Polymeric binder and a polymeric composite material based on it

 

(57) Abstract:

The invention relates to a polymeric binder and composite materials on their basis, which can be used as structural materials in aerospace, electronic industries. Binder includes aromatic epoxy resin (75-95 m H.), surfactant - dihexadecylnaphthalene or tetradecylammonium or their mixture (0.1 to 0.2 m H.), metal-complex compound (5-25 m h) and the solvent is acetone, ethanol or their mixture (25-40 m o'clock). Composite material is obtained from the polymeric binder of the composition and a fibrous filler at a ratio (30-50):(50-70). The invention allows to obtain a binder with long-term viability (up to 6 months), to increase the tensile strength and the bending of a composite material. 2 AD. and 1 C.p. f-crystals, 3 tables.

The present invention relates to the field of creation of polymeric binder of epoxy type and polymer composite materials (PCM) based on them, which can be used as structural materials in the aerospace industry, electronics and other engineering fields. In addition, we offer the s, etc.

Known epoxy composition comprising an aromatic or cycloaliphatic epoxy resin and amine hardener, which is a product of interaction-acetylhydrazine and steam(dimethylamino)-benzaldehyde (Ed. St. USSR №1641832, IPC C 08 G 59/50).

The disadvantage of this composition is its low viability because of the high reactivity of the hardener. Application of known epoxy composition in PKM is not possible to obtain a composite material with high physical-mechanical properties.

Use for curing epoxy resins curing catalyst, which is a complex salt of divalent metal adduct of polyepoxide and imidazole, allows for the curing of epoxy compositions at temperatures above 50C, but has virtually no effect on the physico-mechanical characteristics of the cured polymer (U.S. Pat. U.S. NO. 5789498, IPC C 08 G 59/40, 08 G 59/68).

The disadvantage of the composition is the high cost of hardener, which significantly increases the cost of polymer composite materials based on it.

Known metal complex compound of General formula:

MLxByor M[SR]xBz,

where M is a metal ion selected from the group vkluchayu the acetylacetone or benzoylacetone;

SR - acid residue of an inorganic acid;

In - imidazole or Mei;

x=1,2; y=1,2,3,4,5; z=7,8;

which is used for polymerization of epoxy resins (U.S. Pat. OF THE RUSSIAN FEDERATION NO. 2086572, IPC C 08 G 59/00, 59/68).

Polymerization known compounds occurs at elevated temperature and physico-mechanical characteristics utverzhdenii epoxy compositions and polymer composite materials based on it is not high enough.

Known polymeric composite materials based on epoxy resin SU-C: fiberglass laminate EPS-30 (filler - fiberglass T-10-80), carbon CMU-7E (filler - carbon tape ALUR-0,1) and CMU-7T (filler carbon cloth WAL-300-1) and the organoplastic Organic 16T (filler - tissue paper art.56313), whose properties are described in the Scientific and technical collection SE “VIAM” SSC RF “Aviation materials at the turn of XX-XX I ever”, M, 1994, S. 442. These materials have a low compressive strength, Flexural and interlaminar shear, especially at elevated temperatures (150-200C).

The closest in technical essence of the present invention is a polymer composition comprising an aromatic or cycloaliphatic epoxy resin (100 wt.h.), aliphatic amine (2-20 IPC 08 G 59/56).

The introduction of the polymeric composition of hydrochlorination does not allow to increase the viability of the songs more than 20 days. The process of obtaining polymeric composition is carried out at a temperature of (9010)C. in Addition, the curing of compositions containing aliphatic amines, accompanied by considerable heat, which adversely affects the properties of the cured material. This specific curing composition also leads to the structural heterogeneity of a polymer material and negative effect on physico-mechanical properties of polymer composite materials on the basis of this composition.

The technical object of the present invention is to provide a polymeric binder based on aromatic epoxy resin, a combination of components which is at room temperature, having a long pot life (up to 6 months) and allowing to obtain a polymer matrix with a homogeneous structure and high values of ultimate strength in tension and bending, as well as receive using the proposed binder polymer composite materials (glass-, organo - and fiber-reinforced plastics) with improved physical and mechanical characteristics.

