DE1545016C3 - Process for the preparation of polythioethers - Google Patents

Description

3 4

a large temperature range can be charged. The bomb was then sealed and

the. The preferred temperature range is between 72 hours at 80 ⁰ C in a constant temperature-on

Room temperature (20 ⁰ C) and 100 ⁰ C. departures Depending on the temperature held water bath and turnin. she

Reaction conditions and the nature of the monomer was then taken out of the water bath,

Materials can reaction 1 to 72 hours, 5 cooled to room temperature, opened, and that

but also take longer. Polymer was filled into a glass bowl. In front

The polymerization can be carried out without the application of any filling into the glass dish

Solvent, like a block polymerization with benzene washed. The washed polymer

process, or in water or methanol to form was then for 24 hours at 5O ⁰ C under 5 mm Hg

latex-like suspensions are carried out; it dried io pressure. The product obtained was a

can to carry out a solution polymerization crystalline polymer of polyethylene sulfide, the

but also any other organic had a melting point 206-211 ⁰ C inert. the

Solvents used as aromatic yield was 23.5 g.
Hydrocarbons, e.g. B. benzene, toluene or xylene;

aliphatic hydrocarbons, e.g. B. Isopentane, 15 B eis ρ ie 1 3
η-hexane or octane; chlorinated hydrocarbons,

such as carbon tetrachloride, methylene chloride or ethy- a lene chloride previously filled with gaseous nitrogen. When a water-soluble catalyst such as a stainless steel polymerization bomb was used with cadmium acetate or cadmium sulfate, 100 ml of benzene, 25.1 g of ethylene sulfide and 2.40 g of zinc is charged to conduct solution polymerization of 20 sulfide. The bomb is then preferably closed , a non-aqueous medium solution to and 2 hours at 8O ⁰ C in a use at a constant. the solvent is used, temperature held water reciprocated, if desired, controlling the speed It was then taken out from the bath, on Aid the reaction as it cools the distribution of room temperature, opens it, and promotes the pot heat of reaction. The reaction mixture can- 25 Product was washed with benzene. The washed product was agitated to facilitate the reaction. Product was then placed in a glass dish given and The pressure at which the reaction is carried out 24 hours at 50 ° C under 5 mm Hg pressure getroc Knead, does not seem to be particularly critical, since the polymer was a white crystalline poly conversion in an open vessel at atmospheric äthylensulfid, which had a melting point of 202 to Schem pressure or below 30 207 ⁰ C in a closed vessel. The yield was 25.1 g.
an autogenous or another pressure can be carried out. If a solvent for example 4
Method is used, it is desirable that

Reaction vessel successively with the solvent, an open glass vessel was filled with 0.473 g zinc catalyst and monomer, albeit 35 chromate and 47.3 g propylene sulfide. The particular order of addition for the jar was covered with a successful implementation of the Invention Metal Foil process to keep dust out. The respondents were not critical. If water is stirred as part of the 16 to 18 hour at room temperature and batch is used, it is often desirable then, if not necessary, a surfactant + o was allowed to stand for 24 days at 23 to 25 ° C without stirring. (These 24 days were not to be added as a dispersant for the particles formed for the polymerization. The attempt was made to unintentionally let a too fast run so long before the growth or agglomeration of the particles - Results have been verified.) Prevent the polypropylene sulfide. As a dispersant, anionic, was obtained in a yield of 32 g, the cationic and nonionic substances, such as alkylaryl 45 product was a rubbery mass with a polyether alcohol and the long-chain alkyl sulfonate intrinsic molecular viscosity of 2.1 in chloroform and sulfate salts, can be used. at 30 ⁰ C.

