SU679591A1 - Method of obtaining polymers of vinyl ethers - Google Patents

Description

(54) METHOD FOR OBTAINING POLYMERS OF SIMPLE VINYL ETHERS

Release butanol breaks the growing chains:

.-CH-HCH-CH-4CH-CHI. °.

CH

 I m I I

L axis OCHjJn .. OS Hg

CH, -CH - fCHj-CH -4-CH-CH-,

"9

and scaltedehyde reduces ferric iron to bivalent, reducing catalyst activity and increasing its consumption. As a result, it has not yet been possible to obtain butylvinyl ether from mol.m. more than 15,000. In addition, a large disadvantage of the polymers thus obtained is the presence in them of significant amounts of an aggressive catalyst — Lewis acids (FeClg, FeClj, and their hydrolyzed forms — which naturally dramatically reduces the thermal stability of products, leads to secondary processes during operation and storage, and thereby significantly limits the scope.

The purpose of the invention is to simplify the process technology and obtain high molecular weight polymers.

This goal is achieved by using 1-5% by weight of sulfur monomer as a catalyst, and the process is carried out at 20-80 ° C,

The versatility of the method is confirmed on a large series of vinyl ethers of various structures, including butylvinyl, methoxyethylvinyl, ethylene glycol divinyl ether, diethylene glycol divinyl ether, 1,3-propanediol divinyl ether, propylthioethoxyethoxyethyl vinyl ether

Depending on the nature of the monomer, soluble or structured (solid and rubber-like) polymers are obtained. The percentage of gel of the polymers is 69-90.

Butylvinyl ether in the indicated yc | ovi x forms solventol polymers with mol.m. 75,000. The process is carried out smoothly, without flashes and emissions, the catalyst is easily separated by decantation. According to the elemental aneshiz, the polymer obtained is not (it contains sulfur, which makes it possible to use it in traditional technical directions.

The identical nature of the solubility, the angshogness of the IR spectra obtained under the influence of sulfur and ferric chloride, confirm the identical structure of the macromolecule.

The polymerization of ethylene, diethylene, 1,3-propylene glycol divinyl ethers produces insoluble solids or rubbery polymers.

The results of IR spectral analysis show that both double bonds are involved in the formation of a macromolecule.

Unlike vulcanization processes, sulfur in this case does not enter 5 into the polymer chain, however its presence is necessary for initiating polymerization.

Example 1, Polymerization of Butyl Vinyl Ether,

5 g of butyl lovy ether, 0.25 g of elemental sulfur in the form of powder are placed in a vial. The ampoule is sealed and thermostatic for 20 hours. The polymer is separated by decantation from sulfur, the monomer is removed by evacuating at 2 mm Hg for 5 hours. To obtain 3.5 g of polymer, which is a light yellow, thick resin with mol.m., 75000,

0 (G | in benzene 0.84, monomer conversion 70%, the polymer is soluble in acetone, chloroform, benzene, hexane, insoluble in methanol and water.

Elemental analysis shows the absence of sulfur in the polymer.

In the IR spectrum of the polymer, the usual double bonds of vinyl alkyl ethers are absent, the frequencies in the region of 1612–1640 cm, the vibrations of the group are represented in the spectrum by frequencies in the region of 2850–2890. The band at 1360 cm is associated with symmetric deformation vibrations of the CND group non-symmetric deformation vibrations of the methyl and methylene groups appear in the absorption spectrum in the form of an intense band 1460. In the region of 990-1200 cm there are frequencies of stretching vibrations C – C and C – 0, external deformation vibrations of –C – H are characterized by a frequency of 980 m.

Example 2 Polymerization of Ethylene Glycol Divinyl Ether,

5 g of monomer is placed in a vial and

5 0.25 g (5%) sulfur. The mixture is thermostatic at 40 ° C for 30 hours. 2.5 g of light yellow non-insoluble powder polymer is obtained, the monomer is washed with diethyl ether,

0 Conversion of monomer 50%, Elemental analysis data; % C 62.25; H 8.87; sulfur is absent; gel 87,

Example 3, Polymerization of 1,3-propanediol divinyl ether,

5 5 g of monomer and 0.05 g (1%) of sulfur are placed in a vial and thermostatic for 50 hours. The mixture obtained is planted in petroleum and sulfur ether in the ratio. 1: 1. After

0 drying gives 1.48 g (29.5%) of a rubber-like insoluble product. The composition according to elemental analysis,%: C 60,50; H 8.45; sulfur is absent

Claims (2)

5 Example 4, Polymerization of diethylene glycol divinyl ether. 5 g of monomer and 0.1 g of sulfur (2%) are placed in a vial, which is sealed, and maintained for 100 hours. 5 g of solid, insoluble glassy product are obtained, the monomer is converted to 100%. The percentage of the gel is 86. Elemental analysis data,%: C, 53.26; H 8.94; sulfur traces. In the IR spectrum of the polymer, the absorption bands of the double bond disappear. Example 5. Polymerization Prilooethoxy ethoxyethyl vinyl ether, 2 g of monomer (5%) and 0.1 g of sulfur are placed in an ampoule, sealed and heated at 80 ° C for 25 h. The dimer is purified in a similar manner to the example. After drying, 0.5 g are obtained (28 , 2%) brown viscous resin with mol. 800 soluble in acetone, chloroform, dimethyl sulfoxide, insoluble in diethyl ether. PRI me R 6. Polymerization of methoxy ethyl vinyl ether. 2 g of monomer and 0.1 g (5%) of sulfur are placed in a vial and thermostatic for 50 hours. The polymer is separated by precipitation into diethyl ether. Obtain 0.5 g of a light yellow resin, mol.v. 700, solvent in beola, chloroform, insoluble in diethyl and petroleum ethers. Thus, the method of producing polymers of simple vinyl ethers 16 is quite simple in technological design, it can be easily implemented in the industry, it allows to carry out a smooth reaction in a wide range of temperatures, to obtain various polymer products with high molecular weight, in particular, to stabilize the properties commercial polybutyl vinyl ether, and extend to an extensive range of simple vinyl ethers. 1. Method for producing polymers of simple vinyl ethers by polymerizing vinyl ethers by heating in the presence of a catalyst, characterized in that, in order to simplify the technology and to obtain polymers with a high molecular weight, 1-5% by weight of monomer is used as a catalyst. sulfur. 2. A method according to claim 1, characterized in that the process is carried out at 20-80 ° C. Sources of information taken into account in the examination 1. US patent 3328468, cl. 260-615, publ. 1967. 2.Salnikov V.V. et al. Vinyl ethers. High Molecular Compounds, 1961, 3, p. 1730.