DL the metal complex compound of General formula:

Mx(LH+)yB-x+y,

where M is a transition metal I, II, VII, VIII group of the periodic table;

LH+- chelate forming ligand, representing monoprotonated connection Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine or their mixture;

In the acid residue of higher aliphatic carboxylic acid or aromatic acid is benzoic, salicylic, or m-oksibenzoynoy;

x is the oxidation state of the transition metal, x=1,2,3;

y is the number of moles of the compounds included in the chelate forming ligand, y=1-3;

moreover, it additionally contains a surfactant - dihexadecylnaphthalene or tetradecylammonium or their mixture, and an organic solvent, acetone, ethyl alcohol or spiroatsetaley mixture in the following ratio, wt.h.:

Epoxy aromatic resin 75-95

Surfactant is 0.1-0.2

Metal-complex compound 5-25

Organic solvent 25-40

A polymer composite material made from the composition comprising the specified polymer binder and fibrous filler, the next autoceste fibrous filler used fiberglass, the fabric of organic fibers, carbon harnesses, carbon tape, carbon cloth.

The essential difference of the present invention is the introduction into the polymer composition metal complex compounds of General formula:

Mx(LH+)yB-x-y,

where M is a transition metal I, II, VII, VIII group of the periodic table;

LH+- chelate forming ligand, representing monoprotonated connection Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine or their mixture;

In the acid residue of higher aliphatic carboxylic acid or aromatic acid is benzoic, salicylic, or m-hydroxy-benzoic acid;

x is the oxidation state of the transition metal, x=1,2,3;

y is the number of moles of the compounds included in the chelate forming ligand, y=1-3;

and optionally a surfactant (dihexadecylnaphthalene (C16H33)NH-CH2-CH2-NH(C16H33or tetradecylammonium (C6H33)2N-CH2-CH2-N(C16H33)2or mixtures thereof) and an organic solvent is acetone, ethyl alcohol or spermazetovoe mixture. The technical result claims the situation (ISS) of any transition metals I, II, VII, VIII group of the periodic table.

In the metal-complex compound (ISS) as the acid residue of higher aliphatic carboxylic acids may be used acid residues with the number of carbon atoms of not less than 6. When using ISS acid residues of aliphatic carboxylic acids of the best technical result is achieved with the use of lauric acid residues (C11), stearic (C16) and margarine (C17) acids.

With positions microcomposite structure of the polymer matrix represent a heterogeneous phase system consisting of a homogeneous dispersion medium (DS), which is divided particles of the dispersed phase (DF). The use of surfactants allows you to adjust the size of supramolecular structures of the polymer matrix, and also leads to the reduction of particle size DF, increase their volume content and ultramicroelectrode patterns that ultimately greatly increases the strength characteristics of polymer composite materials. In addition, the proposed surfactants act as chemically active components and are involved in the process utverjdeniyu allows to make the process of obtaining a polymeric binder at room temperature and facilitates its processing in the manufacture of polymer composite materials.

As the metal complex compounds are used synthesized by the authors of the present invention compounds that get in two stages:

1) processing of aliphatic polyethylenepolyamines (Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine or mixtures thereof) higher aliphatic carboxylic acid or aromatic acid (benzoic acid, salicylic acid or m-oksibenzoynoy) in equimolar ratio with obtaining a homogeneous system;

2) the combination monoprotonated of polyethylenepolyamines with salts of transition metals (zinc salicylate, stearate, copper, cadmium benzoate, etc.,).

Examples of the implementation of

Example 1

Preparation of binder

In a clean dry reactor load 33 wt.h. acetone (GOST 2603-79), 15 wt.h. metal complex compounds - monoprotonated Diethylenetriamine musk (TR 1.595-12-200-2001), 0,2 wt.h. surfactant - dihexadecylnaphthalene (test sample obtained from the University to them. D. I. Mendeleev), include a stirrer and stirred at a temperature of 20-25C for 10 minutes. After complete dissolution of the metal complex compounds and surfactants charged to the reactor 95 wt.h. epoxy resin ED-20 (GOST 10587-84) and pogie get a polymeric binder in examples 2-7, shown in table 1.

Manufacturer of fiberglass

Prepared a binder of example 1 is applied to the fiberglass T-10-80 (GOST 19170-73), placed in the package and pressed at a temperature of 90-120C and specific pressure of 3-5 kg/cm2within 1-3 hours.

The fiberglass composition, wt.h.:

Binder 30

Fibrous filler 70

Manufacturer organoplastic

Prepared binder according to example 2 is applied to the tissue paper art. 56313 (TU RS-9575-80), placed in the package and pressed at a temperature of 90-120C and specific pressure of 3-5 kg/cm2within 1-3 hours.

