Amino-derivatives of c60-fullerene and composition material comprising indicated amino-derivatives

FIELD: polymers, chemical technology.

SUBSTANCE: invention relates to polymeric composition materials used in construction members in aviation and cosmic technique. Amino-derivatives of C60-fullerene combine functions of polyamine hardening agent, electron-active nanomodifying agent of permolecular structure of matrix, function of plasticizer reducing fragility of matrix, function of microcrack stopper and function of reinforcing members. Invention provides preparing amino-derivatives of C60-fullerene - products of chemical interaction of C60-fullerene with benzylamine (BA) of the empirical formula C60(BA)_n wherein n = 4-6, and the composition material made from epoxy-base polymeric binding agent and fibrous filling agent wherein polymeric binding agent comprises additionally indicated amino-derivatives of C60-fullerene in the amount 10.2-60.6 mas. p. p. per 100 mas. p. p. of epoxy base.

EFFECT: valuable properties of material.

3 cl, 2 tbl, 5 ex

The invention relates to the field of polymer composite materials used in the structural elements of aviation and space technology.

Known amine - curing thermosetting epoxy oligomer. In particular, the well-known benzylamine used cold curing Dianov and Novolac epoxy resins [ENCYCLOPEDIA of POLYMERS. M.: Publishing house "Soviet encyclopedia", 1972, Vol. 1, str; Volume 3, str]. Monofunctionality this hardener, however, do not provide the extensive cross-linking and to ensure the heat resistance of the polymer matrix.

Known bifunctional amine hardener epoxy - dicyandiamide used to obtain the heat-resistant polymer matrices with extensive stitching [HANDBOOK OF COMPOSITES, Edited by George Lubin, Van Nostrand Reinhold Company Inc., New York, 1982, p.107]. Known epoxy binder based diglycidylether ether of bisphenol a and dicyandiamide [Lee H. and Neivlle K., HANDBOOK OF EPOXY RESINS, Mc Graw-Hill, NewYork,1967, p.p.11, 48]. The multifunctional epoxy oligomer and the amine hardener provide the density of crosslinking and high temperature binder in dry condition. However, advanced stitching gives at the same time and the negative effect it according to the material of the polymer matrix increased fragility and limited to 0.3-0.5% deformation.

To increase the deformation part of epochs is-breaking compositions injected plasticizers, for example, diglycidyl ether generalizatio acid [J. Rinde, Mones E.T., Newey H.A., "Flexible Epoxides for Wet Filament Winding", 32^ndAnnual Conference, Reinfoced Plastics/Composites Institute, SPI, Washington, D.C., February 8-11,1977, Section 11-D]. The plasticizer can increase the elongation utverzhdenii polymer matrix 8 times, but at the same time reduces by half its strength in comparison with the initial value.

Known polymer composite materials containing diglycidyl ether of bisphenol a, dicyandiamide and fibrous reinforcing fillers [HANDBOOK OF COMPOSITES, Edited by Georg Lubin, Van Nostrand Reinhold Company Inc., New York, 1982, p.299]. These composites are heat resistant up to 180°have a high uprugoopticheskii properties in the longitudinal direction, however, show limited resistance to transverse and shear loads due to the low deformation brittle polymer matrix.

Known composition containing diglycidyl ether of bisphenol a, 4,4'-diaminodiphenylsulfone and fullerene [U.S. Patent No. 5281653, CL 524/490, publ. 15.01.1994]. Introduction to composition 5 parts by weight of Fullerene C60 provides reduced in 2 times the elastic modulus of the binder in dry condition without strength drop. The disadvantage of the composition is increased fluidity when heated to the stage of gel formation, which creates significant technological difficulties in the manufacturing process of the composites with formiruemymi composition. In deresinated polymer composites decreases the level of implementation strength reinforcing fibers, particularly substantially in compression and shear.

Closest to the claimed derivatives is 4,4'-diaminodiphenylsulfone [Japan's Bid No. 55-25217, IPC C 08 G 59/50, publ. 04.07.80], adopted for the prototype. This tetrafunctional curing agent performs its intended purpose, but has no other features that would make the composite material new and useful properties.

Closest to the claimed composite material adopted for the prototype are:

- carbon fiber CMU-7E containing epoxy-amine oligomer EDMS (N, N,N',N'-tetraglycidyl-3,3'-dichlorodiphenylmethane), the curing agent is 4,4'-diaminodiphenylsulfone and the reinforcing filler is carbon tape ALUR-P;

- organoplastic - organic 16 T containing epoxy-amine oligomer EDMS, the curing agent is 4,4'-diaminodiphenylsulfone and reinforcing filler is an organic fabric RAS (art);

- fiberglass - fiberglass laminate EPS-30 containing epoxy-amine oligomer EDMS, the curing agent is 4,4'-diaminodiphenylsulfone and reinforcing filler is fiberglass T-10-80 [AVIATION MATERIALS AT the TURN of XX-XXI CENTURIES, Scientific and technical proceedings, Moscow, SE VIAM SSC RF, 1994, s].

