JPS6019773B2 - Aromatic polyamide copolymer - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel aromatic polyamide copolymer.

More specifically, it relates to an aromatic polyamide copolymer containing terephthalic acid and isophthalic acid as dicarboxylic components, a diamine containing two ether bonds and four benzene nuclei, and a diamine containing two benzene nuclei as diamine components. . Aromatic polyether amide resin, which uses terephthalic acid and isophthalic acid as dicarboxylic acid components and diamine containing two ether bonds and four benzene nuclei as the diamine component, has mechanical properties such as tensile strength, bending strength, and impact strength. Although this resin has excellent electrical properties such as arc resistance, yield rate and yield loss, chemical resistance, abrasion resistance, flame retardance, and dimensional stability, it has insufficient moldability. be.

The present inventors have arrived at the present invention as a result of intensive studies aimed at improving the moldability of aromatic polyetheramide.

That is, the aromatic polyamide copolymer of the present invention has the following formula (
1) to (W), (1) (b) (m) (W) [In the above formulas (1) to (N), R, to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine. and may be the same or different from each other.

R5 and R6 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. X is -CH2-, 10- or 1S02-, and is bonded to the benzene nucleus at the meta or para position relative to the nitrogen atom. ], the carbonyl group (=C=○) of the unit of formula (1) and formula (0) is replaced by the imino group (=NH) of the unit of formula (m) or formula (W). and the imino group of the unit of formula (m) and formula (W) is bonded to the carbonyl group of the unit of formula (1) or formula (b) in the bonding order of formulas (1) to (W). has no regularity, and p ke for formula (1), formula (n)
has q for formula (m), r for formula (m), and s for formula (W), p:q is 2:8, none is 8:2, and r
:s is Satoshi: 2 none, 70:30, p 10 q + r +
It is characterized in that s is 20 or more.

The above "p1q+r1s and 20" is a descriptive expression that can be replaced with the molecular weight of the copolymer of the present invention. Usually, one equivalent of the acid component reacts with one equivalent of the diamine component.

In this case, the diamine components are formulas (m) and (N), and the acid components are formulas (1) and (D). Therefore p+q±r+s
= 20 or more / 2 = 10 or more, that is, the degree of polymerization is 10 when (Ar; or AJ' is or R, ~R6, and the operations indicated by That's all.

In this way, the degree of polymerization is 10 or more, but the molecular weight varies depending on what Ar' is selected, and r/s = 70.
/30, r+s=10, R, ~R6 are all hydrogen, X is C
In the case of H2, the molecular weight is the smallest, 4573.

In other words, the aromatic polyamide copolymer according to the present invention is an aromatic poly-IJ amide copolymer having a molecular weight of 4573 or more and containing a return unit.

As shown in the examples described later, the intrinsic viscosity is 0.78 d'/t, 0.
In the case of 73 d'/unit and 0.74 d'/unit, the number average molecular weight is 12,000 to 16,000.

The diamine component for obtaining the copolymer of the present invention is represented by the following two general formulas.

(In both formulas, R, ~R6, x have the same meanings as those in formulas (m) and (W), and X and N ratio are in a meta- or para-position relationship.

) The aromatic polyamide copolymer of the present invention has significantly improved moldability and exhibits extremely excellent mechanical performance compared to a polymer in which the diamine component is only a diamine represented by the general formula.

