Method for the synthesis of energetic thermoplastic elastomers in non-halogenated solvents
View Patent ↗A method is provided for preparing thermoplastic elastomers. A blocks of the thermoplastic elastomers are crystalline at temperatures below about 60° C. and are derived from oxetane derivatives and/or tetrahydrofuran derivatives. B blocks of the thermoplastic elastomer are amorphous above about −20° C. and are derived from oxetanes, tetrahydrofuran, oxiranes, and derivatives thereof. According to this method, the A and B blocks are dissolved into solution containing a non-halogenated solvent, preferably tetrahydrofuran, then dried by azeotropic distillation. The dried blocks are end-capped with a diisocyanate, preferably a diisocyanate having one isocyanate moiety substantially more reactive with the terminal groups of the blocks than the other isocyanate moiety of the diisocyanate. The end-capped blocks are then linked together with a linking compound.
1. A method of preparing a thermoplastic elastomer, comprising:
dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprising at least one non-halogenated solvent selected from the group consisting of at least one organic ether, at least one organic ester, and at least one organic ketone, the A blocks being crystalline below about 75° C. and derived from monomers comprising at least one member selected from the group consisting of oxetane derivatives and tetrahydrofuran derivatives, the B blocks being amorphous above about −20° C. and derived from monomers comprising at least one member selected from the group consisting of oxetane and derivatives thereof, tetrahydrofuran and derivatives thereof, and oxirane and derivatives thereof;
drying the dissolved A blocks and the dissolved B blocks of water by azeotropic distillation of the at least one non-halogenated solvent;
end-capping the dried A blocks and the dried B blocks in the at least one non-halogenated solvent by reacting the dried A blocks and the dried B blocks with at least one diisocyanate in which a first isocyanate moiety thereof is substantially more reactive with the terminal groups of the A blocks and the B blocks than a second isocyanate moiety thereof, wherein the more reactive first isocyanate moiety is capable of reacting with the terminal groups of the A blocks and the B blocks, leaving the less reactive second isocyanate moiety free and unreacted; and
linking the end-capped A blocks and the end-capped B blocks together in the at least one non-halogenated solvent with at least one linking compound comprising two isocyanate-reactive groups which are sufficiently sterically unhindered to react with the free and unreacted isocyanate moieties of the end-capped A blocks and the end-capped B blocks.
2. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises separately dissolving the A blocks and the B blocks into respective solutions.
3. The method as defined in claim 1 , wherein end-capping the dried A blocks and the dried B blocks in the at least one non-halogenated solvent comprises separately end-capping the A blocks and the B blocks in the respective solutions.
4. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution, drying the dissolved A blocks and the dissolved B blocks, end-capping the dried A blocks and the dried B blocks, and linking the end-capped A blocks and the end-capped B blocks are conducted in the absence of a halogenated solvent.
5. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks in an organic ether that comprises at least one member selected from the group consisting of tetrahydrofuran, ethylene glycol dimethyl ether, and 1,4-dioxane.
6. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks in tetrahydrofuran.
7. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks in ethyl acetate.
8. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks in methyl ethyl ketone.
9. The method as defined in claim 1 , wherein linking the end-capped A blocks and the end-capped B blocks together in the at least one non-halogenated solvent with at least one linking compound comprises linking the end-capped A blocks and the end-capped B blocks with at least one linking compound derived from at least one diisocyanate and at least one difunctional urethane oligomer comprising two functional groups which are reactive with isocyanate moieties of the at least one diisocyanate.
10. The method as defined in claim 1 , wherein:
end-capping the dried A blocks and the dried B blocks in the at least one non-halogenated solvent with at least one diisocyanate comprises end-capping the dried A blocks and the dried B blocks with at least one diisocyanate in which the first isocyanate moiety of the diisocyanate is at least five times more reactive with the terminal groups of each of the A blocks and the B blocks as the second isocyanate moiety, wherein the more reactive first isocyanate moiety is capable of reacting with and end-capping the terminal groups of the A blocks and the B blocks, leaving the less reactive second isocyanate moiety free and unreacted; and
linking the end-capped A blocks and the end-capped B blocks together in the at least one non-halogenated solvent with at least one linking compound comprises linking the end-capped A blocks and the end-capped B blocks with the at least one linking compound that has two isocyanate-reactive hydroxyl groups which are sufficiently sterically unhindered to be reactive with the free and unreacted second isocyanate groups of the end-capped blocks.