The composition organoplastic, wt.h.:

Spanning 50

Fibrous filler 50

Manufacture of carbon fiber

Prepared binder according to example 3 is applied on a carbon tape ALUR-01P (GOST 28006-88). The formation of carbon is carried out at a temperature of 90-120C and specific pressure of 3-5 kg/cm2within 1-3 hours.

The composition of carbon, wt.h.:

Binder 30

Fibrous filler 70

On the similar technology received the plastics described in examples 4-7 (table 3). In examples 8 and 9 of table 3 polymer binder prototype received PCM using 00, carbon tow Chis-5000 in the same ratio of polymer binder and fibrous filler, as in examples 1, 2, 5, 6, respectively.

Table 2 shows the physico-mechanical properties and parameters of the microphase structure of the polymeric binder of the proposed structure (examples 1-7) and prototype (examples 8 and 9). The study of microphase structure was carried out using high-resolution scanning electron microscopy at magnifications from H2000 to kh20000. From the table 2 data shows that the polymer binder of the proposed composition has a significantly higher viability (from 35 to 180 days) in comparison with the prototype (8-10 days). The proposed composition of the binder allows to carry out the process at room temperature, which is a significant advantage over the prototype, where the process is carried out at a temperature (9010)C. the Limits of tensile strength and bending the proposed polymeric binder are 99-118 MPA and 132-152 MPa, respectively. Similar binding characteristics of the prototype significantly lower 19-31% when tensile and 11-13% in bending. Microphase structure of the polymer matrix of the proposed structure also has a significant difference of about 5%. Accordingly, the proportion of the dispersion medium polymer matrix of the proposed structure is reduced to 18-33% compared to the prototype (35-40%). The structure of the polymer matrix of the proposed structure is more homogeneous, as evidenced by the uniform distribution of ultrafine particles in DC, their sizes (0.2-0.5 µm) and short distances (less than 0.2 μm) between them. For the prototype of these structural parameters have a greater range, the particle size DF are in the range of 0.5 to 1.5 μm, and the distance between them reaches 0.3-0.5 µm.

Comparison of properties of composite materials obtained using the proposed binder and binder on the prototype (table 3), in terms of Flexural strength, compressive and interlaminar shear also demonstrates the significant benefits of the proposed binding: strength interlaminar shear for fiberglass increases from 85 to 117 MPa, organoplastic from 43 to 50 MPa and plastics with 72-76 up 87-89 MPa.

Characteristics of Flexural strength and compression PCM based on the proposed binder also have higher rates (average 17%).

Thus, the proposed polymeric binder has a high viability (up to 6 months), increased f is expressed in the reduction of particle sizes of the dispersed phase, the increase in their volume content and packing density. The process of obtaining a polymeric binder is carried out at room temperature.

Composite materials (glass-, organo - and fiber-reinforced plastics) on the basis of the offered binders have high physical and mechanical characteristics that allow them to be used as structural materials for the next generation of aerospace engineering.

1. A polymeric binder comprising aromatic epoxy resin and a metal complex compound, characterized in that it additionally contains a surfactant - dihexadecylnaphthalene, or tetradecylammonium, or their mixture and the organic solvent is acetone, ethanol or spiroatsetaley mixture, and as the metal complex compound is a compound of General formula

Mx(LH+)yIN-x+y,

where M is a transition metal I, II, VII, and VIII groups of the periodic table;

LH+- chelate forming ligand, representing monoprotonated connection Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine or their mixture;

In - acid residue Inoi;

x is the oxidation state of the transition metal, x = 1, 2, 3;

y is the number of moles of the compounds included in the chelate forming ligand, y = 13,

in the following ratio, wt.h.:

Epoxy aromatic resin 75-95

Surfactant is 0.1-0.2

Metal-complex compound 5-25

Organic solvent 25-40

2. Polymer composite material made of a composition including a polymer binder and fibrous filler, characterized in that it contains as a binder a polymer binder under item 1 in the following ratio, wt.h.:

Polymer binder 30-50

Fibrous filler 50-70

3. Polymer composite material under item 2, characterized in that as the fibrous filler used fiberglass, fabric of organic fibers, carbon harnesses, carbon tape, carbon fabric.

 

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