For example, it has excellent impact strength, tensile strength, bending strength, abrasion resistance, hardness, electrical properties, and flame retardancy. Specific examples of aromatic diamines represented by the general formula used in the present invention include 2,2-bis[4
1(4-aminophenoxy)phenyl]propane, 2.
2-bis[3-methyl-4-(4-aminophenoxy)
phenyl]propane, 2,2-bis[3-chloro4-(4-aminophenoxy)phenyl]propane, 2,2
-bis[3-bromo4-(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, 2,2-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-pis[3,5 -dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[
3,5-dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-pis[3,5-dibromo4
1(4-aminophenoxy)phenyl]propane, 2.
2-bis[3,5-dimethoxy4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro4-(4-aminophenoxy)-5-methylphenyl]propane, 1,1-bis [4-(4-aminophenoxy)phenyl]ethane, 1,1-pis[3-methyl-4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis[3-chloro4-(4-aminophenoxy)]
phenyl]tan, 1.1-bis[3-fromo-41 (
4-aminophenoxy)phenyl]ethane, 1,1-bis[3-ethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-propyl-4-(4-
aminophenoxy) phenyl]ethane, 1,1-bis[
3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(
3-sec-butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methoxy-4-(
4-aminophenoxy)phenyl]ethane, 1,1-bis[3-ethoxy4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl] Ethane, 1.1-
Bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]ethane, 1
・1-bis[3,5-dimethoxy4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4 -(4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4-
aminophenoxy)phenyl]methane, bis[3-chloro4-(4-aminophenoxy)phenyl]methane,
Bis[3-furomo-4-(4-aminophenoxy)phenyl]methane, bis[3-ethyl-4-(4-aminophenoxy)phenyl]methane, bis[3-propyl-4
-(4-aminophenoxy)phenyl]methane, bis[
3-isopropyru-4-(4-aminophenoxy)phenyl]methane, bis[3-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-sec-butyl-4-(4-aminophenoxy)phenyl] methane,
Bis[3-methoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-ethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy) c) phenyl]methane, bis[3,5-dichloro4-(4-aminophenoxy)phenyl]methane, bis[3,5-dibromo4-(4-aminophenoxy)phenyl]methane, bis[3
・5-dimethoxy4-(4-aminophenoxy)phenyl]methane, bis[3-chloro4-(4-aminophenoxy)-5-methylphenyl]methane, 1.1.1
・3・3・3-Hexafluoro2・2-bis [41(
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-hexachloro-2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 3,3-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane , 1・1-bis [3
・5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.3-hexafluoro2.2-bis[3.5-dibromo4(4-aminophenoxy) ) Phenyl] Pro/Gun, 1・1・1・3・
3,3-hexachloro2,2-bis[3,5-dibromo4-(4-aminophenoxy)phenyl]propane, 3,3-bis[3,5-dibromo4-[4-aminophenoxy] phenyl]pentane, 1,1-bis[3,
5-dibromo 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3-methyl-4
-(4-aminophenoxy)phenyl]butane, 2.2
-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]butane,
Examples include 1,1,1,3,3,3-hexafluoro2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane.

Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is representative. if,
If desired, mixtures of the above diamines can be used. Specific examples of aromatic diamines represented by the general formula [B} used in the present invention include 4,4-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfoso, and 4,4-diaminodiphenyl. Sulfone, 4.4
-diaminodiphenyl ether, etc., but the commonly produced and representative ones are 4,4'-diaminodiphenyl methane and 4,4-diaminodiphenyl ether, with the latter being preferred from the viewpoint of heat resistance.

The aromatic polyamide copolymer of the present invention can be produced by polymerizing terephthalic acid, isophthalic acid, or functional derivatives thereof and the diamines by a solution polymerization method, a melt polymerization method, or JP-A-52-12.
3198, by any known aromatic polyamide synthesis method.

The proportion of the diamines represented by the above general formula to the total diamines is preferably 2 to 30 mol%.

If the proportion of the diamine represented by the general formula (B} is less than 2 mol%, the effect of improving moldability will not be sufficient, and conversely, even if it is greater than 30 mol%, the melting temperature will become too high, This is not preferable because it has a negative effect on moldability.
In order to improve the heat resistance, weather resistance, etc. of the aromatic polyamide copolymer of the present invention, a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber may be present in the resin composition.

In addition, plasticizers, pigments, lubricants, etc. may also be present. The aromatic polyamide copolymer of the present invention can be made into powder, chips, or other shapes, and can be used to make various useful products by commonly known plastic molding methods such as press molding, injection molding, and extrusion molding. I can do it.

Examples of such products include gears, bearings, electrical parts containers, etc. As described above, the aromatic polyamide copolymer of the present invention can be used as an engineering plastic in applications requiring high performance. Next, the present invention will be explained in more detail using Examples.

