Method for bulk polymerization of vinyl chloride

• US 4,098,972 A
• Filed: 03/16/1976
• Issued: 07/04/1978
• Est. Priority Date: 03/24/1975
• Status: Expired due to Term

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Ogawa, Kinya, Kuwata, Satoshi, Eguchi, Yoshitugu, Kurimoto, Kazuhiko
• Primary Examiner(s): Holler, Alan
• Application Number:
  US05/667,303
• Time in Patent Office: 840 Days
• Field of Search: 526/62, 526/74, 528/484
• US Class Current: 526/62
• CPC Class Codes: B01J 19/0066 Stirrers mixing per se B01F
• CPC Class Codes: B01J 19/02 Apparatus characterised by being constructed of material selected for its chemically-resistant properties
• CPC Class Codes: B01J 2219/0236 Metal based
• CPC Class Codes: B05D 5/08 to obtain an anti-friction or anti-adhesive surface rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30
• CPC Class Codes: B05D 7/227 of containers, cans or the like
• CPC Class Codes: C08F 2/004 by a prior coating on the reactor walls

Abstract

Vinyl chloride monomers or a monomeric mixture composed mainly of vinyl chloride is bulk-polymerized in a polymerization vessel. The inner walls and other surfaces of said vessel, coming into contact with the monomer or monomers, are coated with one or more specifically selected inorganic or organic compounds having a solubility greater than 0.5 g in 100 g of water at 25° C and a boiling point higher than 60° C. This bulk polymerization method serves to greatly reduce the deposition of polymer scale on the vessel walls and other surfaces. In addition the polymer scale deposited can be readily separated and removed by merely washing with water or gas under pressure. The present method provides high quality polymers.

Claims

1. A method for the bulk polymerization of a vinyl chloride monomer or a monomeric mixture thereof with a copolymerizable monomer or monomers which comprises carrying out the polymerization in a polymerization reactor in which the inner walls and other surfaces coming into contact with the monomer or monomers are provided with coatings of a compound having a solubility greater than 0.5 g in 100 g of water at 25°

C. and having a boiling point higher than 60°

C.

2. The method of claim 1 wherein said compound is a hydroxide of an alkali metal or an alkaline earth metal.

3. The method of claim 1 wherein said compound is a boron-containing acid, a silicon-containing acid, a metal-containing acid or an alkali metal salt thereof.

4. The method of claim 1 wherein said compound is a phosphorus-containing acid.

5. The method of claim 1 wherein said compound is an alkali metal salt of an acid selected from the group consisting of carbonic acid, phosphoric acid, polymetaphosphoric acids and polyphosphoric acids.

6. The method of claim 1 wherein said compound is a salt selected from the group consisting of sulfates, nitrates and halides of metals other than the metals belonging to Group V of the Periodic Table and double salts thereof.

7. The method of claim 1 wherein said compound is a salt selected from the group consisting of thiocyanates, ferrocyanides and ferricyanides of alkali metals and double salts thereof.

8. The method of claim 1 wherein said compound is an acid selected from the group consisting of carboxylic acids, aminocarboxylic acids, organic sulfonic acids, and an alkali metal salt thereof.

9. The method of claim 1 wherein said compound is a polyvalent aliphatic alcohol.

10. The method of claim 1 wherein said compound is a water-soluble high polymer.

11. The method of claim 1 wherein said compound is a water-soluble surface active agent.

12. The method of claim 1 wherein said compound is a water-soluble organic dye.

13. The method of claim 2 wherein said hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide and barium hydroxide.

14. The method of claim 3 wherein said boron-containing acid is boric acid.

15. The method of claim 3 wherein said alkali metal salt of said acids is selected from the group consisting of borates, silicates, titanates, chromates, bichromates, manganates, permanganates, molybdates, tungstates, phosphotungstates, phosphomolybdates, aluminates and stannates of alkali metals.

16. The method of claim 4 wherein said phosphorus-containing acid is selected from the group consisting of phosphoric acid, hypophosphorous acid, phosphorous acid, diphosphorous acid, pyrophosphorous acid, hypophosphoric acid, ultraphosphoric acid, polymetaphosphoric acids and polyphosphoric acids.

17. The method of claim 6 wherein said sulfate is selected from the group consisting of lithium sulfate, sodium sulfate, potassium sulfate, copper sulfate, magnesium sulfate, zinc sulfate, aluminum sulfate, titanium sulfate, tin sulfate, iron sulfate, nickel sulfate, cobalt sulfate, chromium sulfate, manganese sulfate, platinum sulfate, sulfates of rare earth elements and zirconium sulfate.

