Thermally stabilized polyamide composition

 

(57) Abstract:

Use: manufacture of constructive purpose. The inventive composition comprises, by weight. h: heat stabilised polyhexamethylenediamine with a ratio of carboxyl and amine groups, equal to 1.2:1 to 1.8:1 - 67-73; bisphenolic antioxidant and 0.2-0.5; sterically hindered, resistant to hydrolysis triarylphosphite - 0,2-0,5; oligocarbonate 0,25-0,6, fiberglass - 27-33. 3 C. p. F.-ly. 4 so

The present invention relates to compositions based on thermally stabilized polyamides, mainly thermally stabilized to polyhexamethylenediamine (PA-66) and may find application in the manufacture of products for structural purposes, for example, for the manufacture of heat exchangers, including details of the cooling and heating of cars, tractors, etc., working in contact with antifreeze at low and high operating temperatures.

Traditional stabilizers for polyamides are a mixture of a halide of an alkali metal, mainly iodotope potassium, and compounds of transition metals, mainly salts of divalent copper.

In the domestic industry produced, the polyamide-66 and mixtures of these stabilizers, and a mixture of aromatic phosphite with spatial difficult phenol with targeted supplements /1/. Products made from this composition are operated in an environment of antifreeze operating temperature -40oC to +120oC. However, the level of mechanical properties (yield strength tensile, impact strength and other) after thermal aging, including antifreeze (glycol), not high enough for the manufacture of advanced heat exchange devices.

There is also known a method of stabilization of polyamides using as the stabilizer is a mixture of salts of copper, iodotope potassium phosphites and polycarbamide /2/. In this patent as polyamide use only the polycaproamide (PA-6), and as phosphites use of Tris(nonylphenyl)FOSFA, diphenylisobenzofuran, diisodecylphthalate and diisooctylphthalate.

Stabilizers introduced at the stage of synthesis. However, the introduction of fofanah stabilizers at the stage of synthesis of polyamide 66 is unacceptable, because in the presence of phosphites due to their hydrolysis branched structure formed of polyamide 66.

In addition, given in the claims phosphites are easily hydrolyzed, resulting in the received composizione in the examples.

Therefore, the composition of the invention by known also cannot be used for the manufacture of advanced heat exchangers operated at temperatures above 100oC. analysis of the current level of technology shows that the closest technical solution (prototype) is a polymeric composition /3/. Thermally stabilized polyamide composition containing an aliphatic polyamide stabilized with copper salts in combination with potassium iodide, the sterically hindered triarylphosphite General formula

< / BR>
where R1tert.butyl, 1,1-dimethylpropyl, cyclohexyl, phenyl;

R2and R3H, methyl, tert. butyl, 1,1 dimethylpropyl, cyclohexylphenol; bisphenolic antioxidant, fiber, and targeted supplements.

In accordance with the prior art (example 5 according to the patent) polyamide composition based on polyamide-12 contains 0.5% of a mixture of stabilizers include sterically hindered resistant to hydrolysis organic postit Tris (2,4-di-tert. butylphenyl)FOSFA and antioxidant bisphenola type - N,N'-hexamethylene-bis(3,5-decret. butyl-4-hydroxyhydrocinnamate) in a 1:1 ratio. While preserving 80% of the initial level of strength properties tensile when temperature is Oh, as shown by our research, the preservation of the strength properties in glycols or their aqueous solutions at temperatures above 100oWith insufficient.

Thus, none of the known technical solutions does not provide the required physical and mechanical properties and their preservation in the conditions.

In this regard, there is a technical problem to reduce the rate of drop of the strength properties of the material when used in glycol at a temperature above 100oC. This is achieved by thermally stabilized polyamide composition containing an aliphatic polyamide, thermally stabilized copper salts in combination with potassium iodide, sterically hindered, resistant to hydrolysis triarylphosphite, bisphenolic antioxidant and fiber, as the aliphatic polyamide thermally stabilized copper salts in combination with potassium iodide contains polyhexamethylenediamine with a ratio of carboxyl and amine groups of 1.2:1 to 1.8:1, and optionally the composition comprises oligarinternational General formula:

< / BR>
where n 10-20 or oligarinternational Stabaxol-R in the following components of the composition, wt. h:

Thermo is:1 67-73

Fiberglass 27-33

Bisphenolic antioxidant 0,2-0,5

Sterically hindered, resistant to hydrolysis triarylphosphite 0,2-0,5

Oligarinternational General formula

0,25-0,6

where n 10-20 or oligarinternational Stabaxol-R.

The composition may further contain additives target in the amount of up to 1.5 wt. h

As bisphenola antioxidant composition comprises N,N'-hexamethylene-bis-3,5-di-tert. butyl-4-hydroxyhydrocinnamate (III) or triethylene glycol-bis-3-(3-tert.butyl-4-hydroxy-5-were)propionate (IV).

As sterically difficult, resistant to hydrolysis triarylphosphite composition comprises Tris(2,4-di-tert.butylphenyl)fosfat (I) or Tris (2,6-di-tert.butyl-4-were)fosfat (II).

Oligoribonucleotide represent a powdery substance white; the softening temperature of from 60 to 165oC; Srednekanskaya molecular weight, determined ebullioscopic in chlorobenzene, are 1100-20000.

To obtain oligocarbonate to 4,4'-diphenylmethanediisocyanate in an inert solvent (toluene) is added the catalyst for the decarboxylation (2-3% phospholine or phospholidine).

Response check the NAT, the ratio of diisocyanate: a blocking agent is from 2:1 to 50:1.

