JPS59131628A - Preparation of polyether amide - Google Patents

Abstract

PURPOSE:To obtain a polyether amide having improved flexibility, good low- temperature impact resistance, solvent resistance, etc. and improved heat resistance, by subjecting a polyamide-forming monomer, a polyalkylene containing an end amino group, a diamine and a dicarboxylic acid to polycondensation. CONSTITUTION:(A) A polyamide-forming monomer (e.g., amino-dodecanoic acid, etc.), (B) a polyoxyalkylene containing an end amino group [e.g., bis(3-aminopropyl)polytetrahydrofuran, etc.] shown by the formula (R<1> and R<2> are >=3C alkylene; n is 2-60), (C) an aliphatic, alicyclic or aromatic diamine (e.g., dimer diamine, etc.), and (D) a dicarboxylic acid (e.g., dimer acid, etc.) in an amount almost equivalent to the amine group of the components B and C are subjected to polycondensation by a conventional method, to give the desired polyether amide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyether amide, particularly a polyether amide having excellent heat resistance.

It is known that dyeability, hygroscopicity, antistatic properties, etc. can be improved by incorporating an ether component into polyamide.

Extrusion by specifying the polyether component.

A method for producing injection moldable polyether amide has been reported (Japanese Patent Application Laid-open No. 136424/1983).

By this method, a polyether amide with good water resistance, temperature stability, solvent resistance, and low-temperature impact resistance has been obtained.

However, if polyether chains are incorporated into polyamide to such an extent that it can actively exhibit properties such as flexibility and good low-temperature impact resistance, it is undeniable that the heat resistance will deteriorate due to its structure. Therefore, it is necessary to pay close attention to the narrow range of polymerization conditions and molding conditions, as well as to increase the coloring and molecular weight.

This becomes a factor that causes a decrease in elastic modulus, etc.

An object of the present invention is to provide a novel method for producing polyetheramide that has improved surface/thermal properties while maintaining various properties such as flexibility, low-temperature impact resistance, ice cutting properties, and solvent resistance. .

According to the invention.

(A) Polyamide-forming monomer.

(Formula 19 H2N-R'-0-+R20%R'-NH2
(In the formula, R1 and R2 are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60.)

(C) a diamine selected from aliphatic diamines, alicyclic diamines and aromatic diamines, and (D) CB)
There is also provided a method for producing a polyether amide, which comprises subjecting the amine groups of (C) to pentapolymer condensation with approximately a light amount of dicarboxylic acid.

Examples of the polyamide-forming monomer (A) include ω-lactams, ω-aminocarboxylic acids, and salts of cyamine and dicarboxylic acids. A specific example of an ω-lactam is
cabrolactano, enanotractam, decalactam,
Landecalafta 11 and dodecalactam are mentioned.

Specific examples of ω-aminocarboxylic acids include 6-aminocagulonic acid, 10-aminodecanoic acid, 11-aminolanticanoic acid, and 12-aminododecanoic acid. Specific examples of salts of diamine and dicarboxylic acid include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, untecamethylenediamine, and dodecamethylene/diamine.

2.2.4-72,4.4-) Limethylhexamethylene/diamine, 1. 1. Cyamines such as 4-bis(aminomethyl)cyclohexane, bis(4,4'-aminochlorohexyl)methane, m-/p-xylylenediamine, and sulfuric acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, speric acid, azelaic acid, sepa7
salts with dicarboxylic acids such as todecane-E-11.4-cyclohexanedicarboxylic acid, terephthalic acid, and inophthalic acid.

(3. Terminal amine polyalkylene - white m (B) is,
It has linear or branched oxy/alkylene repeating units with a carbon number or more in the molecular chain, and has amine groups at both ends of the molecular chain.1 For example, propylene 2'-quizite, tetrahydrofurano alone Alternatively, it can be synthesized by introducing an amine group at the end of a polymer obtained by copolymerization. The terminus terminus (B) includes a polymer having at most 50 moles of oxyethylene repeating units in the cO main chain. Specific examples include polyoxyprohinamine, bis(3-
(aminopropyl) polytetrahydrofuran.