Example 1 In a separable flask, set a thermometer and a dropping funnel. Dissolve 171.8 g of NaOH in 800 g of water and pour into the flask.

Next, 594 g of 2,2-pis[4-(4-aminophenoxy)phenyl]propane and 66 g of 4,4-dianodiphenyl ether were dissolved in 3.4 k9 of cyclohexanone, poured into the flask, and poured into the flask. Cool to 200 ℃. On the other hand, 182 parts of terephthalic acid dichloride and 182 parts of isophthalic acid dichloride were mixed with 2.4 parts of cyclohexanone.
Soluble in k9. This acid chloride solution is poured through the dropping funnel, making sure that the reaction temperature does not exceed 10°C. 3 hours after dropping, penzoyl chloride 18.9
Dissolve 200 g of cyclohexanone and add. After another 2 hours, the reaction solution is poured into methanol to isolate the polymer. After drying, it is granulated using an extruder, and the intrinsic viscosity is 0.78 d'/min (dimethylformamide solution, 300 d'/min).
0, the same applies hereafter) Obtain a pellet. A test piece was prepared using a 4.5 ounce screw type injection molding machine, and a physical property test was conducted.

The results are shown in the table below. When the infrared absorption spectrum of this polymer was measured, stretching vibrations of the amide carbonyl group were observed near 1660 k-1, and stretching vibrations of the aromatic ether bond were observed near 1230 k-1. Example 2 A test was carried out using the same equipment and method as in Example 1 using raw materials having the following composition.

The results are shown in the table below. The intrinsic viscosity of the resulting pellet was 0.73.

NaOH 159
．． 4 ta water 800'4,4-diaminodiphenylsulfone 33 evening 2.
2-pis[4-(4-aminophenoxy)phenyl]propane 627 cyclohexanone 3.4k9 terephthalic acid dichloride 171 terephthalic acid dichloride 171 cyclohexanone
2.4k9 Penzoyl chloride
17.5 Tacyclohexanone
Example 3 The same method as in Example 1 was carried out using raw materials having the following composition.

The results are shown in the table below. The intrinsic viscosity of the obtained pellet was 0.74/h.

NaOH 162.
6 ta water 800 skin 4
・4'-diaminodiphenylmethane 33rd evening 2.2
-Bis[4-(4-aminophenoxy)phenyl]propane 627 Tacyclohexanone
3.4k9 Terephthalic acid dichloride 172 Tysophthalic acid dichloride 172 Tacyclohexanone
2.4k9 Penzoyl chloride
17.9 Tacyclohexanone
500 ta Comparative Example Using raw materials with the following composition,
The same apparatus and method as in Example 1 were used.

The results are shown in the table below. The intrinsic viscosity of the resulting pellet was 0.76.

Claims (1)

[Claims] 1. The following formulas (I) to (IV), (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Numerical formulas, chemical formulas , tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formulas (I) to (IV), R_1 to R_4 represent hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine. , may be the same or different. R_5 and R_6 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. X is -CH_2
-, -O-, or -SO_2-, and is bonded to the benzene nucleus at the meta- or para-position relative to the nitrogen atom. ], the carbonyl group (=C=O) of the unit of formula (I) and formula (II) is replaced by the imino group (=NH) of the unit of formula (III) or formula (III). Formulas (I) to (IV) except that the bond and the imino group of the unit of formula (III) and formula (IV) are bonded to the carbonyl group of the unit of formula (I) or formula (II).
has no regularity in the bonding order, and for formula (I) p
ke, q for formula (II), r ke for formula (III),
Formula (IV) has s, and p:q is 2:8 to 8:
2, r:s is 98:2 to 70:30,
An aromatic polyamide copolymer, characterized in that p+q+r+s is 20 or more. 2 R_1 to R_4 of the units of formula (III) are hydrogen,
The aromatic polyamide copolymer according to claim 1, wherein R_5 and R_6 are methyl groups. 3. The aromatic polyamide compound according to claim 1 or 2, wherein Polymer.