Epoxide composition

FIELD: chemistry.

SUBSTANCE: epoxide composition can be used as binder during production of composite materials, adhesive and filling compositions in automobile, electrical and other industries. Described is an epoxide composition which contains epoxy diane resin, phosphate modifier, amine hardener and hardening initiator - complex of tris(halogenalkyl)phosphate (THAP) with tin or titanium chloride with general formula 2[(RO)3 P=O]•ECl4, where E=Sn,Ti, R= -CH3C6H4, -CH2CH2CI, -CH2CH(CI)CH3.

EFFECT: proposed epoxide composition can be used to make articles with good strength properties and fire resistance.

1 cl, 2 tbl, 6 ex

 

The present invention relates to the chemistry of macromolecular compounds, namely epoxy compositions that can be used as a binder for the production of composite materials, as adhesives and coating compositions, automotive, electrical and other industries.

Known flame-retardant epoxy composition comprising an epoxy resin hardener - trihalogen phosphorus (PCl3or POCl3preferably with a ratio of Cl : epoxypropyl = 1:3-3:1 [Kevin M. Foley, Bell Reuben K. Fire-resistant ES, cured by trigliceride phosphorus. // Rehim., 1977, TP., Pat. U.S. CL 260-07 EP, (C08G 51/10, G08G 30/10), No. 3971750, Appl. 21.04.75, No. 569905, publ. 27.07.76].

The disadvantage of the composition is used as hardeners highly volatile, toxic compounds.

Known composition with reduced Flammability, intended for the manufacture of foams, adhesives and water-resistant paints containing (%) epoxy resin (Dianova), the modifier is an ester of phosphoric acid (RO)3RO (R is alkyl (C1-6halogenated, aryl) 15-30 (by weight ES), fillers - phosphate (for example, phosphate, guanidine, melamine, urea, dicyandiamide) 3-20 and starch (wheat, potato) 5-15, and the hardener is a polyamine and/or a polyamide. Samples are tested for fire resistance (ASTM D-635-63) (figures in brackets for brazzeres additives (I), behavior in flame: does not melt, is decaying; (melts, burns, lots of smoke); samostojatelnosti: after removal of the flame is burning within (): 0; (10-15); the remainder after keeping in a flame for 30 s; very large; (0). [Sakamoto, Norihiko. A flame retardant composition based on epoxy resin. Jap. Pat., CL(5)C, (C08G 59/44), No. 50-13836].

The disadvantage of this composition is complexity and low strength properties.

The task of the claimed invention is to provide epoxy resin compositions with improved processing and performance characteristics that extend the range of compositions of this assignment.

The technical result of the invention is to improve the technological and operational characteristics of the composition, namely the increased durability and fire resistance.

This is achieved by the fact that the epoxy composition comprising epoxygenase resin, phosphate modifier, amine hardener, according to the invention it as a modifier contains a phosphate compound selected from the group including tricresylphosphate, three(2-chloroethyl)phosphate, three(2-chloropropyl)phosphate, and the curing catalyst is a complex of Tris(halogenated)phosphate (THAT) chloride tin or titanium General formula (I)

,

where e=Sn, Ti, R=-sub> 3With6H4, -CH2CH2Cl, -CH2CH(Cl)CH3,

when the ratio of the components in mass:

epoxygenase resin ED-20100
specified phosphate modifier20,0
the specified catalyst0,26-1,69
the hardener10,0

The epoxy composition is prepared as follows: first, a portion of the complex THAT with chloride of tin or titanium dissolved in the corresponding phosphate, the resulting solution was added to epoxygenase resin and stirred for 15 minutes Then to the resulting mixture add the hardener of Triethylenetetramine (THETA) and again mix until smooth. As a control composition was prepared containing 100 mass epoxy resin and 10 mass THETA. Curing is carried out at 80°C for 4 h the three Complexes(2-chloroethyl)phosphate and three(2-chloropropyl)phosphate with the chlorides of tin and titanium were obtained according to patent RU 2324697 20.05.2008. The method of obtaining complexes of Tris(halogenated)phosphate chloride Sn, Ti or Si. Authors: Zinoviev Mrs x, Efimov V.A., Koltsov N.I.

