SU507601A1 - The method of obtaining heat-resistant resins - Google Patents

Description

/ There is a known method for producing thermosto I of these resins, both on the basis of various monomeipes by converting them to elevation of precursory compounds, and by modifying high molecular weight compounds, including plant and vegetal; origin It is widely used to produce heat-resistant resins I, organic compounds T Resins, which are more heat-resistant, would be obtained from the wood component — the whole I lulose and its simple and complex esters. According to a known method, cellulose and its esters are treated with common formulas of the formula R-R, Sr Cl i. - - - H Specificity of the reaction; chl (phylans & from cellulose | ZOY consists in the necessity of using large amounts of pyridine I to prevent the destructive effect of the released; SYa HC1. On cellulose, nosTMviy is recommended 1 h | pyridine chlorosilane solution added; to suspension of cellulose in pyridine. However, for this method it is necessary to use significant amounts of toxic heterocyclic amines and to use as a raw material for the purpose of scrap, a shortage of material widely used in paper, fibers and Products. I Goal This invention is a simplification of the method and an increase in the heat resistance of the resins. This is achieved by using the E quality Hydroxyl-containing lid.,} a large-tonnage waste industry I chemical processing 10) The three-neck round of heat resins for these resins are as follows. flask; supply; with a stirrer, drip and reverse with a 1N refrigerator, at temperatures you: above room temperature (dry weight of lignin (less than | 3% humidity) and excess 1 monoalkyldichyls silane G (not more than 4 times, at the rate of 1 ml) poured from the funnel . | lana per 1 g of lignin) and, constantly peremv "; shiva, withstand the mixture up to 3 hours npjn 39 I given, temperature. You can not protect the air from moisture. The use of dry inert atmosphere does not materially affect the output and the properties obtained resin. After a specified time, toluene is added to the reaction mixture and the flax Shuffle I

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wow. The solid residue is separated from the liquid phase by centrifugation, washed in a centrifuge with toluene to colorless slaves Oi rntl-I, and the toluene washes-W1) e are combined with the main toluene soluble E product. Brilliant light brown coatings can be obtained from toluene resin. The finished resins contain about 30% silicon, partially dissolved.

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in organic ipacTB poresL51x

air dry and persist; Without decomposition at a temperature of over 150 ° Ci, pep is from a to 13% of its mass at up to and from 1 to 22% of its mass when heated to at a heating rate of 12 deg / min.

The reaction can be carried out in the presence of dilution of 1 bodies, for example, toluene, which ensures a more uniform wetting of the lignin at i „. using small ratios mono, al; kildichlorosilane (C) to lignin (L), i.e. . In this case, toluene is added in an amount of dosage to the weight of the nin. the sample was wetted (2 ml of talonuide for 1 g of lignin), and the rest of the treatment was done according to the scheme described. The thermal characteristics of the resins obtained in the presence of diluents do not change.

In order to increase the output of smolze and higher “Q NIN degrees using lignin, it is possible not to use a solid residue, but a solid residue; vyu reaction mixture. In this case, it is convenient to treat the lignin monoa; psidichlor, silane in the absence of toluene, and to remove it; Volatile solvents, such as acetone, should be used for the total reaction product. However, the heat resistance of such a resin decreases, the loss in grams, 1 sleeves at a speed of 12, 40 at 200 ° C reaches.

In terms of heat resistance, the obtained resins are close to pure organic poly. The measures are significantly higher than opra3iH: for 24 hours at 25 ° C, the mass of 45 caj is 15 to 28% for them, while for polyorganosiloxanes the mass loss is (depending on:; type of polymer) for caprone reached-. 55.5% for polystyrene — 65.6%, —GW 50 glyptal polymer — 93.4%.

Example. 1g of dry lignin (9% hy; foxenh5 x groups) is placed; in reactivity) &. j a vessel, add 2 ml of tochuol and 4 ml

Ethyl Chlorosilane (CHSiHCl) and you .55 "with O2.

they are kept at room temperature for 3 hours in an air atmosphere with constant stirring. The solid residue is separated, centrifuged, washed, toluene washed

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the solutions are combined with 1x; norns, moptomaplastic product. After drying on air and drying in a vacuum cupboard at. 50 ° C, with a yield of 236%, relative to the lignin, a homogeneous csmkorichna blesh elastic resin with a content of 33.0% silicon, 36.6% carbon, 7.7% hydrogen is obtained. The resin dried ceases to dissolve in toluene, is completely soluble, decomposing into concentrated KOH and, to a significant extent, solution; Rome in acetone and MeTHn3TH.iKeTOHe, partially soluble in dioxane, methylene chloride and dichloroethane.

| The preheating of the resin at 22 ° C at a rate of 12 degrees / min does not see a loss in weight, it further heats up to 410 ° C and causes a mass loss, and when heated to .C, 10% of the mass of smog is lost. After 24 hours of heating with a mass loss of 15%.