These composite materials are characterized by high is Kimi indicators of static strength in the direction of the reinforcement, heat resistance, long service resource. However, due to the low deformation matrix they have limited strength in the transversal direction, as well as reduced stamina and endurance in conditions of dynamic loading due to avalanche-like character degradation by multiple mechanism of brittle fracture.

The technical task of the present invention are:

- development of derivatives of fullerene C60, combines the functions of a hardener of epoxy, modifier interphase boundaries, plasticizer, stopper microcracks, a reinforcing element;

- decrease the brittleness of epoxy polymer matrix in castelvania dry condition, the increase of the range of plastic deformation of the matrix in front of the advancing fatigue or shock cracks;

- development on the basis of the modified polymer matrix composites - carbon-, organic-, glass-reinforced plastics with high fracture toughness, endurance and vitality.

For the technical solution proposed:

Amino derivatives of fullerene C60 - products of chemical interaction of fullerene C60 with benzylamine (BA) gross formula C60(BA)n, where n=4-6.

Composite material made of a fibrous filler and a polymeric binder based on epoxy resin, sod is rasego these amino derivatives of fullerene C60 in the amount of 10.2-to 60.6 parts by weight of on 100 parts by weight of epoxy base.

Polymer binder and fibrous filler is taken in the ratio (wt.%):

As the fibrous filler is carbon, glass or organic fabrics, fibers, strands, ribbons.

A significant difference of the present invention is the synthesis and application of amino derivatives of fullerene C60 formula C60(BA)_4-6combining several useful technical functions: function polyamino hardener, providing thick stitching epoxy polymer matrix, its resistance; the function of the electro-active nano modifiers supramolecular structure matrix (improvement of morphology by reducing the share of excluded volume, reduce the grain size of the dispersed phase) and phase boundary "reinforcing fiber - polymer matrix (increasing the strength of adhesion); the function of a plasticizer, reducing the brittleness of the matrix; the function of the stopper of microcracks; finally, the function of reinforcing elements that are directly related to the solid matrix by covalent bonds that form the bulk of the frame, contributing to the increase of the specific energy of fracture in polymeric matrices and Amirova the different plastics based on it.

It is important to note that, if, due to steric interaction of one or more amino derivatives of fullerene C60 formula C60(BA)_4-6will not be able to take part in the reaction and disclosure of epoxy-oligomeric ring binder molecule of fullerene C60 will not remain inert ballast, and will be able to play the active role of a different quality.

Examples of implementation

Example 1.

Obtaining derivatives of fullerene C60 formula C60(BA)_4-6.

A portion of the Fullerene C60 (TU-001-13800624-2003) dissolved in benzylamine and the reaction mixture is intensively stirred on a magnetic stirrer. Excess benzylamine distilled off in vacuum. Amino derivatives of fullerene extracted with chloroform and precipitated with hexane. The obtained solid is washed repeatedly with methanol and dried in vacuum for 24 hours at T=60-80°C. a Yield of 63%. Amin - benzylamine. Elemental analysis: found (%) : - 91,85; N - 2,92; N - 4,85; calculated (%): 92,0; N - 3,1; N - 4,9. UV-spectrum (benzene) (nm): 286 (square), 575 (square).

Obtaining a composite material

a 20.2 parts by weight of 4,4'-diaminodiphenylsulfone (TU 6-02-2735-86) and 40.5 parts by weight of amino derivatives of fullerene C60 formula C60(BA)_4-6mechanically mixed with 100 parts by weight of epoxy-amine oligomer EDMS (TU 6-05-1725-75 with notice No. 4 of 09.11.82). A binder is dissolved in acetone to 50%concentration to ensure wetting effect. Receiving the major binder impregnated carbon cloth UT-900-2,5 (TU 1916-165-05763346-95). The prepreg is dried at room temperature in air to remove solvent. Produce a display package of the prepreg with the laying [0] on the thickness of the CFRP plates 1, 2, 3 mm and implement hot molded carbon fiber extrusion method. Samples of carbon have on the interlayer shift τ_xz(MP 49-82), compression in longitudinal σ⁰ _- and transversal σ⁹⁰ _- directions (GOST 25602-80) and specific toughness And_to(GOST 4647-80).

Example 2.

Obtaining derivatives of fullerene C60 formula C60(BA)_4-6,as in example 1.

Obtaining a composite material

of 3.7 parts by weight of bis-(N,N'-dimethylcarbamyl)difenilmetana (TU 6-14-22-159-83) and 10.2 parts by weight of amino derivatives of fullerene C60 formula C60(BA)_4-6mechanically mixed with 100 parts by weight of compound KDA (epoxy Dianova resin ED-20 and diglycidyl ether of diethylene glycol deg-1 in the ratio 9:1). The composition is dissolved within 60-90 minutes in spermazetovoe mixture (1:1) at a temperature of 60-70°With concentrations up to 55-60%Poluchennym solution impregnated fabric on the basis of organic fiber RAS (art. 56313) (GOST 17-62-9575-80). The prepreg is dried at room temperature in air to remove the solvent, manufacture of the prepreg lay-up in packages and perform hot forming organoplastic forging method. Samples of plastic ispy is to see the shift, the compression and bending (GOST 604-82).