Example. For example

50 A lemonade bottle was filled with 4.72 g of Zmk-

An open glass vessel was charged with 0.473 g of zinc oxide oxalate, 200 g of propylene sulfide, and 212 ml of benzene and 47.3 g of propylene sulfide, and then charged with it. The bottle was closed and covered 45.5 of a metal foil to exclude dust. Hours in a constant temperature of 8O ⁰ C, the reactants were 16 to 18 hours at toggle held water bath and turnin. It was stirred at room temperature. The reaction mixture 55 then taken out from the bath, to room was then 167 hours at 23 ⁰ C without stirring temperature is cooled and opened. Let the pot product stand. The rubbery poly obtained was washed with benzene and then in a Glasmerisat 22 hours at 23 ⁰ C under 5 mm Hg was added cup. The polymer was dried several times. The propylene sulfide polymer ^{dried for hours at 23 °} C. under 5 mm Hg pressure was obtained in a yield of 21.3 g. The 60 and was a rubbery polymer of propylene polymer had an intrinsic viscosity lensulfid having an intrinsic viscosity of 5.7 at 3O ⁰ C in chloroform. . 0.758 had at 30 ⁰ C in chloroform. The yield

was 187 g.

; ■. Example-2 Example 6

• 65

A polymerisation bomb previously filled with nitrogen gas. Two sealable 850.5 g polymerisation bomb Stainless steel was with 100 ml ion bottles were cleaned, dried and like Benzene, 25.1 g of ethylene sulfide and 1.20 g of zinc peroxide are charged as follows:

bottle 1 2 Zn (OH) ₂ , g
Distilled water, ml ..
1,2-butylene sulfide, g
Thioglycidyl acrylate, g ... 0.4
150
88 0.4
150
79.2
14.4

46% haul achieved. At 30 ⁰ C in chloroform the polymer showed an intrinsic viscosity of 0.569.

Example8

A 11 capacity stainless steel reaction vessel was sequentially filled with 100 ml of benzene, 25.11 g Ethylene sulfide and 1.78 g of cadmium sulfide filled. the

The bottles were then closed and STUN 17 above the feed vorden in the reaction vessel in a bath maintained at 65 ⁰ C (± 3) water ίο lying free space was then placed with gaseous. The bottles were purged out of the bath with nitrogen. The principal was then removed, cooled to room temperature, opened, closed, placed in a water bath that was constant and the water was decanted from each bottle. was maintained at 8O ⁰ C, and departures 2 hours, and the contents of each bottle was then hergerollt itself with. The reactor was then washed from the water-200 ml of methanol, taken out in 200 to 300 ml. 15 bath, cooled to room temperature, benzene dissolved and the polymer opened in 2200 ml of methanol, and the polymer was removed, reprecipitated. The polymer of each bottle was the product was dried at 5O ⁰ C and a reduced pressure three to four times each with 200 ml of methanol overall of less than 5 mm Hg to a constant wash. The polymeric products were then weight dried. The yield was 18.1 g. Dried under a vacuum at 50 ^{° C. for 20 hours.} 20 the product concerned it is a white crystalline yields were 82.9 g (94.2% of theory) powder which had a melting point of 200-213 ⁰ C of Butylensulfidhomopolymerisates and 68 g (72.5%.

the theory) of butylene sulfide thioglycidyl acrylate example 9

Copolymer obtained.

10 g of each of the elastomeric polymeric products. An 850.5 g glass lemonade bottle was then placed separately in two glass jars. The were successively with 0.2 g of cadmium silicate, 85 ml of polymers were dissolved in chloroform; The benzene, 5 ml of distilled water and 47.4 g of propylene solution of the copolymer were filled with mild heating sulfide. The bottle was then closed as required. 10 drops of 2,5-di- were added to a water bath, which was constantly added to methyl-2,5-di (tert-butylperoxy) hexane and kept at 3 ° 65 ° C., and in the bath for 17 hours mixed with each of the solutions. Around the chloroform and rolled over. The bottle was then removed from the, the two solutions were taken out during bath, cooled to room temperature and placed in a vacuum oven ^{at 50 ° C. for 3 hours.} and open. The product was then dissolved in methanol were Samples 80 hours then placed in an oven and vortexed given to solvent and at 112-135 ⁰ C. After this time, the unreacted monomer had to be removed. The solid homopolymer was soluble in hot chloroform, the polymerization product was then separated by decan while the copolymer was separated into a hard animal from the methanolic washing liquid, elastomer was hardened, which divided 87% of its weight into small particles and then kept it twice if it was used for 46 hours in one Soxhlet extraction tube extracted with hot chloroform with methanol, swirling and decanting. Wash 4 °. The solid polymerization product was

