JPH0710916B2 - Crosslinkable polyetheramide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat resistant polymer, and more particularly to a crosslinkable polyether amide.

[Conventional technology]

Among resins which are practically used as engineering plastics today, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether amide, etc. are considered to be heat resistant. Although they are provided with rigidity and thermal stability by containing an aromatic ring in the molecular chain at a high rate, they are essentially linear polymers. Therefore, unlike the thermosetting heat-resistant resin that becomes a three-dimensional cross-linked polymer by molding, they are unavoidably deformed at high temperature and under load even after molding,
There was some enthusiasm that I could not extend the application range to the high temperature side.

[Problems to be solved by the invention]

The object of the present invention is to increase the heat distortion temperature of molded articles and improve the characteristics such as creep at high temperatures, especially for polyether amides.

[Means for solving problems]

In order to enhance the mechanical properties of the polymer at high temperature, a method such as addition of a reinforcing material or a filler and formation of intermolecular crosslinks can be adopted. Whereas the former method applies to polymers, the latter may be more fundamental in methods from the polymer formation stage. By this method, a polymer containing a crosslinkable group is obtained by adding a crosslinkable component to a monomer and polymerizing, and by causing the reaction of the group to occur only early during molding of the polymer. Thus, a cross-linked product that is smoothly molded can be obtained, and the object can be achieved.

The polyether amide of the present invention is based on such a viewpoint, and has at least the following formula [I]: (In the formula, R ₁ and R ₂ are H, --CH ₃ , --CF ₃ , Is one of the R _{3 to} R ₆ are any of H, a lower alkyl group and a lower fluoroalkyl group, and may be the same or different from each other. In addition, m is 1 or 2
Is. ] The crosslinkable polyether amide which has a structural unit represented by these.

2. At least the following formula [I] And formula [II] (In the formula, R ₁ and R ₂ are H, --CH ₃ , --CF ₃ , Is one of the R _{3 to} R ₆ are any of H, a lower alkyl group and a lower fluoroalkyl group, and may be the same or different from each other. In addition, m is 1 or 2
Is. Also, A ₁ is (In the formula, X ₁ is nothing, -CH _2- , -O-, -COO-, -S-,
-SO ₂ -, Is one of the R _{1 to} R ₆ and m are the same as above. ). ] It is providing the crosslinkable polyether amide which has at least 2 types of structural units represented by these.

[Action]

The polyetheramide of the present invention is synthesized by polycondensing a dicarboxylic acid component containing a crosslinkable monomer 5- (4-ethynyl) phenyloxyisophthalic acid dichloride with a diamine component. The crosslinkable monomer is a polymer of Chemistry Edition (Jour. Polymer Sci .: Po
lymer Chem. Ed.) 1985, 23, pp. 2234-2236.

As the acid component, it is preferable to use at least one of terephthalic acid dichloride and isophthalic acid dichloride, particularly the former. In addition, 4,4'-oxydi (benzoic acid chloride), 4,4'-methylenedi (benzoic acid chloride) 4,4'-carbonyldi (benzoic acid chloride), 4,4'-sulfonyldi (benzoic acid chloride) ,
4,4'-biphenyldicarboxylic acid dichloride) and the like may be added. These dihalides can be replaced by the corresponding dicarboxylic acids.

The crosslinkable monomer is preferably used in the range of 5 to 50 mol% of the acid component as much as possible. It is also possible to use it at a higher rate, but in that case, a molecule with a large number of bulky side chains will eventually be converted into a molecule with a dense cross-link by cyclotrimerization of the ethynyl group, resulting in elongation. It provides a polymer with less mechanical properties, similar to conventional thermosetting heat resistant resins. If the amount of the crosslinkable monomer is too small, the effect of the crosslinking reaction cannot be expected.