Examples of specific performance are shown in table 1 and an example of the x 1-6.

The difference between the claimed invention is the use of the composition of the curing agent complexes THAT with the chlorides of tin or titanium, by means of which a first pre-cationic polymerization of epoxy resin with obtaining oligomers, and then curing them amine hardener type polycondensation.

Preliminary cationic polymerization leads to an increase in the share of simple ester groups, the binding energy which Elink(C-O)=358 kJ/mol above Elink(C-N) - groups (305 kJ/mol)formed by conventional amine curing, resulting in improved strength characteristics of the compositions. The presence of ester groups also helps to improve the elasticity of the composition and resistance to shock loads.

The General scheme of curing a mixed polymerization-polycondensation type can be represented as follows:

1 stage. Cationic polymerization:

where R is the residue of epoxy oligomer ED-20:

stage 2. Polycondensation with Amin:

where.

Introduction as modifiers THAT caused, first, by the presence in their structure of phosphorus atoms and chlorine, which can give polymeranalogous to burn; secondly, due to the presence of polar phosphate and chloralkali groups of molecules THAT capable of forming strong hydrogen bonds with the polymer and increase its strength properties. In addition, the introduction THAT lowers the viscosity of the composition that is favorable technological factor. Thus, the claimed invention with the use of initiators, curing allows you to create a composition with high performance properties.

To obtain epoxy composites used the following compounds: tricresylphosphate (GOST 5728-76), three(β-chloroethyl)phosphate (TU 2493-319-05763441-2000, three(β-chloropropyl)phosphate (TU 2493-320-05763441-2000), tin tetrachloride (BC. smoke. J., d420=2,232 g/l, TKip.=113,7°C), titanium tetrachloride (BC. smoke. J., d420=cash consideration of USD 1,726 g/l, TKip.=136,5°C), epoxy resin grade ED-20 (GOST 10587-84) and Triethylenetetramine (clear W., TPL=-35°C; TKip=277,5°C, nD20=1,4986, d2020=0,9818).

Properties of the obtained compositions was characterized using standard or conventional methods. Ultimate tensile stress (σp), the deformation at fracture (εRel.) under uniaxial tension was determined according to GOST 11262-76 on universal testing machine R is 0.5. Impact strength (A) was evaluated according to GOST 19109-73 on BM-5, the resistance by the method of "fire chimneys" (Δm - mod is to sample mass after combustion).

Example 1. Epoxy composition prepared by dissolving the catalyst bis(tricresylphosphate)tetrachlorogallate (TCF·SnCl4) 1,04 g modifier TKF (20 g) and then adding the mixture obtained in epoxy resin (100 g). The mixture is stirred for 15 minutes, then add the amine curing agent of Triethylenetetramine (THETA) and again mix thoroughly for 10-15 minutes the mixture is Then poured into a Teflon-coated forms and utverjdayut at 80°C for 4 hours. The catalyst TCP·SnCl4get the addition of 3.54 g (to 0.007 mol) of tin tetrachloride is used to 10,00 g (0.014 mol) TKF. The reaction proceeds spontaneously with evolution of heat, thus increasing the viscosity of the reaction system and forms a viscous yellow complex TCP·SnCl4with a density equal to d420=1,46.

Example 2. Epoxy composition prepared by dissolving the catalyst TCP·TiCl41,04 g modifier TKF (20 g) and then adding the mixture obtained in epoxy resin (100 g) analogously to example 1. The catalyst TCP·TiCl4get addition to 2.57 g (to 0.007 mol) of titanium tetrachloride to 10,00 g (0.014 mol) TKF. The reaction proceeds spontaneously with evolution of heat, thus increasing the viscosity of the reaction system and forms a viscous brown complex TCP·SnCl4with a density equal to d420=1,31.

