SU1368316A1 - Method of obtaining oligovinyl-n-butyl ether - Google Patents

Abstract

The invention relates to polymer chemistry and technology and makes it possible to obtain reactive oligovinyl-n-butyl ether using the one-stage method with a density of 0.93-1.05 g / cm, which is achieved by heating at 90-120 ° C. 20-150 wt. rosin with 100 mach. vinyl n-butyl ether in the presence of zinc chloride or tin dichloride. 4 tab.,

Description

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The invention relates to chemistry and polymer technology, namely, to a method for producing reactive oligovinyl-n-butyl ether, and can be used in the chemical industry to create varnishes, adhesives, plasticizers for unsaturated rubbers.

The aim of the invention is to obtain oligovinyl-n-butyl ether containing unsaturated bonds capable of crosslinking under the action of sulfur.

Example. A 75.0 g finely ground rosin (with a melting point of 62–65 ° C and an acid number of 160–162 mg con / g), 50.0 g (0.5 mol). Vinyl n-butyl ether (150 parts by weight of rosin per 100 parts by weight of monomer) and 0.4 g of tin dichloride. The mixture is heated with vigorous stirring to 100 ° C. After 2.0 hours, the temperature is raised to 120 ° C and kept in this mode for another 0.5 hour to complete the process. The resulting by-products are then removed in a vacuum. 106.3 g (85.1%) of dark red resin were isolated with the following | Blowing characteristics: mol. 450, viscosity at 3.04 Pa; s; 1,5001, d4 ° 1008 kg / m (oligomer,: obtained by a known method has a density at 900-920 kg / m).

Example 2: 10.0 g of rosin, 50.0 g (0.5 mol) of vinyl-n-butyl ether (20 mash of rosin per 100 mash of monomer) and 0.15 g of dichloride tin are placed in a flask. . The contents of the flask are heated to 90 ° C, at which the further self-heating of the mixture begins to 120 ° C. After passing through the temperature maximum, the mixture was additionally kept at 110 ° C for 0.5 h. The total oligomerization process time was 1.0 h. The target product was worked up as in Example 1. 57.1 g (95.2%) of oligovinyl-n- was obtained. butyl ether: ml. m. 810; viscosity at 0.85 Pa-s; including 1.4650; d / 940 kg / m.

Example 3, the reaction is carried out for a period of 1.5 hours and additionally for a period of 0.5 hours. 75.0 g of rosin 100.0 g (1 mol) of vinyl-n-butyl ether and 0, 2 are taken. .g

, 20 G

83162

zinc chloride. The product is isolated as in example 1. 154.5 g (88.6%) of a dark red resin are obtained with the following properties: mol. m. 590; viscosity at 20 ° С 1.06 Pa С; h 1.4851; 989 kg / m

Example 4. Similarly to the examples presented above, the wire oligomerization process of 37.5 g of rosin AND 100.0 g (1 mol) of n-butyl ether in the presence of 0.2 g of dichloride tin at 90 ° C for 1.0 h with further additional exposure at 110 ° C with a duration of 0.5 h. The resulting mixture is then treated with rto example 1. 128.8 g (93.7%) of resin oligome m.720 were isolated; viscosity () 0.82 tight0

stew at 20 ° C 960 indicator

0

refraction h 1.4743.

Example 5. Oligovinyl n-butyl ether (100.0 g) prepared according to example 1 and 5.0 g (5%) of elemental

5 sulfur is introduced into a glass ampoule, which is sealed on a gas burner. The ampoule is placed in a thermostat heated to 80 ° C and kept in this mode for 96 hours. After separation of the formation.

The coarse polymer has a viscosity at 20 ° C of 60.5 mol / m. 3000

Synthesized red-brown resins are substances from oily to

with viscous, well soluble in most common organic solvents: aliphatic, halogen-containing and aromatic carbon. hydrogens, alcohols, etc., are not soluble in water. The output of oligomers 85-95% with the following physico-chemical characteristics: mol. 400-800 m;

raft0

viscosity at 20 ° C 0.8-3.0 Pa-s,

,ten

d 4

930-1050 index of refraction, 1.46-1.50,

0

five

In the IR spectra of oligovinyl-n-butyl ether, taken in a thin layer, there is no doublet in the region of 1620–1640 cm belonging to the vinylyloxy group of the vinyl-n-butyl ether. With an increase in the amount of monomer during the synthesis, the intensities of the absorption bands in the 1700– / 1730 cm region characteristic for stretching C O vibrations and in the 1250 region for ester groups, as well as the intensity of C deformation vibrations, decrease (915, 985 CM V). C-0 ether linkages (1100), which indicates the preservation of double bonds in the rosin fragment and confirms the above structure of the oligomer.

