TELECHELIC COPOLYMERS OF DIENES AND POLYMERIZABLE FERROCENE OR CARBORANE COMPOUNDS

• US 3,816,380 A
• Filed: 06/18/1971
• Issued: 06/11/1974
• Est. Priority Date: 06/18/1971
• Status: Expired due to Term

• Current Assignee: Samuel F. Reed Jr
• Original Assignee: Samuel F. Reed Jr
• Inventors: Reed, Samuel F. Jr.
• Primary Examiner(s): Padgett, Benjamin R.
• Assistant Examiner(s): Miller, E. A.
• Application Number:
  US05/155,669
• Time in Patent Office: 1,089 Days
• Field of Search: 260/439CY,83.5,85.3R,85.3C,82.1,86.3,66.5B 149/19.2
• US Class Current: 526/215
• CPC Class Codes: C06B 23/007 Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
• CPC Class Codes: C06B 45/10 the organic component containing a resin
• CPC Class Codes: C08F 236/04 conjugated

Abstract

Copolymers of a diene selected from butadiene, isoprene, and chloroprene and a polymerizable monomer selected from ferrocenylmethyl methacrylate, isopropenylferrocene, 1ferrocenylbutadiene, 2-ferrocenyl-butadiene, vinylcarborane, isopropenylcarborane and carboranylmethyl acrylate are disclosed along with preparative procedures therefor. Copolymerizations are carried out in solution (toluene or dioxane) with a suitable polymerization initiator selected from an azo compound to introduce either carboxyl or hydroxyl functionality into the copolymers.

Claims

2. The copolymers prepared by the reaction of claim 1 wherein said polmerizable monomer is selected from ferrocenylmethyl methacrylate, and 1-ferrocenylbutadiene and wherein weight ratios of said diene to said polymerizable monomer is varied from about 1:

1 to about 19;

1 and wherein said copolymers are further characterized by having an iron content up to about 15 weight percent.

3. The copolymers of claim 2 wherein said diene selected is isoprene;

said polymerizable monomer selected is ferrocenylmethyl methacrylate;

said initiator selected is 4,4'"'"''"'"'-azobis(4-cyano-n-pentanol); and

wherein said copolymers are still further characterized by having a molecular weight from about 3,300 to about 4,400, a weight percent of OH terminal groups from about 0.25 to about 1.20, and a weight percent Fe from about 1.1 to about 6.3.

4. The copolymers of claim 2 wherein said diene selected is butadiene;

said polymerizable monomer selected is 1-ferrocenylbutadiene;

said initiator selected is azobis(2-methyl valeric acid); and

wherein said copolymers are still further characterized by having a molecular weight from about 1,900 to about 2,800, a weight percent of CO2H terminal groups from about 3.20 to about 4.33, and weight percent Fe from about 2.0 to about 15.

5. The copolymers prepared by the reaction of claim 1 wherein said polymerizable monomer is selected from vinylcarborane and isopropenylcarborane and wherein weight ratios of said diene to said polymerizable monomer is varied from about 1:

1 to about 19;

1 and wherein said copolymers are further characterized by having a boron content up to about 30 weight percent.

6. Copolymers of a diene selected from butadiene, isoprene, and chloroprene and carboranylmethyl acrylate;

said copolymers being the carboxyl terminated copolymers that are prepared by reacting said carboranylmethyl acrylate and a suitable polymerization initiator in an inert organic solvent with said diene at a reaction temperature and for a reaction time period sufficient for said reaction to take place after which solvent removal is effected and said copolymers are dried at a suitable drying temperature while under reduced pressure;

said initiator being selected from the azo initiators consisting of azobis(2-methyl valeric acid), and 4,4'"'"''"'"'-cyanopentanoic acid) to introduce carboxyl functionality into said copolymers;

said inert organic solvent being selected from dioxane and toluene;

said reaction temperature being from about 66*-67*C.;

said reaction time being from about 72-96 hours;

said drying is accomplished at a suitable temperature in the range of about 70*C. to about 75*C. and said reduced pressure is in the range of about 1 millimeter;

said diene and said carboranylmethyl acrylate being reacted in weight ratios from about 1;

1 to about 19;

1;

said copolymers being characterized by molecular weights in the range from about 1,500 to about 10,000, a CO2H end group from about 0.1 to about 5 weight percent, and by a boron content up to about 30 weight percent of said copolymers.

7. The copolymers prepared by the reaction of claim 6 wherein said diene selected is butadiene;

said initiator selected is azobis (2-methyl valeric acid); and

wherein said copolymers are still further characterized by having a molecular weight from about 2,500 to about 3,500, a weight percent of CO2H terminal groups from about 1.45 to about 2.56, and a weight percent boron from about 2.55 to about 20.