PROCESS FOR GRAFTING POLYMERIC VINYL AND VINYLIDENE CHLORIDE SIDE-CHAINS TO POLYOLS AND FLUID DISPERSION COMPOSITIONS

• US 3,655,553 A
• Filed: 03/12/1970
• Issued: 04/11/1972
• Est. Priority Date: 03/12/1970
• Status: Expired due to Term

• Current Assignee: Occidental Chemical Corporation (Occidental Petroleum Corporation)
• Original Assignee: Raymond C De Wald
• Inventors: De Wald, Raymond C.
• Primary Examiner(s): Goolkasian, John T.
• Assistant Examiner(s): McCamish, M. E.
• Application Number:
  US05/019,105
• Time in Patent Office: 761 Days
• Field of Search: 252/1 260/2R,2.5R,2.5AP,2.5P,890,899,857,858,873,88.1,77.5
• US Class Current: 252/1
• CPC Class Codes: C08F 214/04 Monomers containing two carbon atoms
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08G 18/638 characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles

Abstract

This invention comprises a process for grafting polymeric sidechains of vinyl and vinylidene chloride to triols such as polyethylenoxy or polypropylenoxy triols and the product produced thereby. It has been found that by the polymerization of specific mixtures of vinyl chloride and vinylidene chloride in the presence of such triols, polymeric sidechains are grafted to the polyols in such a manner that the grafted products have much lower viscosities than are obtained when either the vinyl chloride or the vinylidene chloride is used alone in otherwise identical grafting operations. The mixture can also contain a chain transfer agent to aid further in reducing the viscosity. The proportions used in the mono-mer mixtures are in the range of 15-88% by weight of vinyl chloride, 12-85%, preferably 15-85% vinylidene chloride, and 0-5 parts by weight of a chain transfer agent. The proportion of monomer in the polyol mixture is advantageously in the range of 21-45%, preferably 25-45% by weight based on the combined weight of monomer and polyol, and the resultant product advantageously has at least 15% by weight chlorine. The resultant chlorinated polyol is particularly useful in the preparation of polyurethanes having fire retardant properties, by the reaction of the polyols with diisocyanates such as toluene diisocyanate.

Claims

2. The dispersion of claim 1 in which said dispersion has a Brookfield viscosity of less than 40,000 centipoises.

3. The dispersion of claim 1 in which said polyol dispersion medium is a polyol having a molecular weight in the range of 1, 500 to 5,000.

4. The dispersion of claim 1 in which said polyol dispersion medium is substantially all triol having a molecular weight in the range of 1,500-5,000.

5. The dispersion of claim 1 in which said polyol dispersion medium is substantially all triol having a molecular weight in the range of 3,000-5,000.

6. The dispersion of claim 1 in which said polyol is a triol and is a polypropylene oxide derivative of glycerine having a molecular weight of at least 1,500.

7. The dispersion of claim 6 in which said triol has a molecular weight of at least 3,000.

8. The dispersion of claim 1 in which said polyol is a triol and is a polypropylene oxide derivative of 1,1,1-trihydroxymethylpropane having a molecular weight of at least 1, 500.

9. The dispersion of claim 1 in which said polyol is a triol and is a polyethylene oxide derivative of glycerine and has a molecular weight of at least 1,500.

10. The process of preparing a stable dispersion having a Brookfield viscosity of no more than 100,000 centipoises comprising the step of polymerizing in the presence of 0.001-10 percent by weight of a free-radical generating catalyst based on weight of monomeric mixture for a period of at least two hours at a temperature of 30*-80* C. a mixture of 21-45 parts by weight of a monomeric mixture consisting of 15-88 percent by weight of vinyl chloride, 12-85 percent by weight of vinylidene chloride and 0-5 percent by weight of a chain transfer agent, with 55-79 parts by weight of a polyol having a molecular weight in the range of 500 to 5,500, said polyol having the formula wherein n is an integer having a value of 2-4, x is an integer of sufficient value to give the polyol a molecular weight of 500 to 5,500, R is hydrogen or an alkyl group of no more than two carbon atoms, and Y is a core radical having a valency corresponding to the value of n, said core radical having a saturated aliphatic hydrocarbon center and amino nitrogen or oxygen atoms through which said core radical is connected to the remainder of said polyol, and said polyol comprising at least 60 percent by weight of a polyol in which said n has a value of 3.

11. The process of claim 10 in which said monomeric mixture contains at least 15 percent by weight of vinylidene chloride.

12. The process of claim 11 in which said catalyst is an azo catalyst.

13. The process of claim 12 in which said catalyst is azobisisobutyronitrile.

14. The process of claim 11 in which said temperature is in the range of 45* to 75* C.

15. The process of claim 11 in which the polymerizAtion is continued until a conversion of at least 50 percent of the monomeric mixture has been effected.

16. The process of claim 11 in which the molecular weight of said polyol is in the range of 1,500-5,000.

17. The process of claim 11 in which the molecular weight of said polyol is in the range of 3,000-5,000.

18. The process of claim 11 in which said free-radical generating catalyst is present in the amount of 0.05 to 1 percent by weight based on the monomeric mixture.

19. The process of claim 11 in which said polyol is essentially all triol.

20. The process of claim 11 in which said polyol comprises a propylene oxide derivative of glycerine and has a molecular weight of at least 1,500.

21. The process of claim 11 in which said polyol comprises a propylene oxide derivative of 1,1,1-trihydroxymethylpropane and has a molecular weight of at least 1,500.

22. The process of claim 11 in which said polyol comprises an ethylene oxide derivative of glycerine and has a molecular weight of at least 1,500.

23. The process of claim 11 in which said polyol comprises the ethylene oxide derivative of 1,1,1-trihydroxymethylpropane.

24. The process of claim 11 in which said polyol consists essentially of a propylene oxide derivative of glycerine having a molecular weight in the range of 1,500 to 5,000 and said temperature is in the range of 45* to 75* C. and said polymerization is continued until a conversion of at least 50 percent of the monomer is effected.

25. The process of claim 10 in which said mixture contains at least 0.1 part of said chain transfer agent.

26. The process of claim 25 in which said transfer agent is trichloroethylene.

27. The process of claim 25 in which said transfer agent is carbon tetrachloride.

28. The process of claim 25 in which said transfer agent is isobutylene.