Composite material based on unsaturated polyester resins

 

The invention relates to the production of composite materials used for manufacture of products for industrial and domestic purposes. The material is produced by impregnating a fibrous filler - nylon, Narodnogo or viscose fibers (18-33%), unsaturated polyester resin grade M-15 (40-61%), and then curing system (12-42%). As a final use 60-80% solution anilinopiperidine resin SF-A in acetone or a mixture containing 9.3 to 9.8 percent resin brand SF-A, 26,5-30.8% of carboxymethylcellulose, 3,1-3,3% acetone and 56.8-60,5% water. Impregnated material thermoablative for 2 hours while gradually raising the temperature from 20 to 180C and then subjected to direct compression. The invention allows the use of cheaper curing system, to improve the strength and heat resistance of the products. 3 tab., 1 Il.

The invention relates to the field of synthetic resins and polymeric composite materials (PCM) based on them for the products of industrial and household purpose.

Known polymer obtained by curing of unsaturated polyester resins MO-1 peroxide curing agent (gitaris), the next soderzhanie,5

[Handbook of plastic masses, so 2./Ed. by C. M. Kataev, V. A. Popov, V. I. Sazhin. - M.: Chemistry. - 1975. - S. 142].

Peroxides are relatively expensive chemical products.

Known polymer obtained by curing of unsaturated polyester resins MO-15, where the curing system used benzoyl peroxide, dimethylaniline, dibutyl phthalate, styrene, with the following content of components of a composite material, wt.%:

The polyester resin MON-15 95,0

Benzoyl peroxide 1,0

Dimethylaniline 0,3

Dibutyl 1,0

Styrene 2,7

[Handbook of plastic masses, so 2./Ed. by C. M. Kataev, V. A. Popov, V. I. Sazhin. - M.: Chemistry. - 1975. - S. 142].

Known composite material (prototype), obtained by impregnation of a fibrous filler unsaturated polyester resin and an alcohol solution rezol phenol-formaldehyde resin, with the following content, wt.%:

The solution of unsaturated polyester resins

the monomer or oligomer of an unsaturated ester of 25-90

Alcohol solution rezol

phenol-formaldehyde resin Else

[EN 2005742 C1, 15.01.1991].

In the specified similar as a curing system for curing the unsaturated polyester resin is redusa system for curing unsaturated poly-ester resins are encouraged to use the acetone solution rezol of aniline-phenol-formaldehyde resin (GOST 18694-80), as well as mixtures of more complex composition that is different from the curing system of the considered similar. Acetone boils at a lower temperature than ethanol, is removed more easily from the material and therefore makes fewer defects in material than alcohol.

In the claimed invention, the aim was to find available, relatively cheap and effective curing system for unsaturated polyester resins, as well as to improve the strength and heat resistance of the obtained materials.

This is achieved by the fact that in the composite material containing unsaturated polyester resin MON-15 and curing system, impose additional fibrous filler, with the following content, wt.%:

Polyester resin MON-15 40-61

Curing system 12-42

Fibrous filler 18-33,

and as curing system is used, wt.%:

Resin, aniline-phenol-formaldehyde SF-A 60-80

Acetone 20-40,

or, wt.%:

Resin, aniline-phenol-formaldehyde SF-A of 9.3 and 9.8

Carboxymethylcellulose (CMC) 26,5-30,8

Acetone 3,1-3,3

Water 56,8-60,5

Conventional hardeners unsaturated ether resin MON-15, which represents the solutions of unsaturated products Conde is dropboxid cumene (gitaris) or benzoyl peroxide. Due to the relatively high costs of peroxide curing agents has been a challenge to replace them with more available and cheap materials.

The method SNK is on reinforcing thread first put the main component of the binder (in this case, the resin MON-15), and then curing system [Studentsov Century. N. theoretical foundations for the processing of polymers and elastomers. - Saratov: Saratov state technical University. - 1995. - 71 S.], [patent 2135530 of the Russian Federation. Studentsov C. N., Karpova I. C. a method of obtaining a reinforced polymeric materials. BI No. 24, 1999].

To obtain prepregs used the following components:

Unsaturated polyester resin grade M-15 (TU 6-05-861-73). Represents 60-75% solution of polyester in styrene oligomer. The oligomer is obtained by polycondensation of maleic anhydride and fumaric acid with ethylene glycol.