Data for examples 6-13 and properties oligovinyl-n-butyl esters are given in table. 1 and 2.

Due to its reactivity, oligomers can be used for various compositions based on unsaturated rubbers (compounds, sealants, etc.).

In tab. Tables 3 and 4 show the formulations and physicomechanical characteristics of unfilled vulcanizates and model mixtures used for the manufacture of sealants based on butyl rubber with an unsaturation of 1, 5% and with the content of the proposed oligomers and oligovinyl-n-butyl ether prepared according to a known method (with a viscosity of 0.78 Pa S and a density of 915 kg / m).

The parameters of the compositions indicating the effectiveness of the used plasticizers are taken as tensile strength (b.), Relative elongation (p), adhesion value to metal (to Art. 3) (A), and amount of extractable plasticizer (B). Model mixtures contain the following components,%: rubber

ten

15

20

25

 quality plasticizer using petroleum oil with a viscosity at 20 200 mPa s and oligovinyl-n-butyl ether, obtained at a ratio of 20 ma.h. on 100 ma.ch.

As can be seen from the table. 4, applied. synthesized oligomers instead of petroleum oil allows 1.5–2 times increase in strength and 2.0–2 times deformation of vulcanizates. In addition, the proposed oligomers, attached to rubber, are not capable of even redistribution, unlike other low molecular weight oils. The non-recovery method of oligovinyl-n-butyl ether, obtained according to a known method, due to the absence of chemical interaction with rubber and due to poor compatibility with neither worsens the physicomechanical properties of vulcanizates.

Claims (1)

Formula invented Method for preparing oligovinyl-nbutyl ether by heating vinyl-n-butyl ether and teloh in the presence of cationic catalysis 30 ra, different in that, in order to obtain oligovinyl n-butyl ether containing unsaturated bonds capable of crosslinking under the action of sulfur, in SKD 9.0; plasticizer 21.0; n-quinone-. 20-dioxime 1.5 is used as telogen; alumina with 150 ma.ch. rosin 100 ma.ch. measure of particles 3-5-10 m 68.5. Cured at 6 hours. monomer, and the process is carried out at 90-120 ° C. five 0 five  the quality of the plasticizer is used: petroleum oil with a viscosity at 20 ° C to 200 mPa s and oligovinyl-n-butyl ether, obtained at a ratio of 20 mph. on 100 ma.ch. As can be seen from the table. 4, the use of synthesized oligomers instead of petroleum oil makes it possible to increase the durability by 1.5-2.0 times and 2.0-2.5 times the deformation of vulcanizates. In addition, the proposed oligomers, grafted to rubber, are not capable of further redistribution, in contrast to low molecular weight oils. The non-reactive oligovinyl-n-butyl ether method obtained by a known method due to the absence of chemical interaction with rubber and due to poor compatibility with it deteriorates the physical and mechanical properties of the vulcanizates. Invention Formula The method of obtaining oligovinyl-n. butyl ether by heating vinyl n-butyl ether and telogen. in the presence of a cationic catalyst, different in that. that, in order to obtain oligovinyl-n-butyl ether containing unsaturated bonds capable of crosslinking under the action of sulfur, 20-150 wt.h. are used as telogen. rosin 100 ma.ch. monomer, and the process is carried out at 90-120 ° C. Table 1 13683166 table 2 Reagents, ma.ch. c, Pa-s Mj ,, y.e Rosin VBE  1501003,04450 751001,06590 37.51000.82720 201000.85810 101001,18940 5100, 2.051100 -., ... AZ Tables Components Contents, May.% in the project EEPGSH :: Butyl rubber Neft maelo Perekiye manganese p-Hinondiokeim Oligomer po. example: 7 61 0.25. 0.51 0.47 0.34 0.23 380 920. 860 780 300 30 3 6 30 3 6 30 3 6 61 Petroleum oil1,7802,220,5 Oligomer2,5851,50,5 Oil oil / / oligomer 1: 12,2821,310,0 Table 4