CZ291289A3 - polymers of (fluorochloroalkyl)-2-propenoates and process for preparing thereof - Google Patents

Abstract

Homopolymers or copolymers of (fluorochloroalkyl)-2-propenoates of the general formula CH2 = CR - COO - CR<1>R<2> - (CF2CFCl)n - H, where R is hydrogen or methyl, R<1> and R<2> is hydrogen, phenyl, pentamethylen or aliphatic alkyl containing 1 to 8 atoms of carbon, n is 1 to 5, and the copolymer consists of at least two monomers. Comonomers are derivatives of 2-propenoic acid, styrene or propenenitrile. The polymers are prepared by radical polymerisation in a block, solution, suspension or emulsion. The prepared polymers are used in microelectronics.

Description

The present invention relates to (fluorochloroalkyl) -2-propenoates polymers and to a process for their preparation, particularly useful as electron or X-ray resistors or as optical fiber coatings.

The field of application of fluorinated polymers is very wide due to their special properties. In addition to the traditional applications utilizing their high thermal and chemical resistance, they have also been used in medical prosthetics, optoelectronics and microelectronics. These are mainly applications in which the relatively high cost of polymers is balanced by their high utility value. Optoelectronics uses low refractive index values of fluorinated polymers in combination with high chemical resistance and low temperature elasticity. In microelectronics, when applied in the form of resistors, their high sensitivity to ionizing radiation is advantageously used.

.................., ____ In_literature_. is a series of homopolymers of .alpha.-copolymers of fluorinated monomers containing one or more fluorine atoms in the molecule. In terms of lithographic properties, some fluorinated polymers have been studied, with particular attention being paid to acrylic acid derivatives, respectively. . methacrylic. The claims include a wide range of methacrylates of fluorinated alkanols, but so far no (fluorochloroalkyl) -2-propenoate polymers characterized by the fact that they consist of homopolymers or copolymers (fluorochloroalkyl) -2-propenoates of the general formula

CH n = CR - C00 - CR ¹ R ² - (CF _O CFC1) - Η,

Wherein n is hydrogen or methyl, R and R is hydrogen, phenyl, pentamethylene or an aliphatic alkyl of 1 to 8 carbon atoms, n is 1 to 5, wherein the copolymer comprises at least two monomers.

An essential advantage of the present invention is the combination of chlorine and fluorine atoms in the ester ligand, providing a higher sensitivity of the polymers to electron and x-ray radiation, with the polymers prepared having a low refractive index. The copolymerization of the above-mentioned (fluoro-chloroalkyl) -2-propenoates with other monomers and the choice of polymerization conditions make it possible to control the molar mass values and the molar mass distribution, solubility, and the like. the T-values and the adhesion of the polymers to the substrate and thereby influence

The lithographic properties of prepared researchers. Not negligible is the fact that the cost of copolymers is lower than the homopolymers of (fluorochloroalkyl) -2-propenoates.

The above polymers are prepared by radical polymerization initiated by thermal or photolytic decomposition. The polymerization may be carried out in a block, solution, suspension or emulsion. The (fluorochloroalkyl) -2-propenoates may be conveniently prepared by acylating the corresponding fluorochloroalkanols with an acid

........ 2-propene, 2-methyl-2-propene, or their chlorides, respectively.

The prepared homo- and copolymers of the above-mentioned (fluorochloroalkyl) -2-propenoates can be used, for example, as sensitive positive electron and X-ray resistors or as optical fiber coatings.

The invention is illustrated by the following examples:

- 3. Example JI.

_A ll ^ .4JUUWWWkF.UW: IILl & W ..-! AW ·

A solution of 7.3 g of (4-chloro-3,3,4-trifluoro-2-methyl-2-methyl) -2-methyl-2-propenoates with a purity of 99.4% and 14.3 mg of 2.2 * The azo-bis * isobutyronitrile in 12 ml dioxane was heated to 60 ° C for 6 hours after removal of traces of oxygen. The resulting polymer solution was precipitated in an excess of n-heptane, the polymer isolated and, after dissolution in chloroform, precipitated again in n-hexane. The isolated polymer was dried at 30 ° C / 0.1 kPa to constant weight (45% conversion). A polymer having Mw = 165,000 g.mol *** and Mw / Mn = 1.67 was used as an electron resist.

Example 2

Copolymer containing 82 mol%. (4-chloro-3,3,4-trifluoro-2-methyl-2-butyl) -2-methyl-2-propenoate, 15 mol.

(4,6-dichloro-3,3,4,5,5,6-hexafluoro-2-methyl-2-hexyl) -2-methyl-2-propenoate and 3 mol. (2,3-epoxypropyl) -2-methyl-2-propenoate was prepared in an analogous manner to that described above. . A copolymer containing 95 mol% was prepared in the same manner. % Of (4-chloro-3,3,4-trifluoro-2-methyl-2-butyl) 2-methyl-2-propenoate and 5 mol. (2-hydroxyethyl) -2-methyl-2-propenoate. Both of these copolymers had better adhesion to the substrate than the homopolymer prepared in Example 1.

Example 3

A copolymer containing 69 mol%. 1- (2-chloro-1,1,2-trifluoroethyl) cyclohexyl] -2-methyl-2-propenoate, 27 mol. % Of 2-methyl-2-propenenitrile and 4 mol. 3-carboxy-3-butenoic acid was prepared by free-radical polymerization in a solution of N, N-dimethylformamide. After 10 hours of polymerization at 70 ° C, a conversion of 56% was achieved. The polymer was processed in a similar manner as in the case of. -. -.

