polyesterimide compound 23. Fl was obtained.

When an infrared absorption spectrum was measured, absorption of imide groups, ester groups, and vinyl-type unsaturated bonds was clearly observed.

The softening point of this product was 125-134°C.

Claims (1)

[Scope of Claims] 1 The following general formula [I] [However, in the formula, R2 is an m-valent aliphatic group, alicyclic group, or aromatic group having 16 or less carbon atoms, and m is 2 to 6 is an integer. ] A polyester cyclic acid anhydride (including its hydrated or alcoholized ring-opened products; the same applies hereinafter); and the following general formula [■] [wherein R represents a hydrogen atom or a methyl group. The following formula (III) is characterized by reacting with allylamine represented by the following formula (III) [wherein R, R2 and m are as defined above]. ] A method for producing an unsaturated polyesterimide compound represented by 2 The following general formula [I] [wherein R2 represents an m-valent aliphatic group, alicyclic group, or aromatic group having 16 or less carbon atoms, and m is an integer of 2 to 6. ] A cyclic acid anhydride (including its hydrated or alcoholic ring-opened products; the same applies hereinafter) and a cyclic acid anhydride represented by the following general formula (III [wherein R represents a hydrogen atom or a methyl group] and an aliphatic, alicyclic or aromatic polyamine; the above polyamine is a compound of formula [I] (including its hydrated or alcoholic ring-opened product; the same shall apply hereinafter). The above allylamine reacts with at least one of m in the formula [■] to form a trimetimide bond;
All of the imide bonds with polyamine in formula [■] form allyl trimellitimide groups with allylamine. A method for producing an unsaturated polyesterimide compound, characterized by the following.