then at 50 ° C and below 5 mm Hg

Example 7 Pressure until a constant weight is reached

. dried. The dried product was in

A closable, 850.5g capacity polymeriza- chloroform dissolved to remove the catalyst tion bottle was cleaned, dried, filtered with nitrogen 45 and evaporated to dryness. The received rinsed and then with 0.2 g of mercury oxide, 90 ml of material was an elastomeric polymer of propylene-benzene and filled with 50 ml of propylene sulfide. sulfide, which has an intrinsic viscosity of 1.11

The mercury oxide had been pre-glowed for 1 hour on red heat at a concentration of 0.5% in chloroform and had under dry 30 ^° C. before use. The yield was 41.1 g.
Nitrogen has been stored. The benzene was dry 5 °
and the propylene sulfide is freshly distilled. . Example 10

The bottle was then closed and 22 hours

and out-turnin 'in a water bath at 8O ⁰ C. An 850.5 g lemonade bottle was made

The bottle was then taken out of the bath one after the other with 0.2 g of cadmium hydroxide, 90 ml of men, cooled to room temperature, opened and filled with 55.4 g of benzene and 47.4 g of propylene sulfide. The bottle's viscous liquid reaction mixture was then closed and placed in a water bath, removed. The reaction mixture was then held in the constant at 65 ⁰ C, and 16 hours a vacuum oven at 5 mm Hg and 40 ⁰ C for back and turnin. The bottle was then evaporated from dryness to remove solvent rather than water bath to remove monomer reacted to room temperature. The rubber-60 cooled and opened. The contents were dissolved in methanol-like residue, then returned to dryness in 200 ml and swirled to take up solvent and benzene to remove monomer unreacted in the benzene overnight. The solid was allowed to stand, and the resulting clear, top-on polymer was then separated by decanting the methanol used to the floating liquid by a No. 1 wash, filtered into small Whatman papers in 21% of methanol. The polymer divided into 65 particles, then washed twice with methanol, then washed with fresh methanol and washed with stirring and decantation. The under vacuum at 4O ⁰ C for 48 hours until a solid polymer was then dried at 50 ⁰ C and a constant weight. A pressure below 5 mm Hg was dried until a

7 8

constant weight was achieved. The dried separated, particulate and then redissolved product was dissolved in chloroform, vortexed twice with methanol to remove and filtered to remove residual catalyst and washed to decant dry. The solid polymer was evaporated down. The polymer was an elastomeric then at 50 ⁰ C and under a less than 5 mm Hg polypropylene sulfide, which has an intrinsic viscosity 5 lying pressure to achieve a equal number of 1.54 for a 0.5 ° / ₀ solution remaining in chloroform weight dried. The dried at 30 ⁰ C had. The yield was 45.6 g. Product was dissolved in chloroform for removal

remaining catalyst filtered and dried to dryness

Example 11 evaporated. The polymer obtained was a

ίο elastomeric copolymer. The yield was An 850.5 g lemonade bottle weighed 96.6 g.

successively with 2.5 g of a nonionic alkylaryl- The elastomeric mixture obtained as above

