Polymer binder and a high-strength heat-resistant composite materials based on it

 

(57) Abstract:

The invention relates to the field of production of high strength heat-resistant non-combustible composite materials - glass and carbon-based polymeric binders which can be used for the products of aviation technology - vane compressors, fire screens, insulating gaskets, air intakes, etc., Describes a polymeric binder for composite materials - oligomer, obtained by interaction of tetranitride aromatic tetracarbonyl acid and an aromatic bis-o-cyanamide, and oligomer get at a temperature of 170-180oWith, as tetranitride aromatic tetracarbonyl acid is used 4,4'-(m-phenyleneoxy)giftionary as bis-o-cyanamide using 3,3'-dicyano-4,4'-diaminodiphenylmethane and added 1,2-bis(cyanoethyl)carboran in the following ratio, wt.h.: 3,3'-dicyano-4,4'-diaminodiphenylmethane 40,7; 4,4'-(m-phenyleneoxy)giftionary 53,3-59,3; 1,2-bis(cyanoethyl)carboran 10-30, and describes a high-strength composite materials containing specified binder and fiberglass or carbon fiber filler. The invention allows paschimi characteristics, keeping these characteristics in the short-term and long-term exposure to temperatures of 400oWith at least 80% of the original value. 3 S. and 1 C.p. f-crystals, 1 table.

The invention relates to the field of production of high strength heat-resistant non-combustible composite materials glass - and carbon-based polymeric binder, a long time at the temperature of 400oWith and while preserving the mechanical strength of not less than 80% of initial value. These composite materials can be used for manufacturing the responsible units of the new generation aviation equipment (blades of compressors, fire screens, insulating gaskets, air intakes, and so on).

Known binder for heat-resistant and high-strength composite materials based on polyimides, polyamidoimides, polybenzimidazole (Aviation materials at the turn of XX-XXI centuries In scientific and technical proceedings, 1994, S. 207-209; B. C. the Korshak. Heat-resistant polymers. - M.: Nauka, 1969, S. 271.).

Known binder SP-SM-50, representing the interaction products dianhydride benzophenonetetracarboxylic acid with bis-methane in a mixture of solvents. Famous stiklplastikas (TU 6-06-5845889-01-91).

Made of heat-resistant plastics known CMU-LP, the CMU-8 based on polyimide SP-97 and polyamidoimides PAIS-104 binder (Reinforced plastics. M., 1997, S. 251.).

These binders provide glass and plastics on the basis of their high initial mechanical strength, long term operation at temperatures of 250-350oWith and briefly at temperatures up to 400oC. However, the synthesis of the above binder requires strict adherence to the stoichiometric ratios of the monomers, the use of toxic high-boiling organic solvents, and the process of forming composite materials is accompanied by the emission of significant quantities of volatile reaction products, hindering monolithic products, and products with high physical-mechanical characteristics of the long-term operation at temperatures of 350-400oC.

The closest in technical essence to the claimed invention is a polymeric binder for composite materials adopted for the prototype, which represents an oligomer-based tetranitride aromatic tetracosanoic acids and bis-o-CinemaNow, the synthesis is carried out in the melt at stachio is raised to its low thermal-oxidative stability in conditions of prolonged exposure to temperatures of 400-450oC.

The fiberglass on the basis of the above binder of the following composition, wt.h.:

Binder - 24-30

Fiberglass filler - 70-76

has high mechanical strengthVI= 60-75 kg/mm2but keeps it at the level of not more than 70% of initial value at short-term (less than 0.5 h) influence of temperature 400oC. Increase duration of exposure to a specified temperature leads to a complete burnout of the binder.

Known carbon-based heterocyclic binder of the following composition, wt.h.:

Binder - 38

Carbon fiber filler - 62

(U.S. patent 5120819, MKI C 08 G 73/00).

As the carbon filler is used carbon cloth from the loom T-300. The carbon fiber has a shear strength of 6.8 kg/mm2at normal temperatures, but keeps it at the level of 55% at a temperature of 343oC. the Prepreg receive mortar technology, which suggests that the use of toxic solvents.

The technical object of the present invention is to provide an environmentally safe powder binder, glass and plastics at its base with improved physical and the 0oWith at least 80% of the original value.

To solve the problem proposed:

1. Polymeric binder for composite materials - oligomer, obtained by interaction of tetranitride aromatic tetracarbonyl acid and an aromatic bis-o-Cyanamid, characterized in that the oligomer obtained when the temperature of 170-180oWith, as tetranitride aromatic tetracarbonyl acid is used 4,4'-(m-phenyleneoxy)giftionary as bis-o-cyanamide using 3,3'-dicyano-4,4'-diaminodiphenylmethane and added 1,2-bis(cyanoethyl)carboran in the following ratio, wt.h.:

3,3'-dicyano-4,4'-diaminodiphenylmethane - 40,7

4,4'-(m-phenyleneoxy)giftionary - 53,359,3

1,2-bis(cyanoethyl)carboran - 1030

2. The fiberglass on the basis of the following composition, wt.h.:

Binder - 24-30

Fiberglass - 76-70

3. Carbon fiber filler, based on the following composition, wt.h.:

Binder - 36-42

Carbon fiber filler - 58-64

As a carbon filler used carbon fiber, strands, ribbons, fabrics.

The essential difference of the present invention is an additional optional nitrile groups allows it to be integrated into the main polymer chain and to perform the role of chemically bound, not evaporating during exposure to elevated temperatures, a highly effective antioxidant of thermo stabilizer. "Oven" effect of closo-carboranes-12 due to the dynamic interaction of EXT-groups of carboran with oxygen and boron-centered radicals free radicals or macroradicals, thereby reducing the likelihood of degenerate branching circuit during thermo-oxidative degradation. The presence of the ethylene groups in the structure of 1,2-bis(cyanoethyl)carboran promotes uniform distribution of residual stresses and increase the packing density of utverzhdenii polymer matrix, which causes the increase of its heat resistance and mechanical characteristics.