As the corresponding amine component, an aromatic diamine containing an ether bond is preferably used. For example, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane,
2,2'-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-chloro-
4- (4-aminophenoxy) phenyl] propane, 2,
2'-bis [3-promo-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-ethyl-
4- (4-aminophenoxy) phenyl] propane, 2,
2'-bis [3-propyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3 -Butyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-sec-
Butyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-methoxy-4- (4-aminophenoxy) phenyl] propane, 1,1'-bis [4-
(4 aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-promo-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane , Bis [3-chloro-4- (4-
Aminophenyloxy) phenyl] methane, bis [3-promo-4- (4-aminophenyl) phenyl] methane,
1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 1,1,1,3,3,3
-Hexachloro-2,2-bis- [4- (4-aminophenoxy) phenyl] propane, 3,3-bis [4- (4-
Aminophenoxy) phenyl] pentane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane,
1,1,1,3,3,3-hexafluoro-2,2-bis- [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3 -Hexafluoro-2,2-bis [3,5
-Dibromo-4- (4-aminophenoxy) phenyl]
Examples include propane and 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane. Among them, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly useful from the viewpoint of raw material circumstances and properties of the obtained polymer. Diamines different from the above types, preferably aromatic compounds such as m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline, 4,4 sulfonyldianiline, 4,4 ' Carbonyldianiline, 3,4 '
-Methylenedianiline, 4,4'-methylenedianiline and the like can also be used as part of the amine component.

Since the compounding ratio of the acid component and the amine component is related to the molecular weight of the polymer to be produced,
The acid component is preferably 0.9 to 1.2 equivalents, and it becomes difficult to obtain a high molecular weight polymer outside this range.

The polycondensation reaction between the dicarboxylic acid component and the diamine component is performed by cyclohexanone, N-methyl-2-methylpyrrolidone,
It can be proceeded smoothly in a solvent such as N, N-dimethylformamide or dimethylsulfoxide in the presence of an acid acceptor as desired. The reaction temperature at that time is not particularly limited, and may be appropriately selected depending on the intended use of the polymer produced. In general, when the reaction is carried out at a temperature of 10 ° C or lower for a long time, high molecular weight is achieved, whereas when the reaction is carried out at a high temperature for a short time, a polymer having a relatively low molecular weight is obtained. A coalesce is generated. The polymer is separated and purified by a known means such as non-solvent coagulation or washing.

The polyether amide resin of the present invention is molded at 300 ° C to 350 ° C, and at that time, the crosslinking reaction proceeds slowly.

The crosslinked polyetheramides of this invention have about 20% less than the uncrosslinked type.
It has a high heat distortion temperature of ℃ or more and is useful as a molding material, coating material, impregnating resin for laminates, etc.

〔Example〕

Example 1 A stirring rod, a thermometer and a dropping funnel were set in a 1000 ml three-necked flask, and 17.2 g of NaOH was dissolved in 80 ml of water and placed in the flask. Next, 73.0 g of 2.2-bis [4- (4-aminophenoxy) phenyl] propane was added to 340 g of cyclohexanone.
Was dissolved in and poured into the above flask, and cooled to -2 ° C. On the other hand, terephthalic acid dichloride 18.2 g and 5-
27.2 g of (4-ethynyl) phenyloxyisophthalic acid dichloride was dissolved in 240 g of cyclohexanone, and this acid chloride solution was poured into the flask from the dropping funnel, while ensuring that the reaction temperature did not exceed 10 ° C. The reaction was carried out for 4 hours. The reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N, N-dimethylformamide and poured into methanol to purify the polyamide polymer.

Reduced viscosity of this polymer (η _SP / c: dimethylformamide
A 0.2% by weight solution was measured at 30 ° C., and the measurement was conducted under the same conditions) 0.98. The heat distortion temperature (HDT) of the test piece of the polymer press-molded at 330 ° C. for 30 minutes was 221 ° C. The sample swelled with the solvent but did not dissolve.

Example 2 A 1000 ml three-necked flask was set with a stirring rod, a thermometer and a dropping funnel, and 17.2 g of NaOH was dissolved in 80 ml of water and placed in the flask. Next, 37 g of 2.2-bis [4- (4-aminophenoxy) phenyl] propane and 18 g of 4,4'-diaminodiphenyl ether were dissolved in 340 g of cyclohexanone, and the mixture was poured into the flask and cooled to -2 ° C. . On the other hand, 18.1 g of terephthalic acid dichloride and 14.5 g of isophthalic acid dichloride, 6.04 g of 5- (4-ethynyl) phenyloxyisophthalic acid dichloride were dissolved in 240 g of cyclohexanone, and this acid chloride solution was poured into the flask from the dropping funnel. At this time, the reaction was carried out for 5 hours so that the reaction temperature did not exceed 10 ° C. The reaction solution was poured into methanol to isolate the polymer. After drying this, it was dissolved in N, N-dimethylformamide and poured into methanol to purify the polyamide polymer.

The reduced viscosity of this polymer is 1.3, and the HDT of the press molded product is 21.
It was 4 ° C.

