JPH0762071B2 - Method for producing thermosetting resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing a thermosetting resin molded product, and more specifically, thermosetting having excellent heat resistance, chemical resistance and mechanical properties. The present invention relates to a method for producing a resin molded product with fast curability and excellent moldability.

(B) Conventional Technology In recent years, with the progress of technology, a resin having excellent heat resistance and mechanical properties and excellent moldability has been required. Among these resins, a reaction-molding type resin using a reactive monomer or oligomer, that is, a resin in which molding and polymerization are simultaneously performed by using a relatively low-viscosity raw material has attracted attention. Polyurethane resins, polyurea resins, nylon resins, epoxy resins, unsaturated polyester resins, etc. are known as such resins, and some have been commercialized.

However, each of these resins has advantages and disadvantages,
For example, a polyurethane resin has a low heat resistance, and an unsaturated polyester resin has a drawback that it takes a long time for reaction, that is, molding. Therefore, it cannot be said that the resin has sufficient performance and moldability.

It is already known that a bis (2-oxazoline) compound and a polycarboxylic acid are heated and reacted to obtain a thermosetting resin. For example, in JP-A-60-137927, the above reaction is
Taking a reaction time of about 30 minutes to 10 hours at a temperature of 200 ° C. or higher, using a catalyst, for example, an electrophile such as phosphite, an oxazoline ring-opening polymerization catalyst such as alkyl halide, It is described that the reaction time can be shortened and the reaction temperature can be lowered.

Further, JP-A-62-104838 discloses a derivative of 2,2 '-(1,3-phenylene) bis (2-oxazoline) having a carboxyl group at the terminal, a polyvalent carboxylic acid and a polyvalent amine. Although a thermosetting resin composition obtained by reacting a resin is described, such a resin is a varnish obtained by adding a solvent such as cresol to a polycondensation reaction for a long time accompanied by the generation of a by-product. It is not related to a thermosetting resin molded product.

(C) Object of the Invention The present inventors have conducted diligent research on a method of increasing the reaction rate of a thermosetting resin using a cyclic iminoether compound, for example, to the extent that reaction molding is possible. The invention has been reached.

(D) Structure and Effect of the Invention That is, the invention is represented by the following formula (I). And / or the following formula (II) A cyclic imino ether compound represented by, an aromatic polyamine compound, and an aliphatic polycarboxylic acid intramolecular acid anhydride are heated in the presence of a catalyst in a mold to produce a thermosetting resin molded product. .

The present invention will be described in detail below.

In the above formula (I) and formula (II) used in the present invention, n represents an integer of 2 to 4. N = 2 of these
Is preferred. R represents an n-valent aliphatic, alicyclic or aromatic hydrocarbon group, and when n = 2, R may be a direct bond. Examples of R include hydrocarbon groups such as ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, p-phenylene, m-phenylene and cyclohexylene when n = 2, and when n = 3. Etc., if n = 4 Etc. can be given.

Ra, Rb, Rc, Rd, Re and Rf are each a hydrogen atom, an alkyl group having 3 or less carbon atoms (eg, methyl group, ethyl group), an aryl group having 7 or less carbon atoms (eg, phenyl group, tolyl group). As shown, these may be the same or different from each other. It is preferable that all of Ra, Rb, Rc, Rd, Re and Rf are hydrogen atoms, or any one of them is a methyl group and the rest are hydrogen atoms, and it is particularly preferable that all of them are hydrogen atoms.

Specific examples of the cyclic imino ethers (oxazoline derivatives) represented by the above formula (I) include 2,2′-ethylenebis (2-oxazoline) and 2,2′-tetramethylenebis (2-oxazoline). , 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-1,4-cyclohexylenebis (2-oxazoline), 2,2 ′ -Bis (4-methyl-2-oxazoline), 2,2′-bis (5-methyl-2)
-Oxazoline), 2,2'-m-phenylenebis (2-
Oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-mm-phenylenebis (5-methyl) -2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2 '
Examples thereof include -p-phenylene bis (5-methyl-2-oxazoline), 1,3,5-tris (2-oxazolinyl-2) benzene and the like. .

Of these, 2,2'-bis (2-oxazoline), 2,2 '
-Tetramethylene bis (2-oxazoline), 2,2'-
m-phenylene bis (2-oxazoline), 2,2'-p
-Phenylenebis (2-oxazoline) is preferred.