EXAMPLE 2. In contrast to example. toluene is not used in the reaction, it is added only after the reaction has been completed, the mixture is thoroughly re-mastered, the toluene-insoluble product is separated and washed with a lyuol in a centrifuge. The remaining operations; similar: described in example 1. The yield of cm7 (L1 22O% j co-silicon-rye-silicon. 28.3%., The mass loss of the obtained Resin after 24 hours of the total heating at 250 ° C was 18%., P and m 6 p 3, 1 g dry lignin psn .: Shay in the reaction vessel, pour 2 ml of toluene and 1.3 ml of monomethyl dd utorosilana

(CH SiHCl) and incubated for 3 hours at, oii.

ksmnatnoy tel: eurature in an airy atmosphere. re with constant stirring. The solid residue is separated by centrifugation, washed with toluene, and the washing toluene solutions are combined with the main toluene rostrum (the "impure product." After drying in air and drying in a vacuum, the cabinet at 5 ° C: in a yield of 78.3%, a homogeneous dark color is obtained with a yield of 78.3% Bleo "- CMuia oil with 27% silicon,

After a 24-hour heating at 250 ° C, the mass loss of the resin was 19%.

Example 4. The treatment of lignin with pr VODIT is similar to that described in Schemer 3, i only used for the reaction 4 ml of mono-1 metidichlorosilane (CH HC). The yield of resin is 222; oh, the silicon content is 30.% ...,. /

When heated at a rate of 12 deg / min, wiped w / o was not detected; ri 420 C loss is 13%, with OO-C-, 22% .--:

After 24 hours of heating at 250, wiping the resin was 16%.

Example 5. The treatment of lignin is carried out as in Example 4 and only a stream of nitrogen is passed through the reaction mixture. The resin yield is 214%, the content. silicon 30%.

When nsreve with scfosti 12 deg / min, mass loss to 150 ° С was not detected, at 420 ° С the loss will be 12%, with

: 600 ° -21%.

Poopa, a flammable liquid at 250 ° C, mass loss: amounted to 18%. . ; Try it on. 1 g of dry pigin (9%; hydroxyl groups) is placed in the reaction of the first vessel, 4 ml are poured; atildichloroschysh (C H H SijHCd „) and incubated for 3 hours: at the temperature of the mixture in the atmosphere of an inerne atmosphere; gas with constant stirring,; after which the total reaction product is rotated into 4 ml of acetone and transferred to the box,: After drying in air and {drying in a vacuum cabinet at 50 ° C with a yield of 263% relative to lignin, a uniform 1 dark brown glitter is obtained Conch resin with a silicon content of 15%. Dried CMCW I la not dissolved in toluene, gasoline, hex; Sana, Malorastfnma in acetone, methylethyl; ketone, nitromethane, dimethylformamide, solution in chloroform em, pyridine.

When the resin was heated at a rate of 12 g deg / min, the mass loss was not detected, at 6OO ° C the loss was 56% t After 24 hours of heating at 250 ° C, the mass loss was 15%.

1- Example. The processing of lignin is carried out as described in example 6

only the reaction mixture is kept 3; HG hours at room temperature ipeaterype, and on a heated-up silicone bath. The resin yield is 220% relative to lignin, the silicon content is 18%.

When the resin was heated at a rate of 12 deg / min, the mass loss to ISO-C was not detected, at 400 ° C the loss was 18%, at 600 ° -38%. After 24 hours, nagr –va jjpw, the mass loss of resin j was 23%.

Formula

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Claims (2)

I 1. The method of obtaining heat-resistant with the processing of gdroksil-containing full. Chlorosilicon-containing organosubstituted chlorides, due to the fact that, in order to simplify the process and increase the thermal stability of the resins, lignin is used as a hygrothermal polymer and the treatment is carried out at 2O..1000C Galkyldy-, HCl with a common formula (H) Cj. where, С Н, with the ratio of isholo i о 1: 1 to 1: 4 for 1 hour. 2. A pop method, 1 characterized in that, in order to reduce the flow rate and the alkyl dichlorides of the silane, the treatment is reduced in toluene. SOURCE: information taken into account when examining 1. US Patent No. 2,532,622, C, 2BY 215, priority 05.12.50.