polyether alcohol, 90 ml of distilled water, 0.2 g of polymer from propylene sulfide and allylthioglycidyl cadmium oxide and 47.4 g of propylene sulfide. The ether was then hardened into a tough rubber. Bottle was then closed and placed in a water bath 15 contained 90 g of the Härtungsansatz Mischpolygegeben, the constant on a temperature merisates, 0.9 g of stearic acid as a lubricant, 4.5 g of 65 ⁰ C was maintained. The bottle was rolled back and forth in the zinc oxide, 45 g carbon black, 1.8 g curing accelerator, and water bath for 16 hours. The 1.53 g of sulfur as a hardening agent. The polymerizate obtained was then mixed in methanol on a roller, formed into sheets and ^{whirled up to remove solvent and at 149 °} C. for 20 and 20 minutes to form a rapidly unreacted monomer. The solid cured rubber cured. The rubber had polymer was separated by decanting the methanol used initially with a tensile strength of 64.0 kg / cm ² and a fraction for washing, an elongation of 65%, a Shore Α hardness of 86 Duro-small particles and then divided twice with methanol meter -Grades and a tensile strength of washed under vortex and decanting. The solid 25 4.08 kg / cm ² .
Polymer was then at 50 ° C and one under Example 13

5 mm Hg lying pressure until reaching a

constant weight. The dried it became a lemonade bottle as a reaction vessel

Product was dissolved in chloroform, successively with 0.2 g of powdered cadmium acetate to remove filtered from residues of the catalyst and to 3 °

Evaporated dry. The polymer obtained [Cd (CH ₃ COO) ₂ ■ 2 H ₂ O]

was an elastomeric polypropylene sulfide, the one

intrinsic viscosity of 1.61 at 30 ° C in 90 ml of benzene and 47.3 g (50 ml) monomeric propylene One of 0.5 ° / ₀ solution in chloroform had. The sulfide filled, capped and in a 65 ° C yield was 40 g. 35 held bath rolled back and forth for 16 hours. To

During this period the vessel was cooled and opened

Example 12 ^UQ d the contents with stirring in a one liter metha

Beaker containing nol is filled. It formed

A lemonade bottle holding 850.5 g became a jelly-like coagulate which settled on the bottom of the glass in succession with 0.2 g cadmium oxide, 0.2 g cadmium-4 ° and quickly distilled to a rubbery hydroxide, 170 ml benzene, 10 ml Water, solid mass hardened. The 78.0 g of propylene sulfide and 24.0 g of allyl thioglycidyl ether floating on top were decanted and the rubber-like liquid was filled. The bottle was closed and cut into pieces of 6 mm in size, which were then kept at a constant temperature of 65 ^° C. twice with amounts of 1 liter of methanol each time. She was washed back for 16 hours and 45 were washed. The washed solids were rolled in and then removed from the water bath, cooled to room temperature to constant weight and opened. The dried in a vacuum oven at 60 ° C under 5 mm Hg. Contents were poured into methanol and removed to remove the dried product was high molecular weight of solvent and unreacted monomer, was water white and a solid elastomeric fluid. The solid polymer was now through 50 polymer. A yield of 82% decaning of the methanol used for washing was achieved.

Claims (5)