- 4 Example 4

A water-soluble copolymer of (3-chloro-2,2,3-trifluoropropyl) -2-methyl-2-propenoate with N- (2-hydroxypropyl) -2-methyl-2-propenamide was prepared by radical heterogeneous polymerization. A solution of 0.7 g of (3-chloro- _2f 2,3-trifluoropropyl) -2-methyl-2-propenoate, 5.8 g of N- (2-hydroxypropyl) 2-methyl-2-propenaniide and 0.8 g 2,2'-Azo-bis-isobutyronitrile in 42.7 g acetone was heated at 50 ° C for 24 hours. The precipitated copolymer was filtered off, dissolved in methanol, precipitated in excess acetone, collected _{in a} vacuum and dried.

Example 5

A copolymer containing 68 mol%. (3-chloro-1-phenyl-2,3,3-trifluoropropyl) -2-methyl-2-propenoate and 32 mol.

4-chlorostyrene was prepared by block photopolymerization using 2-phenylazo-2,4-dimethyl-4-phenylvaleronitrile

-3 —1 as the initiator. Initiator concentration 5.10 mol.l, polymerization temperature 20 ° C, polymerization time 3 hours. The 436 nm wavelength was generated by three Tesla RVL 25OW mercury luminescent lamps equipped with liquid filters positioned at a distance of -20 cm from the reactor. The resulting polymer was precipitated in excess n-hexane and after isolation dried to constant weight under reduced pressure (0.1 kPa).

Example 6 'g of a mixture of (1-chloro-3-ethyl-1,2,2-trifluoro-3pentyl) -2-propenoate and (ethylhexyl-2-propenoate (3: 1 wt)) in which 2.2 * -azo-bis- isobutyro nitrile (1.10 ² mol / ^l ) was poured into 200 ml of a 1% solution of polyvinylpyrrolidone in distilled water.

The batch was bubbled with nitrogen for 15 minutes

LU ^ ΛΜ.4Ιίίίί · ΑΑίΙΒ> · 4'1Ο1! · 11-1 ^ ... ^. ^. 111.111 ^ .11 ^. ^ 11,11 .. ^ .Muiu 1, UI. 1. . ...

poured into a mixed glass autoclave. After 8 hours of stirring (5 s @ ¹⁾ at 80 ° C was isolated spherical copolymer was washed with water and ethanol and dried.

Example 7

65% wt. (4-chloro-3,3,4-trifluoro-2-methyl-2-butyl) -2-methyl-2-propenoate, 10 wt. (methyl) -2-methyl-12-propenoate, 20 wt. (butyl) -2-methyl-2-propenoate,

5%. hm. Of (2-hydroxyethyl) -2-methyl-2-propenoate and 2,2'-azobis-isobutyronitrile (5 x 10 4 mol / ^l ) were heated to 70 ° C for 60 minutes after removal of the stop oxygen. The resulting polymer, which was processed and isolated analogously to Example 1, was used as an electron and X-ray unit. - ..........

Example 8

A copolymer containing 72 mol%. (4-chloro-3,3,4-trifluoro-2-butyl) -2-methyl-2-propenoate and 28 mol. (butyl) · -1

2-methyl-2-propenoate having an Mw = 365,000 g.mol was prepared by free-radical polymerization in toluene solution at 70 ° C. The initial concentration of dibenzoyl peroxide was 6-104. Isolation and treatment of the copolymers was carried out as in Example 1.

Claims (6)

PATENT CLAIMS 1. Polymers of (fluorochloroalkyl) -2-propenoates characterized in that they consist of homopolymers or copolymers of (fluorochloroalkyl) -2-propenoates of the general formula CK _"with CR - COO - CR ¹ R ² - (CP.CPC1) - Η, ή" · ^ nt 1 JP 2 wherein R is hydrogen or methyl, R and R is hydrogen, phenyl, pentamethylene or an aliphatic alkyl group containing 1 to. N is 1 to 5, wherein the copolymer consists of at least two monomers. 2. The (fluoro-chloroalkyl) -2-propenoate copolymers of claim 1 which contain 2-propenoic acid derivatives of the general formula: CH ₂ = CZ -COOR ³ wherein Z is H, -CH 2, -CH ³ COOH and R ³ is hydrogen, 2,3-epoxypropyl, 2-hydroxyethyl, 2- (2'-hydroxyethoxy) ethyl, aliphatic or cycloaliphatic alkyl containing 1 to 8 - · - · - - carbon atoms. * · (Fluorochloroalkyl) -2-propenoate copolymers according to items 1 and 2, characterized in that they contain 2-propenamide derivatives J of the general formula CH ₂ = CX ¹ - COHR ⁴ , 1-4 wherein Z is hydrogen or methyl and R is hydrogen, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl or C 1 -C 4 aliphatic alkyl. 4. Copolymers of (fluorochloroalkyl) -2-propenoates according to items . -r | 'in XU4') ”/ VW fcj j-Vřp ^: c ± -ii --v 2. U CC 2-methyl-2-propenenitrile. 5. Copolymers of (fluorochloroalkyl) -2-propenoates according to the styrene derivatives 1, 2 and 3, characterized in that they contain the general formula R 5 CH ₂ = CX ^U - <--- ^Λ , where X is hydrogen or methyl and or chlorine, methyl or vinyl. is a hydrogen atom 6. A process according to claim 1 wherein the monomers or mixture, solution, suspension or emulsion is treated with a free radical initiator. :,: ,, cs &