CS270650B1 - Copolymers of 2,3-epoxypropyl- and (2,3-epithiopropyl) -2-propenoates and a process for its preparation - Google Patents

Abstract

Copolymers of 2,3-epoxypropyl- and (2,3- -epylthopropyl)-2-propenoate containing in the polymer chain the groups -CH2-pXCOOCH, - CH-CH, and 2 x / 2 Y C -OH2-φχwhere X is hydrogen or methyl and Y is an oxygen or sulfur atom. The copolymers are prepared by radical polymerization in block, solution or suspension.

Description

The invention relates to copolymers of 2,3-epoxypropyl-α (2,3-epithiopropyl) -2-propenoates and to a process for their preparation which can be used as electron and X-ray scattering in microelectronics. .

2,3-Epoxypropyl (2,3-epithiopropyl) -2-propenoates are generally used as monomers where their double reactivity can be advantageously used, i.e. the presence of a reactive double bond with a reactive three-membered heterocycle. The axis describes polymers prepared by anionic or catlonic polymerized cycles, as well as homo- 1. copolymers * prepared by radical polymerized running on a vinyl group.

Oxlrenových reactivity, Reap, thiirane cycles present in the side-chains along a polymer prepared by ¹ O- radical polyaerizad kopolýaerizad or 2,3-epoxypropyl, respectively. (2,3-epithiopropyl) -2-propenoates can be used for various purposes. For example, electronic sorbents and catalysts were prepared by polymeronological reactions of various reagents and oxirane groups of 2,3-epoxypropyl methacrylate-ethylene dimethacrylate copolymers (Kálal □ Švec F., Maroušek V., 3. Polym, Sel., Symp. No. 47, 155/1974 /). The ability of the thiirane group to bind mercury, gold and some other metals from aqueous solutions of their salts was used in the preparation of macroporous sorbents (Czechoslovak author's certificates No. 220145 and No. 235768).

Applications of homo- copolymers of 2,3-epoxypropyl and (2,3-epithiopropyl) -2-propenoates as polymer spreads in photolithography and electron lithography have also been studied. The 2,3-epoxypropyl methacrylate homopolymer is one of the most highly sensitive electron scatterings, but has a low contrast value and also poorer resistance to plasma etching. These disadvantages can be suppressed by copolymerization with styrene or even better with chlorinated styrene derivatives.

A number of copolymers of 2,3-epoxypropyl methacrylate with halogen derivatives of styrene have been prepared, and the preparation of copolymers with chlorinated derivatives of .beta.-methyletyrene, as well as copolymers of 2,3-epithlopropyl methacrylate and chlorinated derivatives of styrene and .beta.-methylstyrene, has not been discussed.

This deficiency is eliminated by copolymers of 2,3-epoxypropyl and (2,3-epithlopropyl) -2-propenoates, characterized in that they contain groups in the polymer chain.

-ch ₂ -cx- -ch ₂ -cxCOOCH ₂ -CH-CH ₂ f ^ x ^ Cl, where X is hydrogen or methyl and Y is oxygen or sulfur.

A significant advantage of the 2,3-epoxypropyl- (2,3-epithiopropyl) -2-propenoate ¹ copolymers according to the invention is the fact that these copolymers have a high sensitivity to ionizing radiation and excellent adhesion to the substrate, as well as good resistance to plasma etching. *

The above copolymers ee prepare radical polymerized made in block, solution or euepenzl. Both polymerization initiators can be used as azo initiators, preferably aliphatic azonitriles, as well as conventional peroxydic initiators such as dibenzoyl peroxide and the like.

The composition of the copolymers and their molar mass can be varied over a wide range depending on the composition of the polymerization batch and the polymerization conditions. With increasing content of halogenated styrene derivatives in the batch, the copolymerization rate decreased. This decrease in the copolymers with 4-chloro-o-methylstyrene was accompanied by a significant decrease in the molar masses of C3 270 650 B1 of the product, the rate of copolymerization being approximately an order of magnitude lower than that of 4-chlorostyrene.