18. The method of claim 6 wherein said nitrate is selected from the group consisting of lithium nitrate, sodium nitrate, potassium nitrate, copper nitrate, silver nitrate, magnesium nitrate, calcium nitrate, barium nitrate, zinc nitrate, aluminum nitrate, tin nitrate, iron nitrate, nickel nitrate, cobalt nitrate, chromium nitrate, manganese nitrate, platinum nitrate, strontium nitrate, nitrates of rare earth elements and zirconium nitrate.

19. The method of claim 6 wherein said halide is selected from the group consisting of lithium chloride, sodium chloride, potassium chloride, copper chloride, magnesium chloride, calcium chloride, barium chloride, zinc chloride, aluminum chloride, tin chloride, iron chloride, nickel chloride, cobalt chloride, chromium chloride, molybdenum chloride, manganese chloride, platinum chloride, strontium chloride, chlorides of rare earth elements, zirconium chloride, tungsten chloride, sodium fluoride, sodium bromide, sodium iodide, potassium fluoride, potassium bromide and potassium iodide.

20. The method of claim 6 wherein said double salt is selected from the group consisting of Mohr'"'"'s salt, potassium alum, sodium alum, ammonium alum and ammonium iron alum.

21. The method of claim 7 wherein said double salt is Reinecke'"'"'s salt.

22. The method of claim 8 wherein said carboxylic acid is selected from the group consisting of formic acid, acetic acid, oxalic acid, tartaric acid, succinic acid, maleic acid, salicylic acid, glycolic acid and gluconic acid.

23. The method of claim 8 wherein said aminocarboxylic acid is glutamic acid.

24. The method of claim 8 wherein said organic sulfonic acid is selected from the group consisting of 1-naphthylamine-2-sulfonic acid and 2-nitrobenzenesulfonic acid.

25. The method of claim 8 wherein said alkali metal salt is selected from the group consisting of the alkali metal salts of formic acid, acetic acid, oxalic acid, tartaric acid, succinic acid, maleic acid, salicylic acid, glycolic acid and gluconic acid.

26. The method of claim 8 wherein said alkali metal salt is selected from the group consisting of the alkali metal salts of glutamic acid and ethylenediaminetetraacetic acid.

27. The method of claim 8 wherein said alkali metal salt is selected from the group consisting of the alkali metal salts of 1-naphthylamine-2-sulfonic acid and 2-nitrobenzenesulfonic acid.

28. The method of claim 9 wherein said polyvalent aliphatic alcohol is selected from the group consisting of glycerin, mannitol, sorbitol, glucose, ethyleneglycol, propyleneglycol and sucrose.

29. The method of claim 10 wherein said water-soluble high polymer is selected from the group consisting of gelatin, gum Arabic, starch, sodium salt of carboxymethylcellulose, methylcellulose, polyethylene oxide, polyvinyl alcohol, polyacrylic acid and polyacrylamide.

30. The method of claim 11 wherein said water-soluble surface active agent is selected from the group consisting of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearate, polyoxyethylene laurate, polyoxyethylene lauryl ether, polyoxyethylene cetylether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene glycerin monostearate, sodium stearate, sodium 4-dodecylbenzene sulfonate, sodium laurylsulfate, laurylamine hydrochloride, dodecylamine acetate, cetyl pyridiniun bromide, cetyl pyridinium chloride, alkyldimethylbenzylammonium chloride and cetyltrimethylammonium bromide.

31. The method of claim 12 wherein said water-soluble organic dye is selected from the group consisting of Acid Fast Black BR, Acid Complex Green BL, Acid Cyanamine Green G, Light Green SF, Soluble Blue I, Chrome Yellow G, Chrome Yellow M, Chrome Blue Black BC, Chrome Brown RH, Fast Light Yellow G, Acid Fast Yellow R, Alizarin Red, Astrazon Yellow 3G, Astrazon Yellow 5G, Basic Cyanine 6G, Methylene Blue, Basic Furanin 8G, Methyl Violet, Direct Fast Brown, Brown RT, Direct Dark Green B, Direct Copper Blue BB, Direct Sky Blue 5B, Direct Fast Blue G, Direct Violet N, Procion Yellow HA, Remazol Yellow G and Remazol Red 3B.

32. The method of claim 1 wherein said compound is selected from the group consisting of purpureo salt, aniline anhydrochloride, guanidine carbonate and sulfamic acid.

33. The method of claim 1 wherein the amount of said coatings is in the range of from about between 0.005 to 500 g/m².

34. The method of claim 1 wherein the amount of said coatings is in the range of from about between 0.05 to 100 g/m².

35. The method of claim 1 wherein said compound is a phenol.

36. The method of claim 35 wherein said phenol compound is selected from the group consisting of hydroquinone, resorcinol, pyrocatechol, pyrogallol, 2-aminophenol and 3-aminophenol.