RU1789527C - Method of producing thermosetting nitrogen containing phenolic resin - Google Patents

Description

is the release of a significant amount of volatile (mainly ammonia): in the melt up to 4.1% in a solvent medium - up to 5.48% by weight of the starting components, as well as a high content of free phenol: up to 19% in the melt and from 3, 2 to 10.8% in a solvent. Among the disadvantages is TQ, which, when the resins cure at 175-200 ° C, a large amount of ammonia G3 is released due to the thermal decomposition of all methyleneamine bridges to form methylene bridges.

The aim of the invention is to obtain a nitrogen-containing resin with a low phenol content, capable of self-hardening without the release of ammonia and other volatile products. 5-0.75 in a melt or solvent. During the melt reaction, the components were mixed in the reaction vessel and heated in the range of 100-140 ° C for 1-4 hours. The synthesis time was determined by the maximum phenol conversion. The reaction mixture throughout the reaction remained a clear and homogeneous light yellow melt. The reaction proceeded without emitting volatile products, as evidenced by the constant weight of the reaction mixture.

The gross formula of tetramethylenediethylenediamine is CaHi6N4 / 6 /.

The resin is characterized by the following characteristics:

Melting point, ° С60-75 Phenol content from the initial one,% 2.5-4.5 Molecular weight 750-1000 Gelatinization time at 180 ° С, 30-60 Mass loss for 20 min at 180 ° С,% less than 1 , 4 Nitrogen content,% 13.9-18.6. For the synthesis of resins in solution, any high boiling polar liquids that dissolve the starting components and the resulting resins, for example, dimethylformamide, can be used as a solvent. Used 50% solutions (total monomers). The mixture was heated at 140 ° C until almost complete phenol conversion (99.0-99.5%) for 4 hours. Received viscous homogeneous solutions of light brown color, stable at room temperature for unlimited time. Solutions can be used for varnishes and adhesives without additional

processing. Isolated from the solvent by precipitation with water and dried resins had the following indicators:

Melting point, ° C 105-110

The phenol content,% 0.1

Molecule RNA mass520-600

The nitrogen content,% 12.0-12.4

Resins obtained both in the melt

and solution, when heated to 180 ° C in

for a short time, they lose their solubility in organic solvents and concentrated alkali solutions, even when boiled. Loss of mass during curing does not exceed 1.4%.

Compared with the prototype, the method allows to reduce the phenol content in the resin to 4.5% in the melt (versus 19% for the prototype) and up to 9.1% in solution (versus 3.3-10.8% for the prototype). Nitrogen content

ranges from 13.7 to 18.6% in the melt (versus 6.3% for the prototype) and from 12 to 12.4% in solution (versus 5.4-6.4% for the prototype). The resins do not contain compounds that emit ammonia during processing and use. Therefore, they can be used in contact with non-ferrous metals.

The invention is carried out as follows.

Example 1.94 g of phenol (1 mol) and 84 g (0.5 mol) of tetramethylenediethylenediamine (TMDEDA) were mixed and heated at 100 ° C for 240 minutes.

Example 2. 94 g of phenol (1 mol) and 100.8 g.

(0.6 mol) TMDEDA was mixed and kept at 110 ° C for 180 minutes.

Example 3. 94 g of phenol (1 mol) and 125.2 g (0.75 mol) of TMDEDA were mixed and kept at 120 ° C for 150 minutes.

Example 4. 108 g (1 mol) of m-cresol and 84 g (0.5 mol) of TMDEDA were mixed and kept at 120 ° C for 60 minutes.

Example 5, 108 g of o-cresol and 84 g of DMEDA were heated at 120 ° C for 180 minutes.

PRI me R 6. 108 g of p-cresol and 84 g of TMEDA were heated at 120 ° C for 180 minutes.

PRI me R 7. 94 g (1 mol) of phenol, 84 g (0.5 mol) of TMEDA and 178 g of dimethylformamide were heated with stirring

240 min at 140 ° С, then the resin was planted with water and dried in vacuum at SO – SO0 С to constant weight. The residual phenol content in the solution at the end of the reaction did not exceed 1%, the phenol content in the resin was not more than 0.1% of the initial amount.

Sample 108 g (1 mol) m-cresol and 84 g

(0.5 mol) of TMDEDA and 192 g of dimethylformamide were kept at 140 ° С with stirring for 240 min. The content of residual m-cresol in the solution did not exceed 1%. The resin was planted with water and dried in vacuo at 60-80 ° C to constant weight. The content of m-cresol in the resin was not more than 0.1% of the initial amount. Characteristics of resins in comparison with the prototype are presented in the table.

Claims (1)

SUMMARY OF THE INVENTION A method for producing a thermosetting nitrogen-containing phenolic resin by polycondensation of phenol or cresol with an active nitrogen-containing compound by heating in a melt or solvent, characterized in that, in order to reduce free phenol in the resin and Resin Characteristics to exclude the release of ammonia and other volatile products during condensation and solidification of the resin, tetramethylene diethylenediamine is used as an active nitrogen-containing compound, condensation is carried out at a phenol: tetramethylene diethylenediamine molar ratio of 1: 0.5-0.75 at 100-140 ° C.