Specific examples of the cyclic imino ethers (oxazine derivatives) represented by the above formula (II) include 2,2-bis (5,6-
Dihydro-4H-1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-
Tetramethylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-hexamethylene bis (5,6-dihydro-
4H-1,3-oxazine), 2,2'-octamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-1,4
-Cyclohexylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2 ' -Bis (5-methyl-
5,6-dihydro-4H-1,3-oxazine), 2,2'-bis (6-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H
-1,3-oxazine), 2,2'-p-phenylenebis (5,
6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (4-methyl-5,6-dihydro-4H-1,3-
Oxazine), 2,2'-m-phenylenebis (5-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-
m-phenylene bis (6-methyl-5,6-dihydro-4H
-1,3-oxazine), 2,2'-p-phenylenebis (4
-Methyl-5,6-dihydro-4H-1,3-oxazine), 2,
2'-p-phenylenebis (5-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (6-methyl-5,6-dihydro-4H-1) , 3-oxazine)
Etc. can be illustrated.

Of these, 2,2'-bis (5,6-dihydro-4H-1,3-
Oxazine), 2,2'-tetramethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine ), 7-p
-Phenylenebis (5,6-dihydro-4H-1,3-oxazine) is preferred.

In the present invention, it is of course possible to use the cyclic iminoethers (oxazoline derivative) represented by the above formula (I) and the cyclic iminoethers (oxazine derivative) represented by the above formula (II) together.

Further, as the cyclic imino ethers, an oxazoline derivative represented by the formula (I) is preferable because of its high reactivity.

The aromatic polyamine compound used in the present invention is an aromatic amine compound having two or more primary amino groups and / or secondary amino groups in the molecule, and specifically, 4,4′-
Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,
4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone,
3,3′-diaminobenzophenone, p-phenylenecyamine, m-phenylenediamine, diaminonaphthalene,
4,4'-diaminodiphenyl sulfide, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2-dianilinoethane, 3,5-diethyl-2,4-diaminotoluene, 3,5-
Diethyl-2,6-diaminotoluene, 2,4,6-toluethyl-m-phenylenediamine, 2,6-dimethyl-4-t-
Butyl-m-phenylenediamine, 4,6-diisopropyl-m-phenylenediamine, 2-chloro-p-phenylenediamine, chlorodiaminotoluene, bis (3,5-
Examples thereof include diisopropyl-4-aminophenyl) methane and polymethylene polyphenyl polyamine. These can be used alone or in combination of two or more.

Next, the aliphatic polycarboxylic acid intramolecular acid anhydride used in the present invention is a compound in which an acid anhydride structure is formed in the molecule in an aliphatic polycarboxylic acid having two or more carboxyl groups in the molecule. , Specifically succinic anhydride, 2
-Methylsuccinic anhydride, 2,3-dimethylsuccinic anhydride,
2,2-dimethyl succinic anhydride, glutaric anhydride, 2-methyl glutaric anhydride, 3-methyl glutaric anhydride, 2,3
-Dimethyl glutaric anhydride, 2-ethyl succinic anhydride,
2-Ethyl glutaric anhydride and the like can be exemplified.
Of these, succinic anhydride and glutaric anhydride are preferable. These can be used alone or in combination of two or more.

The ratio of the cyclic iminoether compound and the aromatic polyamine compound used in the above components is preferably such that the amine equivalent is 10 to 120% with respect to the total cyclic iminoether equivalent, and the ratio is 30 to 100%. Is more preferable, and a ratio of 50 to 90% is particularly preferable. Further, the proportion of the aliphatic polycarboxylic acid intramolecular acid anhydride used is preferably such that the acid anhydride equivalent is 50 to 200% with respect to the amine equivalent of the aromatic polyamine compound, and is 50 to 140%. The ratio is more preferable, and the ratio of 50 to 120% is particularly preferable. Further, the acid anhydride equivalent is preferably 120% or less, more preferably 100% or less, and particularly preferably 90% or less with respect to the total oxazoline equivalent.

The thermosetting resin of the present invention is obtained by heating and reacting the above cyclic imino ether compound, aromatic polyamine compound and aliphatic polycarboxylic acid intramolecular acid anhydride in the presence of a catalyst. The catalyst used here is not particularly limited as long as it promotes the above reaction, and examples thereof include protonic acid, protonic acid ester, Lewis acid and its complex, alkyl halide, halogen, and formula (III) A halogenated phenol compound represented by the formula (IV) Or formula (V) [In formula, Z and q are synonymous with Formula (IV). ] The phthalic acid derivative shown by these can be mentioned.

