Polymer composition

 

(57) Abstract:

The invention relates to the chemistry and technology of macromolecular compounds, in particular to composite polymeric materials that can be used in various sectors of the economy where these materials have high requirements for such properties that allow you to composite materials to withstand prolonged exposure to harsh factors of the cold climate and deep solar UV radiation with minimal loss of physical and mechanical properties. The inventive polymer composition comprises, by weight. % : polyamideimides 4-phenyl - 2,2, 5,5-tetramethyl-3-imidazoline-3-oxide-1-oxime 1.0 to 1.5; soot 0.9 to 1.0. table 1.

The invention relates to the chemistry and technology of macromolecular compounds, in particular to composite polymeric materials that can be used in various sectors of the economy where these materials are subject to high requirements, in particular, to such properties, which allow composite materials to withstand prolonged exposure to harsh factors of the cold climate and deep solar UV radiation with minimal loss of physico-chemical, MTSA ensuring long-term performance of products based on them in extreme climatic conditions of the Far North with a sharp seasonal temperature extremes from -70 to 40aboutC.

Known polyamides by solid state polycondensation in a stream of inert gas on the basis of diamines and dicarboxylic acids, in particular obtained by the polymerization of-caprolactam, or on the basis of the diamine and sabatinovka acid. But all the manufactured polyamides are not stable to the influence of factors of the cold climate and deep UV radiation.

Known also polyamideimides obtained by polycondensation in the melt based on bis-o-phenylendiamine, diphenyl ether dicarboxylic acid and diamine, based on the specified polymers having high molecular weight (CR=3,0-6,00 DL/g HCOOH), are characterized by high physical and mechanical strength properties, flexibility and elasticity. Compression-based materials have ap= 30-55 MPa, Ep= 3-6%.

The closest in technical essence to the achieved positive effect is material, comprising heterocyclic polymer - polybenzimidazole and 4-phenyl-2,2',5,5'-tetramethyl-3-imidazoline-3-oxide-1-oxime.

The disadvantages of the known synthetic polymeric materials on the basis of the above polyamides and polybenzimidazoles closely in cold climates and deep UV radiation is observed whitening samples after 9-12 months of exposure on the surface of the material cracks, which leads to the destruction of material;

if polyamideimides compression material equivalents during the year 2 times reduced, after 12-18 months. exposure on the sample surface gets scratched and cracked, which also leads to the destruction of the material;

compression-based materials polybenzimidazole containing 4-phenyl-2,2', 5,5'-tetramethyl-3-imidazoline-3-oxide-1-oxime in the same conditions almost retain their strength properties for 2 years, but further exposure they become brittle.

The aim of the invention is to stabilize the physical-mechanical properties of polybenzimidazole in cold climates and harsh UV radiation and expansion of assortment of composite materials.

This objective is achieved in that polyamideimides (PABI), obtained by polycondensation of aromatic tetraamines, diphenyl esters of dicarboxylic acids and diamines or-caprolactam in the melt when heated in a current of inert gas dissolved in concentrated formic acid or dimethylformamide with stirring, add as a hundred the AC.%.

Stirring is continued until a homogeneous suspension and subjecting it to heat treatment for 1.0 to 1.5 hours at a temperature of 20-50aboutC. Later in suspension add ammonia solution for planting fine powder polyamideimide, separate stable powder on a filter, washed with water and dried.

Polyamideimide press the pressed powders by direct extrusion at temperatures 180-260aboutWith and specific pressure of 800-1000 kg/cm2and get the compression materials having sourcep= 65-85 MPa, Ep= 3.5 to 4.5% . "After the impact of cold climate and deep UV radiation during the exposure in a period of 36 months in the conditions, Yakutsk compression materials have high physical and mechanical strength parameters:p49-63 MPa, Ep= 2,5-3,2%.

For the synthesis of polyamideimides can be used bis-o-phenylendiamine different structure, preferably, as 3,3'-diaminobenzidine, 3,3', 4,4'-tetraaminodiphenyl, 3,3',4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraaminodiphenyl and diphenyl esters of adipic, sabatinovka acids, various diamines, preferably hexamethylenediamine were>/BR>H - O

Melting point 103-105aboutC.

Decomposition temperature 170-190aboutC.

The proposed method is confirmed by the following examples.