Specific examples of cyamine (C) include ethylenediamine,
Trimethylenediamine, tetramethylenenonamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, dimer diamine (oleic acid,
Dimeric aminated products of unsaturated fatty acids such as linoleic acid and lylunic acid).

2.2.4-/2,4.4-) aliphatic diamines such as lymethylhexylylene diamine; 1,3-71,
4-bis(aminomethyl)cyclohexane, bis(a
, 47-amylanchlorohexyl)methane, and aromatic diamines such as m/p-xylylene diamine. Among these diaminos, dimer diamines are preferably used.

A specific example of dicarboxylic acid (D) is shiulic acid.

Succinic acid, glutaric acid, adipic acid, pimelic acid.

Speric acid, azelaic acid, dodecanoic acid, 1,4-chlorohexanedicarboxylic acid, terephthalic acid.

Isophthalic acid, a long chain dicarboxylic acid listed below.

HOOC(CH2), 4COOH, Hooc(cH2)
5aH(aH2)6cooH.

H2CH3 HOOC(CH2)6 CH= CH(CH2)6 C
0OH, HOOC(CH2)5 CH(CH2')6
C00H1H-CH2 Hooc(cH2), 8coon, HOOC(CH2
)50H(CH2), oCOOH.

HCH3 HOOC(CH2)6CH= OR(CH2)2 CH
= CH(CH2)6 C00H1HOOC(C!H,
, )5CH(CH2)20H= CH(CH2)6CO
Oh.

CH= CH2 Fortune H3 C)! 3 Preferred dicarboxylic acids in the present invention have 8 carbon atoms.
It is a trimerized aliphatic dicarboxylic acid (dimer acid) obtained by campling 1 to 24 monobasic fatty acids, such as oleic acid, linoleic acid, lylunic acid, etc. Among dimer acids.

From the viewpoint of reducing the degree of coloration of the produced polyetheramide, those with a low degree of unsaturation are particularly preferably used [11].

In the present invention, the above (A), , (B), (0)
and (D) are polycondensed to produce polyetheramide.

The ratio of component (A) used to all components is preferably 15 to 95% by weight, particularly 40 to 90% by weight. The ratio of component (B) used to the total amount of component (B) and component (0) is preferably 30 to 90% by weight, particularly 40 to 80% by weight. Component (D) is used approximately in proportion to the amine groups of component (B) and component (C).

Polycondensation is carried out by known methods. For example, 150-35
Melt polycondensation is carried out at a temperature of 0°C, preferably 200 to 000°C. When a salt of a lactam or a diamine and a dicarboxylic acid is used as component (A), an appropriate amount of water is coexisted, and polycondensation is started under pressure in a pressurized container with a width of about 1 to 5 degrees K7/-. Depending on the situation, the pressure may be reduced to complete the heating polycondensation.

When ω-aminocarboxylic acid is used as component (A), polycondensation is started under normal pressure and, if necessary, the heating polycondensation is completed under reduced pressure.

The polyetheramides according to the invention can contain additives such as antioxidants, light and heat stabilizers, flame retardants, pigments, fillers, glass fibers and the like. These gun cuttings can be added during or after the single line combination.

The polyether amide obtained by the present invention can be easily processed and provides molded products with excellent heat resistance, water resistance, flexibility, low-temperature impact resistance, and rubber elasticity. Such molded products include injection molded products, pipes, hoses, and profiles.

Examples include extruded products such as notebooks, monofilaments, and fibers. The polyetheramides according to the invention can also be used as coating materials. Furthermore, the polyether amide according to the present invention has good compatibility with polyamide resins, and when used in a blend with polyamide resins, its impact resistance, flexibility, and elasticity can be significantly improved.

The present invention will be explained below with reference to Examples. In addition.