Examples of implementation

Example 1

Obtaining binding

In a three-neck flask equipped with stirrer, thermometer and a bubbler for supplying inert gas load of 40.7 wt.h. (0,163 mol) of 3,3'-dicyano-4,4'-diaminodiphenylmethane (TL6-06-27-91), 53.3 wt.h. (0,163 mol) 4,4'-(m-phenyleneoxy)littleitaly (prototype) and 10 wt. including 1,2-bis(cyanoethyl)carboran (prototype). The contents of the flask are heated with vigorous stirring at the point of argon at 170-180oWith up to full IP the monomers. Melt synthesized thus oligomer is poured into a metal pan and after cooling is ground in a ball mill. Get a powder binder with a melting point of 100-120oC.

Getting fiberglass

Powdered binder is applied on aluminosilicate fiberglass (GOST 19170-73) satin patterns in an electrostatic field, cut into sheets of the required size, is placed in the package and pressed at a temperature of 200-250oWith and specific pressure of 10-15 kgf/mm2followed by heat treatment without pressure at a temperature of 300-400oC.

The fiberglass composition, wt.h.:

Binder - 24

Fiberglass - 76

Getting carbon fiber

Manufacturing of semi-finished product was carried out by spraying a binder on a carbon tape LU-P (TU 6-06-31-560-86) in an electrostatic field with subsequent reflow. Forming carbon was carried out at a temperature of 200oC and a pressure of 10 kgf/mm2in press, with further heat treatment in the free state in the temperature range 250-400oC.

The composition of carbon, wt.h.:

Binder - 36

Carbon fiber filler - 64

Example 2

Getting swiatowej the o-4,4'-diaminodiphenylmethane - 40,7

4,4'-(M-phenyleneoxy)giftionary - 59,3

1,2-Bis(cyanoethyl)carboran - 20

Getting fiberglass

Analogously to Example 1 are fiberglass with the following ratio of components, wt.h.:

Binder - 24

Fiberglass - 76

Getting carbon fiber

Analogously to Example 1 get the carbon fiber using as a carbon filler - fabric brand "UT-150" with the following ratio of components, wt.h.:

Binder - 42

Carbon fiber filler - 58

Example 3

Obtaining binding

Analogously to Example 1 are as binder in the following ratio, wt.h.:

3,3'-Dicyano-4,4'-diaminodiphenylmethane - 40,7

4,4'-(M-phenyleneoxy)giftionary - 59,3

1,2-Bis(cyanoethyl)carboran - 30

Getting fiberglass

Powdered binder is applied in an electrostatic field on quartz glass (TL6-11-216-71) satin patterns and get the fiberglass analogously to Example 1 with the following ratio of components, wt.h.:

Binder - 30

Fiberglass - 70

Getting carbon fiber

Analogously to Example 1 get the carbon fiber using as a carbon filler - harness brand "L
Properties (approved binder, glass, plastics based on it is shown in the table, where Examples 1, 2, 3 - proposed, 4 - prototype.

The table shows that the proposed composition of the binder has a high heat resistance and mechanical characteristics in comparison with the prototype. For example, the proposed binding temperature of 10% weight loss in the conditions of dynamic thermogravimetric analysis in air increases with 540oWith (prototype) to 630oWith 150oincreases the glass transition temperature significantly increases the value of the ultimate strength in compression, and save this indicator in 400oC is 82-90% (for prototype - 30%).

Fiberglass obtained on the basis of the proposed binder, has a high mechanical strength (63-88 kg/mm2depending on the brand of fiberglass), stores it at a level in excess of 80%, as in the short-term (0.5 h) and long (30 hours) the influence of temperature 400oC. under these conditions, the mechanical strength of the proposed GRP greatly exceeds the strength of the prototype fiberglass that is virtually ove offer fireproof binder, have a very low porosity (0.9 to 1.75 per cent).

The carbon fiber obtained on the basis of the proposed binder, has high mechanical properties at a temperature of 400oWith the saving strength is 75-80% of the original. The carbon fiber has a low porosity, located at 0.5-2%. In addition, the carbon fiber receive powder technology, which is more environmentally friendly compared with mortar.

Thus, the application of the proposed binder and glass - and carbon fiber-reinforced plastics based on it will allow you to create promising products aerospace appointment with enhanced strength indicators, with a simultaneous increase in operating temperatures up to 400-450oC and reducing the weight of structural elements by 30-40%.

1. Polymeric binder for composite materials - oligomer, obtained by interaction of tetranitride aromatic tetracarbonyl acid and an aromatic bis-o-cyanamide, characterized in that the oligomer obtained when the temperature of 170-180oWith, as tetranitride aromatic tetracarbonyl acid is used 4,4'-(m-phenyleneoxy)giftionary as bis-o-cyanamide using 3,3'-dizinine, wt. including :

3,3'-Dicyano-4,4'-diaminodiphenylmethane - 40,7

4,4'-(M-phenyleneoxy)giftionary - 53,3-59,3

1,2-Bis(cyanoethyl)carboran - 10-30

2. High-strength composite material containing a polymer binder and fiberglass, wherein as the polymer binder used binder under item 1, in the following ratio, wt. including :

Binder - 24-30

Fiberglass - 76-70

3. High-strength composite material containing a polymer binder and a carbon filler, characterized in that as the polymeric binder used binder from p. 1, in the following ratio, wt. including :

Binder - 36-42

Carbon fiber filler - 58-64

4. High-strength composite material under item 4, characterized in that a carbon fiber filler carbon fibers, strands, ribbons, fabrics.

 

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