More specifically, examples of the protic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-
Organic protonic acids such as toluene sulfonic acid; sulfuric acid,
Inorganic protic acids such as phosphoric acid, phosphorous acid, phosphinic acid, phosphonic acid, perchloric acid and the like can be mentioned. Examples of the protic acid ester include methyl benzene sulfonate, ethyl benzene sulfonate and methyl p-toluene sulfonate. , Sulfonic acid esters such as ethyl p-toluenesulfonate, esters of inorganic protonic acids such as dimethyl sulfate, trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, triphenyl phosphite, and the like. . Examples of the Lewis acid and its complex include titanium tetrachloride, tin tetrachloride, zinc chloride, aluminum chloride, trifluoroborane, trifluoroborane ether complex and the like, and alkyl halides such as methyl iodide, ethyl iodide, and iodo. Examples thereof include propyl iodide, butyl iodide, benzyl iodide, and benzyl bromide. Examples of the halogen include iodine. Specific examples of the halogenated phenol compound represented by the formula (III) include 3,5-dibromo-4-hydroxybenzoic acid and 3,5-dichloro-4.
-Hydroxy-benzonitrile, 3,5-dibromo-4-
Hydroxybenzonitrile, 3,5-dichloro-4-hydroxynitrobenzene, 3,5-dibromo-4-hydroxynitrobenzene, bis (3,5-dichloro-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4) −
Hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) ketone, bis (3,5-dibromo-4-hydroxyphenyl) ketone, methyl 3,5-dichloro-4-hydroxybenzoate, 3, 5-Dibrom-
Methyl 4-hydroxybenzoate, 3,5-dibromo-4-hydroxybenzoate methyl, 3,5-dibromo-4-hydroxybenzoic acid amide, 3,5-dibromo-4-hydroxybenzoic acid N-ethylamide, 3, 5-dichloro-4-hydroxybenzenesulfonic acid amide, 3,5-dibromo-4-hydroxybenzenesulfonic acid amide, 3,5-dibromo-
4-hydroxybenzene sulfonic acid N-methylamide etc. can be illustrated.

The phthalic acid derivative represented by the formula (IV) or (V) includes 3,4,5,6-tetrabromophthalic acid and 3,4,5,6-
Tetrabromophthalic anhydride, 3,4,5,6-tetrachlorophthalic acid, 3,4,5,6-tetrachlorophthalic anhydride, 3,
4,5,6-Tetrabromophthalic acid monomethyl ester, 3,
4,5,6-Tetrachlorophthalic acid monomethyl ester, 3,
4,5,6-Tetrabromophthalic acid monoethyl ester, 3,
Examples include 4,5,6-tetrabromophthalic acid monoamide, N-methyl-3,4,5,6-tetrabromophthalic acid monoamide, and 2-carboxy-3,4,5,6-tetrabromophenylmethylketone. can do. These catalysts can be used alone or in combination of two or more. The amount of these catalysts used is not particularly limited, but preferably 0.01 to 20 mol% with respect to the cyclic imino ether compound used, and more preferably 0.
The amount is 05 to 15 mol%, particularly preferably 0.1 to 10 mol%.

As a reaction method, a solid and / or liquid of each of a cyclic imino ether compound, an aromatic polyamine compound, an aliphatic polycarboxylic acid intramolecular acid anhydride and a catalyst is physically intimately mixed, and the mixture is molded into a mold having a desired shape. And heat reaction in the mold; cyclic iminoether compound, aromatic polyamine compound, aliphatic polycarboxylic acid intramolecular acid anhydride, and catalyst separately, or as a two-liquid system by appropriately combining each A method may be mentioned in which the mixture is melted, mixed with a mixing means such as a mixing head, and then directly injected into a mold having a desired shape heated to a reaction temperature to cause a reaction. In the case of the latter method, it is preferable to use them as two liquids of a first component mainly containing a cyclic imino ether compound and an aromatic polyamine compound and a second component mainly containing a fatty acid polycarboxylic acid anhydride and a catalyst.

The reaction temperature varies depending on the type of each of the above components and the use ratio thereof, but is preferably 50 to 300 ° C., more preferably 60.
~ 280 ° C, particularly preferably about 70-260 ° C.

The reaction time may be a time sufficient for the target resin to be sufficiently cured, and this time varies depending on the type of raw material used, the ratio used, the reaction temperature, etc., but is preferably 10 seconds to 60 minutes, more preferably Is 20 seconds to 30 minutes, particularly preferably 30
Seconds / 15 minutes.

The reaction can be carried out under normal pressure to increased pressure, but in this case, it is preferable to carry out under an inert gas atmosphere of nitrogen, argon or the like in order to prevent oxidative deterioration of water in the air or the resin.

In the reaction of the present invention, first, an aromatic polyamine compound and an aliphatic polycarboxylic acid intramolecular acid anhydride are reacted in a low temperature range to form a polycarboxylic acid having an amide bond in the molecule, and a cyclic imino ether is added to the polycarboxylic acid. It is presumed that the compound is reacting. At this time, if an aliphatic compound is used as the amine compound or an aromatic compound is used as the acid anhydride, imidization reaction is likely to occur and problems such as foaming due to generation of water are not preferable.