< / BR>
n 10-20

"Stabaxol-R" has the following chemical formula

< / BR>
where n 10-20.

Using oligoamenorrhea, especially when mixed with the bisphenol containing in the structure of the amide group, is providing a synergistic effect in thermally stabilized compositions based on PA-66 at a certain ratio of carboxyl and amine groups due to better compatibility with the polyamide.

As shown by our research, the use of a mixture of oligoanalgesia with a degree of polymerization of 10-20 with bisphenol containing an amide group, in proportions that are beyond the stated ratios, leads to a significant decrease in strength properties as in the dry test, and operating conditions of the glycol at elevated temperatures (see examples 14, 15).

The same result is observed when using PA-66 with a ratio of [COOH] and [NH2] groups beyond the boundaries of 1.2 to 1.8:1 (see examples 16, 17). The effect of a non-additive increase of the strength properties of the composition under operating conditions due to sharing oligoamenorrhea and besenoseje.action new level of technology.

The invention is illustrated by the following examples.

Example 1. Pre-mixed in the mixer dried, thermally stabilized idestam potassium and copper acetate of polyhexamethylenediamine (PA-66) with a ratio of [COOH][NH2] 1,4 TU N 6-06-15-88 in the amount of 70 wt. with 0.25 m Tris (2,4-di-tert. butylphenyl)postitem (1) (IRGAFOS 168), then added a mixture of bisphenol-N, N'-hexamethylenebis(3,5-di-tert.butyl-4 hydroxyhydrocinnamate (III) 0,25. (Irganox 1098) oligoamenorrhea 0.5. with a degree of polymerization of 10 (Stabaxol-R).

The mixture is fed to the twin screw extruder where it is mixed and homogenized. Then in the melt serves 30 wt. fiberglass and the mixture ekstragiruyut when the temperature of the melt has reached 270-290oWith subsequent granulation and drying. Samples for testing are made by casting under pressure modes specified in THE 6-06-15-88.

Properties of the resulting composition are shown in table 1.

Examples 2-9 carried out in accordance with the invention, analogously to example 1.

Example 10. Pre-mixed in the mixer thermally stabilized PA-66 with a ratio of terminal [COOH][NH2] groups of 1.4 (TU N 6-06-15-88) in an amount of 70% from 0.25% of Tris(2,4-di-tert.butyl is himeda (n 20). The mixture is fed to the twin screw extruder where it is mixed and homogenized. Injected into the melt 30% fiberglass. The mixture is extruded at a temperature of the melt has reached 270-290oWith subsequent granulation and drying.

Examples 11-13 is carried out in accordance with the invention with separate introduction of bisphenola and oligoamenorrhea, analogously to example 10.

Examples 14-20 carried out analogously to examples 1 and 10 when the content and the characteristics of the components beyond the stated intervals.

Examples 21 and 22 are known from the prior art.

Formulation and properties declared and known compositions are given in table 1.

Test samples carried out by the following methods:

the aging of standard samples for 14 days. at 140o(A) OST 6-05-452-80;

the aging of the standard samples in the monoethylene glycol within 72 hours. when 135oWith the method of accelerated testing of glass fibre reinforced PA 66 on resistance to antifreeze firm Sofico (b);

the aging of the melt in the heating cylinder device for determining the melt flow (IIRC) at a temperature of 275oTo download 7 g of the polymer and kept at this temperature under a load of 1.2 kg over 40 is th viscosity of laboratory methods;

impact strength in the initial state and after aging (a) GOST 464780;

ultimate tensile stress tensile in the initial state (a) and after ageing (b) GOST 11262-80;

the relative viscosity of a solution in 96% sulfuric acid at 25oFrom the source and after ageing (in) GOST 11034-82;

the number of solution viscosity of the polyamide in 96% sulfuric acid source and after ageing (b) laboratory method.

As can be seen from the table, the operating conditions of the glycol at a temperature of 135-140oWith in compositions using published correlations toughness increases (examples 1-13), while known compositions (examples 21, 22) it decreases; ultimate tensile stress tensile them in 2-3 times above, than in the known compositions; reducing the viscosity number does not exceed 15% of the initial value, whereas in the known compositions, the value of reduction 30-45%

When the content of components that are beyond the stated ratios (examples 14-20) in the above conditions is a decrease in the strength properties, especially the destructive tensile stress in 2-4 times.

1. Thermally stabilized polyamide composition is difficult ski, resistant to hydrolysis triarylphosphite, bisphenolic antioxidant and fiber, characterized in that as the aliphatic polyamide thermally stabilized copper salts in combination with potassium iodide, the composition contains polyhexamethylenediamine with a ratio of carboxyl and amine groups of 1.2 to 1.8:1, and optionally the composition comprises oligarinternational General formula

< / BR>
where n 10 20,

or oligarinternational Stabaxol R in the following ratio of the components of the composition, wt.h.

Heat stabilised polyhexamethylenediamine with a ratio of carboxyl and amine groups of 1.2 to 1.8:1 67 73

Bisphenolic antioxidant 0,2 0,5

Sterically hindered, resistant to hydrolysis triarylphosphite 0,2 - 0,5

Oligarinternational specified formula or Stabaxol R 0,25 0,6

Fiberglass 27 33

2. The composition according to p. 1, characterized in that it further contains a special additive in the amount of up to 1.5 wt.h.

3. The composition according to PP. 1 and 2, characterized in that as bisphenola antioxidant contains N,N1-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) or triethylene glycol-bis-3(3-tert-butyl-4-hydroxy-5-were)propionate.

 

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