Example 3. The epoxy composition is otomat by dissolving the catalyst bis(three(2-chloroethyl)phosphate)tetrachlorogallate (THAT·SnCl 4) 1,3 g modifier TCHEPH (20 g) and then adding the mixture obtained in epoxy resin (100 g) analogously to example 1.

Example 4. Epoxy composition prepared by dissolving the catalyst bis(three(2-chloroethyl)phosphate)Tetrachloromethane (THAT·TiCl4) 0.26 g at the modifier TCHEPH (20 g) and then adding the mixture obtained in epoxy resin (100 g) analogously to example 1. The method of producing catalyst THAT·TiCl4described in the patent.

Example 5. Epoxy composition prepared by dissolving the catalyst bis(three(2-chloropropyl)phosphate)Tetrachloromethane (THPP·SnCl4) 1,69 g modifier TCHEPH (20 g) and then adding the mixture obtained in epoxy resin (100 g) analogously to example 1.

Example 6. Epoxy composition prepared by dissolving the catalyst bis(three(2-chloropropyl)phosphate)Tetrachloromethane (THPP·TiCl4) 1,04 g modifier TCHEPH (20 g) and then adding the mixture obtained in epoxy resin (100 g) analogously to example 1.

Table 1
№ p/pComponentsThe composition, in mass
123 4567 control
1Epoxygenase resin100100100100100100100
2Bis[tricresylphosphate]tetrachloroaurate1,04------
3Bis[tricresylphosphate]Tetrachloromethane-1,04-----
4Bis[three(2-chloroethyl)phosphate]tetrachloroaurate--1,3----
5 Bis[three(2-chloroethyl)phosphate]Tetrachloromethane---0,26---
6Bis[three(2-chloropropyl)phosphate]tetrachloroaurate----1,69--
7Bis[three(2-chloropropyl)phosphate]Tetrachloromethane-----1,04-
8Tricresylphosphate2020-----
9Three(2-chloroethyl)phosphate--2020 ---
10Three(2-chloropropyl)phosphate----2020-
11Triethylenetetramine10101010101010

The obtained epoxy compositions have enhanced mechanical strength: the impact strength increases by 1.2-1.5 times the strength at break in the 1.5-2.3 times. All songs are self-extinguishing.

Thus, the claimed invention allows to expand the range of compositions with self-extinguishing properties and improved physical and mechanical properties (see table 2).

Table 2
Physico-mechanical properties, the balance of mass after combustion and the time of gelation of epoxy compositions
No. of songs and τGeel, hBut, kJ/m2σp, MPaεRel., %G %τGeel, hΔm, %
11,7410588,7891,74Do not burn after removal of the source of fire
21,9012827,9901,90
3of 2.2115,5548,283of 2.21
42,2513727,5852,25
51,521873 8,1841,52
62,2514566,9832,25
7 control0,538,2361,0970,5316
Legend: G - gel-fraction (output three-dimensional product), τGeel(gelation time), were measured at T=20°C for the sample consisting of 20 g of resin.

Epoxy composition comprising epoxygenase resin, phosphate modifier, amine curing agent, characterized in that it as a modifier contains a phosphate compound selected from the group including tricresylphosphate, three(2-chloroethyl)phosphate, three(2-chloropropyl) phosphate, and the curing catalyst is a complex of Tris(halogenated)phosphate (TGIF) with chlorides of tin or titanium General formula (I)

where e=Sn, Ti, R=-CH3With6H4, -CH2CH2Cl, -CH2CH(Cl)CH3
when the ratio of components, parts by weight:

epoxygenase resin ED-20100
specified phosphate modifier20,0
the specified catalyst0,26-1,69
the hardener10,0



 

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