KR910009827B1 - Polyimide resin composition - Google Patents

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Description

Polyimide Resin Composition

The present invention relates to a resin composition for molding. More specifically, the present invention relates to a polyimide-based molding resin composition excellent in heat resistance, chemical resistance, mechanical strength, and the like and excellent in molding processability.

Conventionally, polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine has excellent mechanical strength, dimensional stability, flame retardancy, electrical insulation, etc. in addition to its high heat resistance. It is used in the field of transportation equipment, and is expected to be widely used in the field where heat resistance is required in the future.

Various polyimide with the outstanding characteristic is developed conventionally

However, even if it is excellent in heat resistance, it does not have a clear glass transition temperature. Therefore, when used as a molding material, it must be processed using a method such as sintering molding, or it is excellent in workability, but it has a low glass transition temperature and a halogenated hydrocarbon. Soluble in water and not satisfactory in terms of heat resistance and solvent resistance.

An object of the present invention is to obtain a polyimide-based resin composition which is remarkably good in moldability in addition to the excellent properties inherent in polyimide.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors discovered that the polyimide resin composition which consists of a novel polyimide and specific amount of aromatic polysulfone is especially effective for the said objective, and completed this invention.

The present inventors first formulated as a polyimide that is excellent in mechanical properties, thermal properties, electrical properties, solvent resistance, etc., and also has heat resistance.

(Wherein X represents a carbonyl group or sulfonyl group, R represents an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic in which aromatic groups are interconnected by a direct or crosslinking source) A polyimide having a repeating unit represented by a tetravalent group selected from the group consisting of groups was found (Japanese Patent Laid-Open No. 62-53388).

The said polyimide is a novel heat resistant resin which has many favorable physical properties peculiar to a polyimide. However, when compared to conventional engineering plastics represented by polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polysulfone, polyphenylene sulfide, etc., it is much superior in heat resistance and other properties, but melts when the molecular weight is increased. The fluidity is lowered, and the molding processability is still less than that of the resin.

An object of the present invention is to provide a polyimide resin composition for molding which is very excellent in terms of fluidity during melting, without impairing the inherent properties of polyimide.

That is, the present invention is formula

Wherein X and R are the same as before, and a resin composition composed of 99.9 to 50% by weight of polyimide having a repeating unit and 0.1 to 50% by weight of aromatic polysulfone.

The polyimide used in the present invention is a formula

Ether diamine represented by (wherein X represents a carbonyl group or sulfonyl group), that is, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone or bis [4- It is obtained by imidizing polyamic acid obtained by reacting [4- (4'-amino-α, α-dimethylbenzyl) phenoxy] phenyl] sulfone with at least one tetracarboxylic dianhydride in an organic solvent.

The tetracarboxylic dianhydride used at this time is a formula

Tetracarboxylic acid dianhydride represented by (wherein R is the same as before).

That is, as tetracarboxylic dianhydride used, ethylene tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzo Phenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,2', 3,3'-biphenyl tetracarboxylic dianhydride, 2,2-bis (3,4- Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) Sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(P-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1, 4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride,, 1,2,3,4-benzene tetracarboxylic dianhydride, 3,4,9,10-phenylene tetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, etc. These tetracarboxylic dianhydrides are used individually or in mixture of 2 or more types.

Moreover, although the polyimide used for the composition of this invention is a polyimide which uses said etherdiamine as a raw material, the polyimide obtained by mixing and using other diamine also in the range which does not impair the favorable physical property of this polyimide also It can be used in the composition of the present invention.

As diamine which can be mixed and used, For example, m-phenylenediamine, O-phenylenediamine, P-phenylenediamine, m-aminobenzylamine, P-aminobenzylamine, bis (3-aminophenyl) ether, (3-aminophenyl) (4-aminophenyl) ether, bis (4-aminophenyl) ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis ( 4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) Sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'- Diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) Phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phen ] Ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2, 2-bis [4- (3-aminophenoxy) phenyl-1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl-1 , 1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis ( 3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy ) Biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, Bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [ 4- (3-amino Phenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] Ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, and the like.

