CS256259B1 - Homopolymers of 1-alkoxy-2,2,2-trifluoroethyl acrylates and 1-alkokyl-N, N-trifluoroethyl methacrylates and a process for their preparation - Google Patents

Abstract

The solution relates to homopolymers of 1-alkoxy2.2.2-trifluoroethyl acrylates and 1-alkoxy2.2.2-trifluoroethyl methacrylates of the general formula I, in which R is GH3 or C5H5 and X is H or CH3 and copolymers of substances of the general formula I with vinyl or diene monomers selected from the group consisting of esters of acrylic or methacrylic acid with 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1,3-butadiene and styrene, wherein the molar ratio of the substance of the general formula I to the comonomers can vary from 0.02 to 50. CF3 , | [ 2 The method of producing the above substances consists in that the monomer of the general formula I or its mixture with vinyl or diene monomers selected from the group consisting of esters of acrylic or methacrylic acid with 1 to 2 carbon atoms in the alcoholic residue, 2-chloro-1,3-butadiene and styrene is treated with a radical polymerization initiator at the decomposition temperature of the initiator at the initiation polymerization center. Homopolymers and copolymers of the substances of the general formula I can be prepared by conventional technological methods of polymerization in block, solution, aqueous emulsion or suspension

Description

The invention relates to homopolymers and copolymers of 1-alkoxy-2,2,2-trifluoroethyl acrylates and 1-alkoxy-2,2,2-trifluoroethyl methacrylates and a process for their preparation.

The present invention provides homopolymers and copolymers of 1-alkoxy-2,2,2-trifluoroethyl acrylates and 1-alkoxy-2,2,2-trifluoroethyl methacrylates of formula I,

CF _q -CH-OCC = CH (I) ³ L 1 L

OR 0 X wherein R is CH _O or H _O H ", and X is H or CH _O and copolymers substances obec5 2 5 j therefrom formula 1 with vinyl or dřeňovými monomers selected from the group consisting of esters of acrylic or methacrylic acid having 1 to 2 the carbon atoms in the alcohol residue, 2-chloro-1,3-butadiene and styrene, wherein the molar ratio of the compound of formula I to the comonomers may vary from 0.02 to 50%;

The homopolymers of the compounds of the formula I and their copolymers have not been prepared. The process according to the invention can be prepared by treating a monomer of the formula I or a mixture thereof with vinyl or pith monomers selected from the group consisting of esters of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1, 3-butadiene and styrene act as initiators of radical polymerization at initiator decomposition temperatures to initiate polymerization centers.

In the copolymerization of the esters of the formula I, all known vinyl or pith monomers known to radically homopolymerize or copolymerize with other olefinically unsaturated compounds, in particular acrylic or methacrylic esters, can be used as comonomers. Such compounds are, for example, methyl methacrylate, styrene, acrylonitrile, butodine, 2-methyl-1,3-butadiene (isoprene), 2-chloro-1,3-butadiene (chloroprene), acrylamide, vinyl chloride,

256 259 vinylidene chloride and 1,2,2,2-tetrachloroethyl acrylate. The homopolymers and copolymers of the compounds of formula (I) can be prepared by conventional technological processes for block, solution, aqueous emulsion or suspension polymerization.

To initiate the polymerization of the monomers of formula (I), it is generally possible to use any conventional initiators or initiator systems used in the free-radical polymerization of known monomers with olefinically unsaturated bonds in the molecule. Depending on the nature of the initiator or initiator system used, the polymerization temperature is chosen such that sufficient initiator decomposes into free radicals. For example, using conventional initiation redox systems, the polymerization rate is already sufficient in the temperature range of 0 to 30 ° C, while in homopolymerization of the esters I in the 2,2'-azobis (isobutyronitrile) initiated block, the polymerization mixture is "heated to 70-90 ° C.

Methods for polymerizing compounds of Formula I are illustrated in the following examples:

Example 1

Weigh 6.75 g of 1-ethoxy-2,2,2-trifluoroethyl acrylate, 0.1443 g of 2,2'-azobis (isobutyronitrile) and 44.92 g of chloroform into a approx. 35 cm glass dilatometer. The dilatometer is cooled in liquid nitrogen and de-aerated by alternating nitrogen gas evacuation and evacuation. It is then sealed and heated in an aqueous thermostat at 0 ° C. After 329 minutes, the volume contraction of the polymerization solution corresponds to ω

0,5624 cur. The dilatometer is cooled, opened and the solution is sucked into a 500 cm glass flask. By adding 300 cm of hexane, a colorless plastic polymer precipitated. The solvent was poured off and the polymer was dried for 6 hours at room temperature in a water pump vacuum. The achieved monomer conversion to polymer (4.1 g) corresponds to 60.75 specific volume contraction at homopolymerization is 0.1372 cm g and η _{β of} polymer is 1.416 The homopolymer thus prepared is well soluble in benzene, chloroform tetrachloromethane, tetrahydrofuran, 1.4 -dioxane, acetone, worse in ether and in alcohols, and insoluble in aliphatic hydrocarbons and water. @ 1 H NMR spectra were identified as poles (1-ethoxy-2,2,2-trifluoroethyl acrylate). Analysis showed 42.44% C and 4.54% H (theory 42.43% C and 4.48% H).