The prototype in the presence of initiator (peroxide benzene or cumene peroxide) is the copolymerization oligomer (unsaturated polyester with styrene.

The aniline - phenol-formaldehyde resin brand SF-A (GOST 18694-80), it is obtained by polycondensation of phenol with excess formaldehyde in the presence of an ammonia catalyst. In normal conditions - solid ve the Sopa)x], where x = 0,4-1,2 (TU 6-12-1020-75) - sodium salt of a simple ester of glycolic acid and cellulose, obtained by treatment of the alkali cellulose with alkylating agent. In normal conditions - solid granular substance of white color.

All these substances are soluble in acetone. As fibrous fillers used technical thread:

- Nitron (TU 6-01 -15-70-85);

- nylon (TU 15897-79);

- viscose (TC 6-06-N-79).

From the obtained prepregs by the method of direct compression produced plates that are then cut out samples of standard sizes.

The present invention is illustrated in the drawing, which shows a diagram of receipt of the prepreg method layer application components, where 1 is the package with the original thread; 2 - bath for applying resin; 3 - tube furnace; 4 - bath for applying a curing system; 5 - receiving device.

Example 1. Technical nylon thread is passed through an impregnating bath containing MO-15, and then through an impregnating bath hardening system - 75 wt.% the solution SF-A in acetone, that is, to obtain the prepreg used method SNK (drawing). The obtained prepreg was subjected to heat treatment for two hours while gradually raising the temperature from 20 to 8 MPa, 15 minutes) made of a plate thickness of 4 mm. of these plates cut out samples of standard sizes and subjected to physico-mechanical tests.

Example 2. The example in example 1, characterized in that after the first impregnation bath impregnated filament is subjected to the magnetic treatment (MO) in a constant magnetic field (RAP) tension A for 1, 3 C. Forth in example 1.

Example 3. The example in example 1, characterized in that as the curing system in a second impregnating bath is used 67 wt.%-s ' solution of SF-A in acetone.

Example 4. The example in example 1, characterized in that as the curing system in a second impregnating bath used 60 wt.%-s ' solution of SF-A in acetone.

Example 5. The example in example 1, characterized in that as the curing system in a second impregnating bath is used 55 wt.%-s ' solution of SF-A in acetone.

Example 6. The example in example 1, characterized in that as the curing system in a second impregnating bath is used 80 wt.%-s ' solution of SF-A in acetone.

Analysis of example 1-6 shows that the optimal concentration of the curing system is in the range of 60-80 wt.%. At a lower concentration of the solution SF-A in acetone (example 5) of adnych resins in net product of about 80% and, respectively, with reduced strength characteristics.

When the concentration of the curing system 80% (example 6) is achieved a relatively high degree of conversion, so that the material becomes more brittle and the impact strength decreases (“embrittlement” of the material).

In addition, an excessive increase in the concentration of the solution in the second impregnating bath creates too high a resistance for moving the thread, making it difficult the treatment, and leads to excessively high content of resins SF-A in the material.

Example 2 illustrates the increase in the degree of conversion and a significant increaseandin the short-MO after the first impregnation bath when using the CPC. The content of reinforcing filler within 23-29 wt.% is determined by the sorption properties of reinforcing filaments. Additional extraction of the binder was not used.

Example 7. Technical thread Nitron is passed through an impregnating bath containing MO-15, and then through the second impregnating bath containing SF-A, acetone, CMC and N2O in the ratio of 9.6:3,3:29:58 wt.%, that is, to obtain the prepreg used method SNK (drawing). The obtained prepreg was subjected to heat treatment for three hours while gradually raising the temperature from 60 to 140

Example 8. The example in example 7, characterized in that after the second impregnation bath impregnated filament is subjected to MO in PPM tension A for 1,3 C. Further example 7.

Example 9. The example in example 7, characterized in that the filler used technical nylon thread.

Example 10. The example in example 7, characterized in that the filler used technical nylon thread and after the second impregnation bath impregnated filament is subjected to MO in PPM tension A for 1,3 C. Further example 7.

Example 11. The example in example 7, characterized in that the filler used viscose technical thread.

Example 12. The example in example 7, characterized in that the filler used viscose technical thread and after the second impregnation bath impregnated filament is subjected to MO in PPM tension A for 1,3 C. Further example 7.

The analysis of polymers 7-12 shows an increaseandand especially abeatscompared to the prototype. pfall in comparison with the prototype as a result of the Yu-reinforced materials.