Example 3.

Obtaining derivatives of fullerene C60 formula C60(BA)_4-6,as in example 1.

Obtaining a composite material

26,0 parts by weight of 4,4'-diaminodiphenylsulfone and 30.3 parts by weight of amino derivatives of fullerene C60 formula C60(BA)_4-6mechanically mix with 27.8 parts by weight of triglycerides of paraaminophenol brand AAF, to 42.0 parts by weight of polyglycidylether low molecular weight of the phenol-formaldehyde novolak brand UE-643, and 3.6 parts by weight of the product of the interaction of diphenylolpropane with epichlorohydrin brand Diplast. The composition is dissolved in spermazetovoe mixture (1:1) to a concentration of 50%. The resulting solution impregnated fiberglass T-10-80 (GOST 19170-73) without removing the sizing. The prepreg is dried at room temperature, put in the packages. Carry out hot molded fiberglass extrusion method. Samples of fiberglass experience in shear and compression.

Example 4

Obtaining derivatives of fullerene C60 formula C60(BA)_4-6,as in example 1.

Obtaining a composite material

the 10.1 parts by weight of 4,4'-diaminodiphenylsulfone and to 60.6 parts by weight of amino derivatives of fullerene C60 formula C60(BA)_4-6mixed with 100 parts by weight of epoxy-amine oligomer EDMS. The resulting composition is dissolved in acetone to 50%concentration. This solution is impregnated with a carbon ribbon ALUR-P (G THE ARTICLE 28006-88). The prepreg is dried at room temperature in air to remove solvent. Produce a display package of the prepreg with the laying [0] on the thickness of the CFRP plates 1, 2, 3 mm and implement hot molded carbon fiber extrusion method. Samples of carbon have on the interlayer shift τ_xzcompression in longitudinal σ⁰ _- and transversal σ⁹⁰ _- directions and specific toughness And_to.

Example 5 (prototype). Obtaining a polymeric binder, coal-, organic-, GRP based on it.

of 40.5 parts by weight of 4,4'-diaminodiphenylsulfone mixed with 100 parts by weight of epoxy-amine oligomer EDMS in accordance with the stoichiometric ratio of functional groups of the reactant. The mixture is dissolved in acetone to 50%concentration. The resulting solution impregnated carbon cloth UT-900-2,5, carbon tape ALUR-P, organic fabric RAS and fiberglass T-10-80. The prepreg is dried at room temperature and produce their lay-in packages. Carry out hot molding plastics extrusion method. Samples of plastics experience in shear, compression, bending and impact strength.

The structures of the prepregs are shown in table 1, the properties of coal-, organic-, glass - in table 2, where the examples 1, 2, 3, 4 - proposed technical solutions, 5 - prototype.

It should be noted that epoxy binder comprising amino derivatives of Fullerene C60 formula C60 C60(BA)_4-6have moderate fluidity when heated to the point of gelation. The compositions are molded plastics conform to the norms of the ratio of reinforcing filler and polymeric binder" (defined as x-ray method).

Table 2 shows that, compared with composites-prototypes of the resistances of the proposed composites in those kinds of loading, where the polymeric binder matrix special responsible, compression, shear has increased significantly. Thus, the compressive strength of CFRP in the transversal direction increased by 86%, traditionally low strength fiberglass shear increased by 44%. Especially important positive result was achieved under shock loading the most fragile of polymer composites - high modulus carbon fiber - indicator ID toughness increased by almost 70%. This demonstrates the achievement of a composite of a fundamentally new structural quality education volume reinforcing frame, absorbing significant additional external energy of destruction.

It should be emphasized that the technical result from the application of the proposed technical solution is achieved not only when WLL the Institute of textile forms of reinforcing fillers - fabrics and tapes, but also when using bundles and individual fibers (for example, when variants of the winding structures of the type "body rotation"). This is due to the deep nature of the physico-chemical interaction of the modified binder with the surface of the individual monofilaments (filaments) of reinforcing fibrous fillers.

1. Amino derivatives of fullerene C60 - products of chemical interaction of fullerene C60 with benzylamine (BA) gross formula C60(BA)n, where n=4-6.

2. Composite material made of a polymeric binder based on epoxy resin and a fibrous filler, characterized in that the polymeric binder further comprises amino derivatives of fullerene C60 according to claim 1 in the amount of 10.2-to 60.6 parts by weight per 100 parts by weight of epoxy base.

3. Composite material according to claim 2, characterized in that the polymer binder and fibrous filler is taken in the ratio, wt.%:

4. The composite material of any one of claim 2 and 3, characterized in that the fibrous filler is carbon, glass or organic fabrics, fibers, strands, ribbons.