256 259

Example 2

A solution of 0.0066 g of 2,2'-azobis (isobutyronitrile) in 1.35 g of 1-ethoxy-2,2,2-trifluoroethyl acrylate in a glass vial, as in Example 1, is heated to air and the vial is sealed. It is then heated at 50 ° C for 6 hours and at 70 ° C for 8 hours. Breaking the ampoule releases the colorless rubbery block. It does not dissolve in aromatic or strongly polar solvents in which only swellable.

Example 3

A mixture of 1.72 g (0.0194 mol) of 2-chloro-13-butadiene (chloroprene), 2 g (0.0101 mol) of 1-ethoxy-2,2,2-trifluoroethyl acrylate, 0.036 g of dibenzoyl peroxide, 7, 2 cm · ^{5 of a} 2.5% aqueous solution of sodium mersolate (alkylsulfonates of the approximate formula (H 2 O 2 SO 4 Na) and 0.0648 g of sodium N, N-dimethylsulfanilane in a glass vial are deoxygenated similar to Example 1, The vial was opened and the emulsion was poured into 90 cm @ 3 of ethanol. The precipitated copolymer is filtered off, washed with 10 cm @ 3 of ethanol on the filter and dried in a water pump vacuum for 3 h. It weighs 3.3 g, is colorless, plastic and contains 47.27% C, 5.15% H and 16.00% Cl. The calculated molar ratio of 2-chloro-1,3-butadiene (chloroprene) / 1-ethoxy-2,2,2-trifluoroethyl acrylate base units is 1.55. The copolymer does not dissolve in organic solvents, only swellable in them.

Example 4

A solution of 6.44 g of 1-ethoxy-2,2,2-trifluoroethyl methacrylate and 0.140 g of 2,2-azobis (isobutyronitrile) in 45.59 g of chloroform is polymerized in the same dilatometer and under the same conditions as in Example 1. 670 minutes. The volumetric contraction of the polymerization solution corresponds to 0.4266 cm @ -1. The polymerization solution is then diluted with 300 cm @ 3 of hexane, the solvents are cast from the precipitated plastic polymer and the polymer is bent in 50 cm @ 3 of pure hexane. After pre-drying in a water pump vacuum, the colorless solid polymer is pulverized and dried to a constant hM (h-2.9% (45% conversion)).

25B 259

-1

Specific volume contraction in homopolymerization! is 0.1471 cm g of 20 an _n homopolymer is 1.4240. The solubility of the polymer is the same as ^{that of the} 1-pole (1-ethoxy-2,2,2-trifluoroethyl acrylate) (in Example 1). HNMR spectra were identified as poles (1-ethoxy-2,2,2-trifluoroethyl methacrylate). The analysis determined 45.44% C and 5.32%

H (theory 45.29% C, 5.23% H).

Example 5

A solution of 0.0039 g of 2,2'-azobis (isobutyronitrile) in 1.449 g of 1-ethoxy-2,2,2-trifluoroethyl methacrylate was polymerized under the same conditions as in Example 2. After breaking the vial, a solid clear block was obtained. the solubility is the same as that of the polymer prepared in solution (Example 4).

Example 6

In the same manner as in Example 5, a mixture of 0.0046 g was polymerized

2,2-azobis (isobutyronitrile), 0.584 g styrene and 0.788 g 1-ethoxy-2,2,2-trifluoroethyl methacrylate. After breaking the vial, a solid, colorless, somewhat cloudy block is obtained. Soluble in ether, acetone, aromatic and chlorinated aliphatic hydrocarbons, insoluble in alcohols and aliphatic hydrocarbons.

Example 7

As in Example 5, a mixture of 0.0042 g of 2,2'-azobis (isobutyronitrile), 0.576 g of methyl methacrylate and 0.754 g of 1-ethoxy-2,2,2-trifluoroethyl methacrylate is polymerized. The resulting block is solid, clear and colorless. Its solubility is the same as the copolymers in Example 6.

Poly (1-ethoxy-2,2,2-trifluoroethyl acrylates) and poles (1-ethoxy2,2,2-trifluoroethyl methacrylates) with a carbon number of seven or six are burnt in the flame of the gas burner, but outside flames go out. They can therefore be used for polymer products with reduced flammability requirements. Poles (1-alkoxy-2,2,2-trifluoroethyl acrylates) and poles (1-alkoxy-2,2,2-trifluoroethyl methacrylates) can, due to their relatively low refractive index, serve as cover layers of glass light pipes.

Claims (3)

BACKGROUND OF THE INVENTION Homopolymers of 1-alkoxy-2,2,2-trifluoroethyl acrylates and 1-alkoxy-2,2,2-trifluoroethyl methacrylates of the general formula I, CF-CH-OCC = CH (i ³ III ²⁾ OR O X wherein R is CH_ or C H_ and X is H or CH_ and copolymers of substances ’ J 2 5 3 of the general formula I with vinyl or pith monomers selected from the group consisting of esters of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue, 2-chloro-1,3-butadiene and styrene, the molar ratio of formula I to comonomers can vary from 0.02 to 50 · 2. A process for the production of homopolymers and copolymers according to claim 1, characterized in that the monomer of the formula I or a mixture thereof with vinyl or pith monomers selected from the group of esters of acrylic or methacrylic acid having 1 to 2 carbon atoms in the alcohol residue is 2-. chloro-1,3-butadiene and styrene, initiate radical polymerization initiator polymerization centers at the initiator decomposition temperature. 3. A process according to claim 2, wherein a solution, aqueous emulsion or suspension is used instead of pure monomers.