Example 1

A solution of 181 g of (2,3-epoxypropyl) -2-ethyl-2-propenoate, 34.3 g of 4-chloro-2. -methylstyrene and 0.99 g of 2,2'-azobisisobutyronitrile in 200 ml of toluene were heated at 60 ° C for 28 hours. The obtained polymer solution was precipitated in ten times the volume of n-hexane. The isolated polymer was reprecipitated in n-hexane after dissolving in chloroform. After isolation was dried in konstentni weight at 25 ° C / O, 1 kPa · afford 51 g (24% conversion) of copolymer containing 4.88 wt% of chlorine and having a Mw of 82,600 gmol ^- ^ a'Mw '/ Mn »1.51. The copolymer was used as a sensitive electron resist.

Example 2 g of a mixture of (2,3-epoxypropyl) -2-propenoate and (2,3-epithiopropyl) -2-methyl-2-propeno-2-one (1: 1 wt.) In which the initiator dibenzoyl peroxide was dissolved ( 15.10 mol.l), was poured into 405 ml of a 1% solution of polyvinylpyrrolidone in distilled water. After bubbling the mixture with nitrogen for 15 minutes, the batch was poured into a stirred thermostated autoclave. After stirring at 80 ° C for 8 hours, the isolated spherical polymer was washed with water and ethyl alcohol and dried.

Example 3

A solution of 3.0 g of (2,3-epithiopropyl) -2-methyl-2-propenoate, 10.88 g of 4-chlorostyrene and 0.74 g of 2,2'-azo-bis-isobutyronitrile in 26 ml of dioxane was heated to temperature of 60 ° C for 270 minutes. The obtained copolymer solution was precipitated in excess petroleum ether and the isolated polymer was dried. Yield 7.02 g (50.6% conversion) of copolymer containing 22 mol% of (2,3-epithiopropyl) -2-methyl-2-propenoate whose Hn 14,500 gmol ^- ^. The negative electron resist prepared from this copolymer had a sensitivity of D 0.5 · 6.5.10 ^-7 -2 9

C.cm.

Example 4

Polymerization of a monomer mixture containing 2.76 g of (2,3-epithiopropyl) -2-methyl-2-propenoate, 5.21 g of (2,3-epoxypropyl) -2-methyl-2-propenoate and 3.1 g of 4- chlorostyrene was performed in a solution of dioxane (volume ratio of the monomers (solvent 1: 2) for the initiation of 2,2'-azo-isobutyronitrile bie (C _Q »15.10" ^ ^{a 2} M) at 60 ° C. After 80 minutes of heating the polymer solution was precipitated in an excess of n-heptane after přeerážení of the chloroform solution is isolated and dried at 35 ° C / 0, l mbar to constant weight. the copolymer (31.1% conversion) having the Hn 11,000 g. ol ^ ^- ^ contained 5.18% by weight of S and 8.47% by weight of Cl.

Example 6

A mixture of 0.5 g of (2,3-epithiopropyl) -2-methyl-2-propenoate, 3.0 g of (2,3-epoxypropyl) -2-methyl-2-propenoate and 6.5 g of 4-chloro-pC -methylstyrene, containing 0.25 g of 2,2'-azo-bis-isobityronitrile, was heated at 60 ° C for 8 hours after purging with nitrogen. The resulting copolymer, isolated similarly to Example 1, had a Hw of 65,400 g.mol ^-1 and was used to prepare a negative resist.

Example 6

Copolymers of (2,3-epithiopropyl) -2-propenoate with 2-chlorostyrene and (2,3-epithiopropyl) -2-methyl-2-propenoate with (2,3-epoxypropyl) -2 were prepared analogously to Example 3. -methyl 2-propenoate and 3-chlorostyrene.

Claims (1)

OBJECT OF THE INVENTION Copolymers of 2,3-spoxypropyl and (2,3-spithiopropyl) -2-propenoate containing groups in the polymer chain - CH_ - CX ² I C00CH _o - CH - ^{CH_ a 2} \ / ² Y wherein X is hydrogen or methyl and Y is oxygen or sulfur. 2. A process for the preparation of copolymers of 2,3-epoxypropyl and (2,3-epithiopropyl) -2-propenoates according to claim 1, characterized in that ss acts on the mixture of monomers or their solution or suspension with a radical initiator.