The aromatic polysulfone used in the present invention

As the polyisulfone having a repeating unit such as

Polyethersulfone, and / or general formula, which is represented by the trademark and is sold under the trademark of "VIC TREX PES" by I.C.I.

And polysulfones sold under the trademark "UDEL POL SULFONE" from the US Union Carbide.

These aromatic polysulfones can be freely produced in various polymerization degrees, and those having a melt viscosity characteristic suitable for the desired blend can be arbitrarily selected.

The molding resin composition of the present invention is adjusted so that the polyimide 99.9 to 50% by weight and the aromatic polysulfone are in the range of 0.1 to 50% by weight.

The polyimide 6-aromatic polysulfone composite resin system of the present invention exhibits a significantly low melt viscosity in the high temperature range of 330 ° C or higher. The favorable fluidization effect of the aromatic polysulfone is recognized in a small amount, and the lower limit of the composition ratio is 0.1% by weight, but preferably 0.5% by weight or more.

In addition, although the mechanical strength at high temperature of the aromatic polysulfone belongs to a superior class in the heat resistant resin, the mechanical strength, particularly the Izod impact strength, is inferior to that of the polyimide. Therefore, if the amount of the aromatic polysulfone in the composition is too high, The original mechanical strength of the mead cannot be maintained, which is undesirable. Therefore, the composition ratio of aromatic polysulfone has an upper limit and 50 weight% or less is preferable.

In preparing the composition according to the present invention, it can be produced by a publicly known method. For example, the following method is a preferred method.

(1) The polyimide powder and the aromatic polysulfone powder are preliminarily kneaded using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a boll millibon blender, or the like to form a powder.

(2) The polyimide powder is first dissolved or suspended in an organic solvent, and an aromatic polysulfone is added to this solution or suspension, uniformly dispersed or dissolved, and then the solvent is removed to form a powder.

(3) After dissolving or suspending the aromatic polysulfone in the organic solvent solution of polyamic acid which is a precursor of the polyimide of the present invention, it is subjected to heat treatment at 100 to 400 ° C or by using an imidating agent which is usually used. After chemical imidation, the solvent is removed to form a powder. The powdered polyimide resin composition obtained as described above is used as it is for various molding purposes, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to melt blend and use it.

In particular, in the preparation of mixing the compositions, it is also a simple and effective method to melt the powders, pellets, or mixed powder and pellets.

As the melt blend, an apparatus used for melt blending ordinary rubbers or plastics, for example, a thermal roll, a Banbury mixer, a brabender, an extruder, or the like can be used. The melting temperature is set above the temperature at which the blending system can melt and below the temperature at which the blending system begins to pyrolyze, but the temperature is usually 280 to 420 ° C, preferably 300 to 400 ° C.

As the molding method of the resin composition of the present invention, injection molding or compression molding, which forms a homogeneous melt blend and is a highly productive molding method, is suitable, but other transfer molding, compression molding, sintering molding, extrusion film molding, etc. There is no problem in applying.

In addition, one or more solid lubricants such as molybdenum sulfide, graphite, boron nitride, lead oxide, lead powder and the like may be added to the resin composition of the present invention. Further, one or more reinforcing agents such as glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, potassium titanate fibers and glass beads can be added.

In addition, to the resin composition of the present invention, at least one conventional additive such as an antioxidant, a heat stabilizer, a UV absorber, a flame retardant, a flame retardant aid, an antistatic agent, a lubricant, and a coloring agent is added within a range that does not impair the object of the present invention. can do.

EXAMPLE

Hereinafter, the present invention will be described in more detail by the synthesis examples, examples and comparative examples.