Example 3 A 10-separable flask was set with a stirring rod and a thermometer dropping funnel, and 171.8 g of NaOH was dissolved in 800 ml of water and placed in the flask. Next, 58.0 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to 340 g of cyclohexanone.
Dissolve in, pour into the flask and cool to -2 ° C. Meanwhile, 44.0 g of 5- (4-ethynyl) phenyloxyisophthalic acid dichloride is dissolved in 240 g of N-methyl-2-pyrrolidone. The acid chloride solution is poured from the dropping funnel, but the reaction temperature should not exceed 10 ° C. 3 hours after dropping, 2 g of benzoyl chloride
Is dissolved in 2 g of cyclohexanone and added. After a further 2 hours, the reaction solution was poured into methanol to separate the polymer. Furthermore, the reduced viscosity of the polymer after purification by the re-dissolution-precipitation operation was 0.65 dl / g, and the HDT of the press-molded sample was 243 ° C.
It was.

Example 4 A solution of the polymer prepared in Example 2 in 2% by weight in dimethylformamide was uniformly coated on a thoroughly washed polyethylene terephthalate film having a transparent conductive film at 3500 rpm using a spinner, After drying at ℃ for 10 minutes and evaporating the solvent, heat treatment was performed from 250 ℃ to 300 ℃ for 40 minutes to form a film with a thickness of 650Å. This film was rubbed with a felt in a certain direction to prepare a substrate filter having an orientation control film.

The alignment control films of the two films thus produced were arranged to face each other, and these films were adhered with a sealing agent made of a polyester adhesive to produce a liquid crystal display element. The sealing agent was cured at 120 ° C for 5 minutes. A phenylcyclohexane-based liquid crystal (ZLI-1132, manufactured by Merck & Co., Inc.) was placed between the orientation control films of this element, and the orientation of the liquid crystal was examined between two orthogonal polarizing plates. Shown (tilt angle 2.4 degrees).

Example 5 A 10% N-methyl-2-pyrrolidone-N, N-dimethylformamide (1: 1) solution of the polymer synthesized in Example 2 was prepared.

Next, the above varnish was dropped onto the element and the lead wire (including wire bonding) of the 1M bit D-RAM memory LSI (18 bins). After that, the temperature was raised from 100 ℃ to 300 ℃ for 2 hours and kept at 300 ℃ for 30 minutes, and 55μm on the device.
A thick coating was applied.

This LSI was sealed with an epoxy resin composition by transfer molding, and then subjected to a moisture resistance test (121 ° C., 2 atmospheric pressure in superheated steam for 2000 hours). The results were good and confirmed to be highly reliable. The soft error rate was 70 feet.

Example 6 In place of 58.0 g of 2,2-bis [4- (4-aminophenoxy (phenyl) propane] in Example 3, 1,1,1,3,3,3-
The polyetheramide was purified under the same conditions as in Example 3 except that 71 g of bis [4- (4-aminophenoxy) phenyl] hexafluoropropane was used. The polyetheramide has a reduced viscosity of 0.51 dl / g and the HDT of the press-molded sample is 247 ° C.
Met.

〔The invention's effect〕

According to the present invention, a heat resistant material having excellent moldability can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Susumu Era 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitate Manufacturing Co., Ltd.Hitachi Laboratory Ltd. Hitachi Research Laboratory (56) Bibliography Journal of Polymer Science, Polymer Chemistry Edition, 23 [8] (1985) p. 2233-2246

Claims (2)

[Claims] 1. At least the following formula [I]: (In the formula, R ₁ and R ₂ are H, --CH ₃ , --CF ₃ , Is one of the R _{3 to} R ₆ are any of H, a lower alkyl group and a lower fluoroalkyl group, and may be the same or different from each other. In addition, m is 1 or 2
Is. ] The crosslinkable polyether amide which has a structural unit represented by these. 2. At least the following formula [I]: And formula [II] (In the formula, R ₁ and R ₂ are H, --CH ₃ , --CF ₃ , Is one of the R _{3 to} R ₆ are any of H, a lower alkyl group and a lower fluoroalkyl group, and may be the same or different from each other. In addition, m is 1 or 2
Is. Also, A ₁ is (In the formula, X ₁ is nothing, -CH _2- , -O-, -COO-, -S-,
-SO ₂ -, Is one of the R _{1 to} R ₆ and m are the same as above. ). ] The crosslinkable polyether amide which has at least 2 types of structural units represented by these.