P R I m e R 1. A mixture of 34,545 g (0.15 mol) of 3,3',4,4'-tetraaminodiphenyl (TDFA), 44,73 g (0.15 mol) diphenylacetate (DFA) and to 11.31 g (0.10 mol) of caprolactam (CL) is loaded into the condensation tube, repeatedly pulling her inert gas: the test tube is placed in a bath heated to 200aboutC. the Reaction mixture is melted, then the temperature within 1.0 to 1.5 h up to 270aboutC and maintained at this temperature for 4 h, then the reaction system create a vacuum of 1.0-2.0 mm RT.article and the reaction continues even 1,0 h at the same temperature. The yield of copolymer is almost quantitative.CR= 4,76 DL/g in concentrated HCOOH, C = 0.5 g/DL, 20aboutC). The copolymer is soluble in cold sulfuric and formic acids, amide solvents, tricresol.

The polymer is dissolved in the condensed formic acid, adding with stirring to 1.0% stabilizer - 4-phenyl-2,2',5,5'-tetramethyl-3-imidazoline-3-oxide-1-oxime and 1.0% carbon black by weight of the polymer, subjecting the heat-treated for 1.0 hour at a temperature of 20-50aboutWith until a homogeneous suspensiononly press the powder on the filter, washed with water and alcohol, dried in a Cabinet at 100-120aboutC.

The resulting powder was pressed into the mold by the method of direct compression at 240-260aboutWith and specific pressure of 800-1000 kg/cm2and get the compression material having the original ultimate tensile stress tensile p= 75-85 MPa and elongation at break Ep= =4,0%. "After the impact of cold climate for 3 years p60-63 MPa, Ep= 3,2%.

The method of obtaining polyamideimides and preparation of polymer compositions in examples 2-4 is similar to example 1.

P R I m m e R 2. Weighed the same as in example 1, the stabilizer 1.5 wt. % + carbon black and 1.0 wt.%pand Epin table.1.

P R I m e R 3. Weighed the same as in example 1, the stabilizer of 1.0 wt.% + soot 0.9 wt.%pand Epin table.1.

P R I m e R 4. Weighed the same as in example 1, the stabilizer 1.6 wt.% + carbon black and 1.0 wt.%pand Epin table.1.

P R I m e R 5. A mixture of to 23.03 g (0.10 mol) of TADPO, are 11.62 g (0.10 mol) of the diamine (GMI) and to $ 70.88 (0.20 mol) of diphenylcarbonate (DFS) is loaded into the condensation tube and then the process is carried out analogously to example 1. Given the viscosity of 0.5% polymer solution in HCOOH equal

Press the powder with the addition of 1.0 wt.% stabilizer and 1.0 wt.% soot receive analogously to example 1 and pressed into the mold by the method of direct compression at a temperature of 180aboutand specific pressure of 800 kgf/cm2and get a compression material having ap= 67-70 MPa, Ep= =4,0%. "After the impact of cold climate for 3 yearsp= 69-70 MPa, Ep= 3,6%.

P R I m e R 6. Weighed the same as in example 5, + stabilizer 1.5 wt.% + carbon black and 1.0 wt.%pand Epin the table below.

The proposed polymer composition resistant to the influence of cold climate. In the exposure process in cold climates and harsh UV radiation within 36 months they almost retain their original physical-mechanical and physico-chemical characteristics (see tab.1).

It should be noted that it is sufficient to type 1.0 to 1.5 wt.% 4-phenyl-2,2', 5,5'-tetramethyl-3-imidazoline-3-oxide-1-oxime and 1.0 wt.% soot in PABI that the copolymers have become resistant to the influence of factors of the cold climate and deep solar UV radiation. Such polymer compositions can be used as compression and composite polymer materials that can withstand factor,5,51-tetramethyl-3-imidazoline-3-oxide-1-oxime, characterized in that, to stabilize the physico-chemical, physico-mechanical properties of the composition when exposed to factors of the cold climate and deep solar UV radiation, it is as heterocyclic polymer contains polyamideimides and further comprises carbon black in the following ratio, wt.%:

4-Phenyl-2,21,5,51-tetramethyl-3-imidazoline-3-oxide-1-oxime 1,0 - 1,5

Soot 0,9 - 1,0

Polyamideimides Else

 

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