I 2 saturated aliphatic episulphide with a non-patent claims: saturated episulphide in the presence of zinc peroxide or zinc carbonate. 1. Process for the production of polythioethers These catalysts can either be used for themselves or can also be used in combination with one another by polymerizing a monomeric episulphide 5, in the presence of a metal compound of the group Preferred catalysts are the hydroxide, sulfide, IIB of the periodic table of the elements as a catalysis silicate, oxide or acetate of cadmium and that Sator, characterized in that peroxide, sulfide, chromate, adipate, oxalate, oxide or one is a peroxide, sulfide, chromate, adipate, oxalate, hydroxide of zinc or mercury. It was Oxide, hydroxide, silicate, acetate or sulfate of one io found to make the catalyst all the more reactive Metal of group IIB of the periodic table, the finer its particle size, being particle elements in an amount of 0.01. up to .1.0 sizes in the _ order of magnitude of less than percent by weight, based on the mono- 1 micron (s) are preferred. mer- episulfide, used as a catalyst, Typical polymerizable monomeric episulfide for except for the polymerization of at least one 15 the process of the invention are: styrene sulfide, saturated aliphatic episulfide with an allyl thioglycidyl ether, thioglycidyl acrylate, thiogly unsaturated episulphide in the presence of zinc cidyl methacrylate, 3,4-epoxy-1,2-butylene sulphide, vinyl peroxide or zinc carbonate. cyclohexene sulfide, butadiene monoepisulfide and alkylene 2. The method according to claim 1, characterized gekenn'- sulfide, such as ethylene sulfide, propylene sulfide, butylene that as a catalyst a hydroxide, sulfide, 20 sulfide, ie 1,2-butylene sulfide and 2,3-butylene sulfide, silicate, oxide or acetate of Cadmium uses isobutylene sulfide and cyclohexene sulfide. It can. also mixtures of two or more of these C 3. The method according to claim 1, characterized in that monomeric episulfides are used as starting material draws that a peroxide, sulfide, and copolymerized as a catalyst. In general are Chromate, adipate, oxalate, oxide or hydroxide 25 which cooks according to the method of the present invention Zinc or mercury is used wildly. Homopolymers and copolymers provided 4. The method according to claim 1 to 3, thereby insoluble in water, and the completely or im characterized in that the polymerization takes place in a polymer made essentially from 'ethylene sulfide inert liquid organic reaction medium are practically completely insoluble; H. to less than is carried out, 30 1 percent by weight soluble in solvents such as 5. The method according to claim 1 to 4, characterized in benzene, acetone, hexane and methylene chloride,
characterized in that the polymerization is carried out at a temperature of 20 to 100 ° C produced by the process of the invention. Homopolymers of ethylene sulfide or isobutylene sulfide are crystalline solids with high melting 35 points. They are valuable high-temperature molding compounds, and when molten they can deformed into flexible films. The one after the From the British patent 893 314 it is invention produced copolymers of Ethy- known, styrene sulfide using zinc sulfide and propylene sulfide and / or butylene sulfide to polymerize chloride as a catalyst. 40 can also be used to form valuable extrudables According to the earlier German patent specification 1 244 415 materials are used. In the melted solid copolymers can also become polythioethers through polymerization of the epi-state sulfides are formed into flexible films in the presence of carbonates of the metals. Mixed poly of Group IIB of the Periodic Table of the Elements merisate from propylene sulfide and / or butylene sulfide manufactured. ■ -. . ■ '. · ..'"■ . 45 and allyl thioglycidyl ether, thioglycidyl acrylate, thio- In the German patent 1495 461 glycidyl methacrylate, 3,4-epoxy-1,2-butylene sulfide, Vi- also a process for the production of mixed nylcyclohexene sulfide and / or butadiene monoepisulfide Proposed polymers in which at least one can be prepared from mixtures of the monomers saturated aliphatic episulfide and an unsaturated one, which are 2 to 20 percent by weight of one or Episulfide, in the presence of a compound of one of the last seven monomers, Metal * of 'Group IIB of the Periodic Table of and such copolymers can be used for vulcanized Elements as a polymerization catalyst polymerizes known methods with the formation of will. ■ - · - valuable elastomers are hardened. The polymers The object of the present invention was, however, of propylene sulfide and / or butylene sulfide are valuable High molecular weight polythioethers in the form of 55 full elastomeric materials that are pliable films from homopolymers or copolymers can be processed, to obtain. This inventive method for details of the polymerization process are in Production of polythioethers by polymerization described in the examples. To be particularly good to achieve a monomeric episulfide in the presence of a result, the starting Metal compound of group IIB of the periodic materials used monomers preferably un- system of the elements as a catalyst is therefore indirectly prior to use from a reduced characterized in that a peroxide, sulfide, chromate agent, such as calcium hydride, is freshly distilled to Adipate, oxalate, oxide, hydroxide, silicate, acetate or oxidation products such as carbon dioxide, and others Sulphate of a Group IIB metal of periodic impurities. The catalyst systems of elements in an amount of 0.01 to 65 is used in an amount of 0.01 to 10 percent by weight, Percentage by weight, based on the one or more mono- based on the one or more monomeric episulfides, meren episulfide is used as a catalyst. The preferred amount of catalyst is 0.1 to excluding the polymerization, at least one 5 percent by weight. The polymerization can take place within