In examples 13-16, the main variable parameter is the mass ratio of CMC and water.

Example 13. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in the ratio of 9.8:3,3:26,5:60,5 wt.%.

Example 14. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in the ratio of 9.3:3,0:30,8:56,8 wt.%.

Example 15. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in the ratio of 10.3:3,4:23,3:63 wt.%.

Example 16. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in the ratio of 8.7:2,9:34,9:53,5 wt.%.

The optimal ratio of CMC and water (examples 13 and 14) is 26.5:60,5-30,8:56,8 wt.%. Low water content leads to the formation of clots CMC in solution and prevents high-quality impregnation (example 15), and excess water content (example 16) results in loose nedootsenennogo material.

Example 17. Prepare a mixture consisting of MO-15 and 75 wt.%-aqueous solution of SF-A in acetone, taken in the ratio of 80:20 wt.%.

The resulting mixture is poured into the cuvette standard sizes and subjected to curing pirnie samples of standard sizes subjected to standard tests (table. 1).

The cost of the material obtained is 37 rubles/kg, while maintaining traditional relationships between prices resins MO-15, SF-A and acetone.

Example 18. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in the ratio of 10.6:3,5:21,1:64,8 wt.%.

Example 19. The example in example 12, characterized in that the components of the curing system: SF-A, acetone, CMC, water is taken in a ratio of 8.5:2,8:37:51,7 wt.%.

Beyond the optimum content of CMC affects the strength characteristics of polymer composite materials (examples 18-19, PL. 1)

Example 20 (composition-similar). Prepare a mixture consisting of MO-1, hyperize and accelerator NC, taken in the ratio 87,7:5,3:7 wt.% respectively [Handbook of plastic masses So 2/ Ed. by C. M. Kataev, V. A. Popov, V. I. Sazhin. - M.: Chemistry, 1975. - S. 142].

Example 21. Prepare a mixture consisting of MO-15, 50 wt.%-aqueous solution of benzoyl peroxide in dibutyl phthalate and 10 wt.%-aqueous solution dimethylaniline in styrene, taken in the ratio 95,2:1,9:2.9% of the mass. respectively [Handbook of plastic masses So 2/ Ed. by C. M. Kataev, V. A. Popov, V. I. Sazhin. - M.: Chemistry, 1975. - S. 142].

Example 22. Example example 11, characterized in that the material contains 35 wt.% polyester is Ola MO-15.

At low content of the polyester resin MON-15 prepreg remains dry and poorly pressed (example 22), and when too large, the content of the polyester resin MON-15 are soft nedootsenennyi samples.

Physico-mechanical characteristics of the materials obtained are shown in tables 1 and 2.

The composition of the proposed compositions are given in table 3.

The cost of the material obtained according to example 17 is 37 rubles/kg, while maintaining traditional relationships between prices resins MO-15, SF-A and acetone. Relatively low strength characteristics of the material caused not only by the properties of the new binder as the difficulty of obtaining a monolithic casting samples. This flaw is easily corrected by the addition of fillers.

The cost of the material obtained according to example 21 is 53,6 RUB/kg while maintaining traditional relationships between the prices of polyester resin MON-15, benzoyl peroxide, dimethylaniline and styrene [Catalog of chemical reagents and high-purity chemicals/ Union reagents. M.: Chemistry, 1971. - 648 S.].

Comparison of examples 17-21 shows that replacing perocet the resulting composite at 31%. This is because the raw materials for the production of resin SF-A much cheaper substances used as a source to obtain a peroxide curing agents. According to the proposed technology new materials able to withstand temperatures of 150-170C.

Claims

Composite material obtained by impregnating a fibrous filler unsaturated polyester resin and curing system, followed by pressing, characterized in that as the fibrous filler used nylon, nitrone or viscose fiber, as unsaturated polyester resin - resin grade M-15, and as a curing system - 60-80% solution anilinopiperidine resin brand SF-A in acetone or a mixture of the composition, wt.%:

The aniline-phenol-formaldehyde resin

brand SF-A of 9.3 and 9.8

Carboxymethylcellulose 26,5-30,8

Acetone 3,1-3,3

Water 56,8-60,5

and at first fibrous filler is impregnated with unsaturated polyester resin grade M-15, and then hardening the system, followed by heat treatment for 2 h with a gradual rise in temperature from 20 to 180With direct pressing, when the trail>twardawa system 12-42

Fibrous filler 18-33

 

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