11. The method as defined in claim 1 , wherein end-capping the dried A blocks and the dried B blocks comprises reacting the dried A blocks and the dried B blocks with a diisocyanate that comprises toluene diisocyanate.
12. The method as defined in claim 1 , wherein the thermoplastic elastomer has a weight average molecular weight of at least 40,000 and a number average molecular weight of at least 10,000.
13. The method as defined in claim 1 , wherein the thermoplastic elastomer has a weight average molecular weight of at least 60,000 and a number average molecular weight of at least 12,000.
14. The method as defined in claim 1 , wherein the thermoplastic elastomer has a weight average molecular weight of at least 80,000 and a number average molecular weight of at least 15,000.
15. The method as defined in claim 1 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks terminated with respective hydroxyl groups as the isocyanate-reactive terminal groups into a solution.
16. A method of making an energetic composition, comprising:
dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprising at least one non-halogenated solvent selected from the group consisting of at least one organic ether, at least one organic ester, and at least one organic ketone, the A blocks being crystalline below about 75° C. and derived from monomers comprising at least one member selected from the group consisting of oxetane derivatives and tetrahydrofuran derivatives, the B blocks being amorphous above about −20° C. and derived from monomers comprising at least one member selected from the group consisting of oxetane and derivatives thereof, tetrahydrofuran and derivatives thereof, and oxirane and derivatives thereof;
drying the dissolved A blocks and the dissolved B blocks of water by azeotropic distillation of the at least one non-halogenated solvent;
end-capping the dried A blocks and the dried B blocks in the at least one non-halogenated solvent by reacting the dried A blocks and the dried B blocks with at least one diisocyanate in which a first isocyanate moiety thereof is substantially more reactive with the terminal groups of the A blocks and the B blocks than a second isocyanate moiety thereof, wherein the more reactive first isocyanate moiety is capable of reacting with the terminal groups of the A blocks and the B blocks, leaving the less reactive second isocyanate moiety free and unreacted;
linking the end-capped A blocks and the end-capped B blocks together in the at least one non-halogenated solvent with at least one linking compound comprising two isocyanate-reactive groups which are sufficiently sterically unhindered to react with the free and unreacted isocyanate moieties of the end-capped A blocks and the end-capped B blocks; and
blending the thermoplastic elastomer with about 50 wt % to about 95 wt % of at least one solid selected from the group consisting of fuel particulates and oxidizer particulates.
17. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises separately dissolving the A blocks and the B blocks into respective solutions.
18. The method as defined in claim 17 , wherein end-capping the dried A blocks and the dried B blocks in the at least one non-halogenated solvent comprises separately end-capping the A blocks and the B blocks in the respective solutions.
19. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution, drying the dissolved A blocks and the dissolved B blocks, end-capping the dried A blocks and the dried B blocks, and linking the end-capped A blocks and the end-capped B blocks are conducted in the absence of a halogenated solvent.
20. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks into at least one organic ether selected from the group consisting of tetrahydrofuran, ethylene glycol dimethyl ether, and 1,4-dioxane.
21. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks into tetrahydrofuran.
22. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks into ethyl acetate.
23. The method as defined in claim 16 , wherein dissolving A blocks and B blocks terminated with respective isocyanate-reactive groups into a solution comprises dissolving the A blocks and the B blocks into methyl ethyl ketone.
24. A method of making a rocket motor propellant comprising making an energetic composition as defined in claim 16 .
25. A method of making a gun propellant comprising making an energetic composition as defined in claim 16 .
26. A method of making an explosive comprising making an energetic composition as defined in claim 16 .
27. A method of making a gasifier comprising making an energetic composition as defined in claim 16 .