Synthesis Example 1

6.68 kg (10 mol) of bis [4- [4- (4-amino-α, α-dimethylbenzyl) phenoxy] phenyl] sulfone in a reaction vessel equipped with a stirrer, a reflux cooler and a nitrogen introduction tube, N, 50.0 kg of N-dimethylacetamide was charged, and 2.14 kg (9.8 mol) of pyromellitic dianhydrides were added under nitrogen atmosphere at room temperature, paying attention to the solution temperature rise, and it stirred at room temperature for about 20 hours.

To the solution was added dropwise 2.02 kg (20 mol) triethylamine and 2.55 kg (25 mol) acetic anhydride under nitrogen atmosphere at room temperature. It stirred at room temperature for 20 hours, and obtained the pale yellow slurry. The slurry was filtered, washed with methanol, filtered, and dried under reduced pressure at 180 ° C. for 8 hours to obtain 8.26 kg (yield about 97.6%) of pale yellow polyimide powder. The logarithmic viscosity of the polyimide powder was 0.83 dl / g. Here, the logarithmic viscosity is a value measured at 35 ° C. after dissolving 0.5 g of polyimide powder in 100 ml of a solvent (p-chlorophenol: phenol = 90: 10 weight ratio) and cooling. Moreover, the glass transition temperature of this polyimide powder was 280 degreeC (measured by DSC method, and the same below), and the 5% weight loss temperature was 545 degreeC (measured by DTA-TG method).

[Examples 1-3]

As a powder of the polyimide powder and the aromatic polysulfone obtained in Synthesis 1, commercially available VICTREX PES 3600P (trademark of ICI Corporation) was dry blended in various compositions as shown in Table 1, and then 330 to 330 using a twin screw extruder. It assembled by extrusion at 350 degreeC.

The obtained pellet was placed on an injection molding machine, and injection molded at a molding temperature of 340 ° C to 380 ° C and a mold temperature of 150 ° C, and the physical and thermal properties of the molded product were measured.

The results are shown in Table 1 as Examples 1-3. Tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ASTM D-790, Izod impact is ASTM D-256, glass transition temperature is TMA penetration method, and heat deformation temperature is ASTM D-648. It depends.

Also in the table, the minimum injection pressure, which is the standard of melt fluidity, is also indicated.

Comparative Example 1

Using the composition outside the range of the present invention, the physical and thermal properties of the molded product obtained by the same operations as in Examples 1 to 3 are measured, and the results are shown in Table 1 as Comparative Example 1.

Table-1

Synthesis Example 2-6

By the combination of various diamines and various tetracarboxylic dianhydrides, the same production as in Synthesis example 1 was carried out to obtain various polyimide powders. Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity of the resulting polyimide powder.

[Examples 4 to 14 and Comparative Examples 2 to 6]

As the polyimide powder and the aromatic polysulfone obtained in Synthesis Examples 2 to 6, commercially available VICTREX PES 3600P (trademark of ICI) or UDEL POLY SULFONE P-1700 (trademark of Union Carbide, USA) was melted in the composition of Table 2. The mixture was kneaded to obtain a uniformly mixed pellet.

Next, the homogeneous mixture pellets obtained above were injection molded under the same conditions as in Example 1, and the physical and thermal properties thereof were measured. The results shown in Table 3-5 were obtained.

TABLE 2

Table-3

Table-4

Table-5

According to the method of this invention, in addition to the outstanding characteristic which polyimide has inherently, the polyimide resin composition which is remarkably good in moldability is provided.

Claims (2)

expression (Wherein X represents a carbonyl group or a sulfonyl group, R represents an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed ring in which aromatic groups are linked to each other by a direct or crosslinking source) A polyimide resin composition comprising 99.9 to 50% by weight of a polyimide having a repeating unit represented by a tetravalent group selected from the group consisting of formula aromatic groups and 0.1 to 50% by weight of an aromatic polysulfone. The method of claim 1, wherein R is Polyimide resin composition, characterized in that the tetravalent group selected from the group consisting of.