In the examples, "1 part" means "part by weight". Solution viscosity (ηr) for eye A is 25°C, o, 5wt in metacresol.
11fi+1 was determined by /vo/=%. The melting point (Tm) and the 0' jj -y transition point (T7) were measured by DSC. The polymer was formed into a film by hot pressing, and the tensile properties of the bone-dry film were determined at 24°C and a relative humidity of 65%. or.

Thermal stability was measured using a differential thermal balance.

Example 1 15.0 Oo parts of ω-aminododecanoic acid, bis(ro-aminopropyl)polytetrahydrofuran (BASF
Co., Ltd., average molecular weight: approximately 750) 5.685 parts, dimer diamine (manufactured by Henkel Japan) 2.467 parts, and dimer acid (manufactured by Emery Co., Ltd., Empol 1010)6.
878 parts were charged into a reaction vessel equipped with a stirrer. This is 24
After polycondensation was carried out at 0° C. for 4 hours under a nitrogen atmosphere, the mixture was cooled to obtain a pale yellow, flexible and tough polymer.

Comparative Example 1 (15.000 parts of V-aminototicanic acid, 8.471 parts of bis(3-aminopropynolypolytetrahydrofuran) and 6.529 parts of dimer acid were charged into a reaction vessel equipped with a stirring device. This was heated at 200°C in a nitrogen atmosphere. After heating for a while at the bottom, it was heated to 270 IC over 1 hour.

The mixture was heated for a further filtration period to complete the polycondensation.

Example 2 15.230 parts of ω-aminototicanic acid, Boriogyi/propylene amine (manufactured by Diefferono Chemical Co., Ltd., Jeffermine D-2ooo)7. o6+ part.

6.027 parts of dimer diamine and 5.14 parts of dimer acid
Two parts were charged into a reaction vessel equipped with a stirrer. This is 24.0
After polycondensing for 4 hours under C1 nitrogen atmosphere, cooling
A pale yellow, flexible and tough polymer was obtained.

Comparative Example 2 15.000 parts of ω-aminototicanic acid, 11.637 parts of polyoxypropylene amine, and 363 parts of dimer acid
Polycondensation was carried out in the same manner as in Example 2.

Table 1 shows the results for the male side and comparative example.

Example 50.000 parts of ω-aminododecanoic acid, 1 portion of bis(3-aminopropyl)polytetrahydrofuran, 281 parts,
4.4.2 parts of hexamethylene diamine and 32.292 parts of dimer acid were charged into a stirrer and a reactor and polycondensed at 240°C under a nitrogen atmosphere for 6 hours. A pale yellow, flexible and IW polymer was obtained.

The ηr obtained by removing the 6th fraction extracted by Knoxhlet extraction with methanol for 8 hours was 1.57. The Tm of the polymer after extraction is 143°C, T? The temperature was -56°C.

Also, the tensile strength is 150 Kg/ct? r, elongation is 470
Person in charge.

The tensile modulus &'+i was 2150 and 9/CA.

Example 4 15.000 parts of ω-aminododecanoic acid, 856 parts of bis(ro-aminopropyl)polytetrahydrofuranf, 6.366 parts of dimer diamine, 3.781 parts of dodecanoic acid
Part was polycondensed in the same manner as in Example 1. A pale yellow, flexible and tough polymer was obtained.

Its characteristics are shown below.

Thermal methanol extraction rate 4.7% ηr, 1.67Tm
148℃ Ty 65℃ Tensile strength Self-Kg/air Elongation 610゜Tensile modulus
121 oKy/ah Patent applicant Ube Industries, Ltd.

Claims (1)

[Claims] (A) Polyamide-forming mo/7- (B) 2H2N
-R'-o(R"o%R' -NH2 (in the formula + R
' and R2 are each an alkylene group having 3 or more carbon atoms, and n is 2 to 60. ) is a terminal acupuncture point or Lukiren-spider = insect. (C) aliphatic diamine/diamine selected from alicyclic diamine and aromatic diamine, and (D) (B)
and (C) a method for producing a polyether amide, which comprises condensing 9 dicarboxylic acids in an approximately equivalent amount to the amine groups.