SU1708815A1 - Liquid dimethylsiloxaneurethandiepoxyde oligomer for the synthesis of thermostable polymers - Google Patents

Abstract

The invention relates to the chemistry of polymers, namely, to a new compound, a di-1-silsilox-urethane-epoxy oligomer of the formula <&lt; ^^ - ag &lt; b- ^ h, T ", | c", 11-c-ac | m {- "1-sa , - "S?! IC - * &lt; &gt; & &lt; R, [Ho. ^ - {o &lt; in, - &lt; - "where n = 14, 19, 29, which can be used to produce heat resistant polymers. The invention improves the Vicat heat resistance of oligomers. hardened with maleic anhydride, up to 230-245 ° C. When using oligomers in compositions based on ED-20 epoxy resin, curable with polyethylene polyamine, the heat resistance of the modified polymers increases to 300–315 ° C. The oligomer is obtained at 40-50 ° C in bulk through the step of forming macro-diisocyanate. Then glycidol and a urethane catalyst are introduced into the macrodisocyanate. The ratio of isocyanate and hydroxyl groups in the first stage is 2: 1, in the second - 1: 1. The first stage is carried out up to 50% conversion, the second - until the complete conversion of the isocyanate groups. Table 3. • • • • • • • • The invention relates to the chemistry of polymers, namely, to a new compound - dimethylsiloxanurethanesic oxide oligomer of the formula “V -” - - - - -K! &Gt; &amp; fcn. | At .-? - ™. |? '”H'-" "t. N. &Gt; & | -H' [" -oc-o-s-k- &lt; ^ si, &quot; - &lt; | -G-SV, -I-CK, ... P = 14, 19, 29, which can be used to produce heat-resistant polymers. The purpose of the invention is to increase the heat resistance of polymers. An oligomer is obtained at 40 -50 ° C in bulk through the stage of formation of macrodisocyanate. 2,4-toluene diisocyanate is used in the isocyanate component.Further, glycidol and a catalyst for urethane formation are introduced into the macrodisocyanate (dilaurienedibutyltin, 0.05% by weight of the mixture). The ratio of "zocyanate and hydroxyl groups in the first stage is 2: 1, on the second is 4: 1. The first stage is carried out up to 50% conversion, the second is carried out until the isocyanate groups are completely transformed. ^ Oso00tLs &gt; &amp;

Description

The identification of the products at the first stage of synthesis (formation of macrodisocyanate) and the second stage (formation of the final product) is carried out by chemical analysis of isocyanate groups using an IR spectroscope and.

The infrared spectra of the macrodiisocyanate, when the degree of conversion of the isocyanate groups reaches 50%, shows absorption bands in the regions 340 &amp; 3,300 cm (vibrations of the urethane group), 2275-2240 (vibrations of the isocyanate group) and there are no absorption bands in the region of 35703580 cm ), which confirms the formation of Macrodiisocyanate,

In the IR spectra of the final product with the complete transformation of the isocyanate groups, absorption bands in the areas of 3400-CSP (vibrations of urethane groups) are noted. 1260-1240 cm (zpoxic cycle oscillations). 80-850, 1235-1240, and 1260-1265 (oscillations of the Sl-CH3 bond), 1020-1090 (vibrations of the S1-0-SI and SI-0-C bonds) and there are no absorption bands in the region characteristic of the and isocyanate groups (3670-3580 and 22752240 cm).

The data of PC-spectroscopy and chemical analysis of isocyanate groups (0% at the end of the synthesis) confirm the formation of dimethylsiloxane epoxide.

Maleic anhydride can be used as hardeners of epoxy oligomers, as well as polyamines and acid hardeners based on pyromellite dianhydride and di- and trmols. Curing is carried out at 160-190 ° C. The ability to change the molecular weight of oligomers through the use of various polydimethylsiloxane rubber compounds improves the heat resistance of polymers based on them.

Example 1. Obtaining macrodisocyanate K-11T.

In a 3-necked flask equipped with an electromechanical stirrer, a thermometer, and a tap to connect to a vacuum system, 11.0 g (0.01 mol) of oligodimethylsiloxanediol (p 14) mol% are charged. May 1100 (;; 1.3 П at 20 ° С, d 0.998 g / cm moisture content 0.01%, concentration of the OH group 3.05–3.10%) and 3.48 g (0.02 mol) freshly distilled 2.4- toluene diisocyanate (2,4-TDI). The mixture is cooled to 2530 ° C and the synthesis is carried out to a 50% conversion of the isocyanate groups. After completion of the synthesis, a vacuum system is connected and deaeration is carried out at a residual pressure of 3-5 mm Hg. during

0.5 hour. Obtain 14.0 g of silicon-containing: chakrodiisocyanate in the form of a transparent pale green liquid.

Example 2. Preparation of Macrodiisocyanate K-15T (yield 96.7%)

The process described in Example 1 is repeated. 15.0 g (0.01 mol) of oligodimethylsiloxandolol (p - 19) are used as starting materials.

mol.mae. 1500 (; 1.27 Pz at 20 ° С, d 0.995 g / cm at 20 ° С, moisture content 0.01%, OH group content 2.25-2.28%) and 3.48 g (0, 02 mol) 2.4TDI, 18.0 g of macrodisocyanate are obtained in the form of a transparent pale green liquid.

Example 3. Obtaining macrodisocyanate K-22T (yield of 97.4%).