In the present invention, if necessary, a filler such as glass fiber or carbon fiber, a pigment such as titanium oxide, an oxidation stabilizer, an ultraviolet absorber, a release agent, a dye, a flame retardant or the like can be added.

Further, a compound capable of addition-reacting with the oxazoline derivative, for example, carboxylic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid and p-oxybenzoic acid may be added in a small proportion.

The thermosetting resin of the present invention does not generate a volatile component in the reaction process and does not require a solvent, and thus is extremely useful as a two-liquid mixed type reactive resin, so-called reaction injection molding method (RIM).

(E) Examples Hereinafter, the present invention will be described in detail with reference to examples, but the examples are for the purpose of explanation and the present invention is not limited thereto. In the examples, "part" means "part by weight". The heat distortion temperature was measured by DMA at a temperature rising rate of 10 ° C / min.

Example 1 2,2'-m-phenylene bis (2-oxazoline) 21.6
Part, 4,4′-diaminodiphenylmethane 13.9 parts, succinic anhydride 14 parts and triphenyl phosphite 1.5 parts were put into a glass reaction mold, mixed well, then nitrogen-substituted, and then 120 ° C.
When heated to, the reaction immediately started and after 30 seconds, heat was generated up to 195 ° C. to cure. The obtained resin was light yellow and transparent and extremely tough, and the heat distortion temperature was 122 ° C.

Example 2 2,2'-m-phenylene bis (2-oxazoline) 21.6
Parts, 3,4′-diaminodiphenyl ether 14.2 parts, succinic anhydride 14 parts and ethyl p-toluenesulfonate 1 part were put into a glass reaction mold and thoroughly mixed with nitrogen, then,
When heated to 120 ° C, the reaction starts immediately and after 40 seconds 191
It was heated to ℃ and cured. The obtained resin was light brown, transparent and tough, and the heat distortion temperature was 128 ° C.

Example 3 2,2'-m-phenylenebis (2-oxazoline) 13
Part, 2,2'-m-phenylene bis (5,6-dihydro-4H-
1,3-oxazine) 10 parts, 4,4'-diaminodiphenylmethane 12.9 parts, glutaric anhydride 14.5 parts and bis (3,5-
2.8 parts of dibromo-4-hydroxyphenyl) sulfone was put into a glass reaction mold, mixed well, and then replaced with nitrogen, and then 18
Heated to 0 ° C. After about 80 seconds the reaction had cured. The resin obtained is yellow and transparent and extremely tough, with a heat distortion temperature of 120.
It was ℃.

Comparative Example 1 In Example 1, phthalic anhydride was used instead of succinic anhydride.
A curing test was conducted in the same manner except that 10 parts were used.
The reaction product became a transparent and uniform solution at 190 ° C., but did not cure, and when heated to 220 ° C., foaming occurred and the reaction liquid became whitish and opaque, but it did not cure.

Example 4 2,2'-m-phenylene bis (2-oxazoline) 21.6
Parts, 4,4'-diaminodiphenylmethane (11.9 parts), glutaric anhydride (13.7 parts) and 3,4,5,6-tetrabromophthalic anhydride (2.3 parts) were put in a glass reaction mold, and after thoroughly mixing, the atmosphere was replaced with nitrogen. When it was then heated to 180 ° C., it was cured after 70 seconds and became a tough resin. The obtained resin was brown and transparent and the heat distortion temperature was 132 ° C.

Example 5 The resins obtained in Examples 1 to 4 were treated under an acetone reflux for 1 hour, but showed no change and were excellent in solvent resistance.

Example 6 216 parts of 2,2′-m-phenylene bis (2-oxazoline) and 139 parts of 4,4′-diaminodiphenylmethane were added at 140 ° C.
Heat the solution to a uniform solution (Solution A), and add glutaric anhydride 160
And 18 parts of triphenyl phosphite were heated to 100 ° C. to prepare a uniform solution (solution B). The two liquids were placed in a cylinder equipped with an extrusion piston heated and maintained at the above temperature, and the cylinder was calibrated to a diameter of 3 mmφ through a collision mixing nozzle, and a mold of 125 mm in length, 60 mm in width and 5 mm in thickness (temperature:
110 ° C).

Next, the liquid A and the liquid B were extruded from the cylinder at a ratio of the liquid A and the liquid B at a weight ratio of 2: 1 and filled in a mold and reacted. After 5 minutes, the molded product was taken out from the mold.
The molded product was light yellow and transparent, was extremely tough, and had a heat distortion temperature of 116 ° C.

Claims (1)

[Claims] 1. The following formula (I) And / or the following formula (II) A cyclic iminoether compound, an aromatic polyamine compound, and an aliphatic polycarboxylic acid intramolecular acid anhydride are heated and reacted in the mold in the presence of a catalyst.