The process described in Example 1 is repeated. 22.0 g (0.01 mol) of oligodimethylsiloxane diol are used as starting materials (n 29 (mol. May. 2200 (; 1.25 P at 20 ° C; d 0.992 g / cm at 20 ° С, moisture content 0.01%:

concentration of the OH group (1.50-1.55%) and 3.48 g (0.02 mol) of 2,4-TDI. 25.0 g of mzcrodiisocyanate are obtained in the form of a transparent pale green liquid.

Example 4 Epoxy Preparation

oligomer K-11TE (yield 98.1%).

After deaeration is completed, 1.48 g (0.02 mol) of freshly distilled glycidyl alcohol and a dilaurienedibutyltin catalyst in the amount of

0.05% by weight of a mixture of macrodisocyanate K-1 IT and glycidol. Synthesis is carried out at 50 ° C until complete disappearance of the isocyanate groups (about 2.5 h). The oligomer is washed with hexane and vacuum under a pressure of 3-4

mmHg. within 1 -1.5 hours. 15.2 g of dimethylsiloxane epoxy oligomer are obtained, yield 95.2%, p 14, silicon content 25.38% (calculated 25.42%), nitrogen content 3.26% (calculated

3.39%).

Example 5. Getting epoxy oligomer K-15TE,

The process described in Example 4 is repeated. The starting materials are taken as

18.0 g of K-15T Macrodiisocyanate and 1.48 g (0.02 mol) of freshly distilled glycidyl alcohol and catalyst are added to the load. Synthesis lead about 3 hours.

The resulting oligomer is washed with hexane and vacuumized under the same conditions. 19.2 g of dimethylsiloxane epoxy oligomer are obtained (yield 98.6%, p 19). silicon content of 27.59% (&amp;

27.70%), nitrogen content 2.65% (2.77% calculated).

Example 6. Getting epoxy oligomer K-22TE.

The process described in Example 4 is repeated. 25.0 g of K-22T macrodisocyanate are taken as starting materials and 1.48 g (0.02 mol) of freshly distilled glycidyl alcohol and the catalyst are added to the load. Synthesis lead about 3.5 g,

The resulting oligomer is washed with hexane and vacuumized under the same conditions. 26.2 g of dimethylsiloxane epoxy oligomer are obtained, yield 98.9%, p 29, silicon content 30.29% (calculated 30.41%), nitrogen content 2.01% (calculated 2.03%).

The resulting oligomers are whitish transparent resins. Their viscosity naturally decreases with increasing molecular weight of the siloxane part. These substances dissolve well in benzene, acetone, and dioxane and do not dissolve in water.

Example. Curing of oligomers with maleic anhydride.

1.57 g (0.01 mol) of maleic anhydride (MA) is added to 0.01 mol of the oligoetherutanediisoxide. The ratio of epoxy and anhydrite groups is 1: 0.5. The components are mixed at room temperature and cured at 190 ° C for 3 hours.

A comparative characteristic of the proposed oligdimethylsiloxane diapoxides and epoxy isocyanurate oligomer is given in Table. one.

Comparative characteristics of the proposed oligomers and epoxyisocyanurate, solidified with maleic anhydride (MA), are given in Table. 2

Testing the films to the effect of a 10% H2SO4 solution and a 10% NaOH solution at 95 ° C for 1 h did not lead to visual changes in the surface of the samples.

Example 8. Curing of oligomers in compositions with epoxy resin ED-20 and polyethylene polyamine (PEPA).

The mixing of the components in chemical cups is carried out with thorough mixing with a glass rod. The composition of the epoxy composition, mach.

Resin ED-20100

Oligomer10

Hardener (PEPA) 10

Liquid oligomeric mass is coated with previously cleaned and degreased surfaces of steel fungi, and the rest of the mixture is poured onto an inert substrate (fluoroplastic, polyethylene). Curing is carried out at 100 ° C for 8 hours.

Comparative characteristics of the modified epoxy composition and composition without oligomer are given in table. 3

Ph o rumula and 3 o bar e and Liquid dimethylsiloxanureand izpoksidny oligomer of the formula

/

CH, -tii-ai, -o-c-M-Q-c ",

.tcH, o "a -", b-cc, II

LJ ,.

where n 14, 19, 29 to obtain heat resistant polymers.

Table 1

table 2

Table 3

Claims (1)

Claim Liquid dimethylsiloxane urethane diepoxy oligomer of the formula where η = 14, 19, 29 to obtain heat-resistant polymers. Table 1 Indicators Epoxyisocyanurate Oligomer Oligodimethylsiloxane urethane diepoxide ΜΜι MM2 MMZ The content of EPOXY groups,% The content of total chlorine,% Stability, months The temperature of combination with the hardener, ° C mol. May. Viscosity at 20 ° С, П 24-25 None More than 18 20-25 850 5.25 4.01 3.19 Missing More than 7 20 1600 2.8710 ³ 20 2200 1.74 <10 ³ 20 2700 1.32 AI ³ table 2 Indicators Epoxyisocyanurate Oligomers of the Invention MM = 1600 MM = 2200 MM = 2700 Heat resistance on Vika, ° C 205-215 245 240 230 bone, ° C 250 290 280 255 Adhesion to steel, kgf / cm ² - 350 360 350 Table 3 Indicators Composition ED 20 + PEPA (10 parts by weight) Composition ED - 20 + PEPA (May 10. H) + oligomer (May 10. H) MM = 1600 MM = 2200 MM »2700 Adhesion to steel. kgf / cm ² 250300 350 365 360 P (three-dimensional fraction content),% 90-95 95 98 97 Heat resistance, ° C 270-290 300 315 310