Process of making poly(glycidyl azide) product and compounds useful therein

Abstract

A method of making a product comprising poly(glycidyl azide) by reacting polyepichlorohydrin and alkali and/or alkaline earth metal azides in the presence of certain quaternary amine compounds.

We claim: 
     
       1. A method of making a product comprising poly(glycidyl azide) polymer the method comprising the steps of: (A) Preparing a mixture comprising: (1) alkali metal and/or alkaline earth metal azides;   (2) an effective amount of a quaternary amine compound which compound is selected from the group consisting of compounds having the following representative formulas:   (R.sup.1).sub.a (R.sup.2).sub.(4-a)N.sup.(+) X.sup.(-),    (I)       (R.sup.3).sub.2 NC.sub.5 H.sub.4 N.sup.(+) R.sup.1 X.sup.(-), (II)       (R.sup.3).sub.2 NC.sub.6 H.sub.4 R.sup.4═ R.sup.4 C.sub.5 H.sub.4 N.sup.(+) R.sup.1 X.sup.(-)                               (III)       [(R.sup.2).sub.3 N.sup.(+) ].sub.2 R.sup.8 X.sup.(-).sub.2 (IV)       [(R.sup.3).sub.2 NC.sub.5 H.sub.4 N.sup.+ ].sub.2 R.sup.8 X.sup.(-).sub.2 (V)        and blends of compounds having the representative formula (I), (II), (III), (IV) and (V), wherein: (a) R 1  can be the same or different and selected from: {[R 5  (OR 6 ) b  ].sub.(2-c) (R 5 ) c  N[C(R 7 ) 2  ] d  } e  C(R 7 ).sub.(3-e)CH 2  --, or {R 5  (OR 6 ) f  O[C(R 7 ) 12  ] d  } e  C(R 7 ).sub.(3-e) CH 2  --, or {R 5  (OR 6 ) b  Q[C(R 7 ) 2  ] d  } e  C(R 7 ).sub.(3-e) CH 2  --, wherein R 5  groups can be the same or different and are selected from hydrogen or a C 1  to C 10 , alkyl group,   R 6  groups can be the same and different and are divalent organic groups,   R 7  groups can be the same or different and are selected from hydrogen and C 1  to C 10  alkyl groups   Q is selected from alkylene, arylene and combinations thereof, and may be substituted with aryl or alkyl groups, oxygen, nitrogen, carbonyl, urylene, carbamato and imino groups, and combinations thereof,     (b) R 2  groups are the same or different and are selected from C 1  to C 10  alkyl groups, and   (c) R 3  groups can be the same or different and are selected from C 1  to C 8  alkyl groups containing oxygen or nitrogen hetero atoms, provided that such hetero atoms are attached only to carbon atoms, and the two R 6  groups together with adjacent nitrogen atom shown in formula (II) can form a heterocyclic ring containing 3 to 7 atoms,   (d) R 4  groups can be the same or different and are selected from --CH═, --CR 2  ═ and --N═.   (e) R 8  groups are defined as --CH 2  [C(R 7 ) 2  ].sub.(d+1) (OR 6 ) b  Q[C(R 7 ) 2  ].sub.(d+1) CH 2  --   (f) a is a number from 1 to 3,   (g) b is a number from 1 to 50,   (h) c is a number from 0 to 1,   (i) d is a number from 1 to 15,   (j) e is a number from 1 to 3,   (k) f is a number from 0 to 50,   (l) X is a suitable anion.       (B) reacting the mixture prepared in step (A) with polyepichlorohydrin polymer to produce a reaction product, and   (C) recovering from the reaction product a product comprising poly(glycidyl azide) polymer.   
     
     
       2. The method according to claim 1 wherein the product recovered from the reaction product in step (C) consists essentially of poly(glycidyl azide) polymer. 
     
     
       3. The method according to claim 1 wherein the alkaline metal or alkali earth metal azide is sodium azide. 
     
     
       4. The method according to claim 3 wherein the quaternary amine compound is selected from the group consisting of: .sup.˜ 30% R(OCH 2  H 4 ) a  N(CH 3 )CH 2  C(CH 3 ) 2  CH 2  N +  (CH 3 ) 3  Cl -     .sup.˜ 70% [R(OC 2  H 4 ) b  ][R(OC 2  H 4 ) c  ]NCH 2  C(CH 3 ) 2  CH 2  N +  (CH 3 ) 3  Cl -a= .sup.˜ 7, b+c=.sup.˜ 7, R is selected from CH 3  and H,   [R(OC 2  H 4 ) b  ][R(OC 2  H 4 ) c  ]NCH 2  C(CH 3 ) 2  CH 2  N +  (CH 3 ) 3  Cl -b+c= .sup.˜ 7, R is selected from CH 3  and H,   CH 3  O(C 2  H 4  O) 11  C(O)NHC 6  H 3  (CH 3 )NHC(O)OCH 2  C(CH 3 ) 2  CH 2  N +  (CH 3 ) 3  Cl - ,   CH 3  O(C 2  H 4  O) 2  C(O)NHC 6  H 3  (CH 3 )NHC(O)OCH 2  C(CH 3 ) 2  CH 2  N +  (CH 3 ) 3  Cl - ,   CH 3  O(C 2  H 4  O) 11  C(O)NHC 6  H 3  (CH 3 )NHC(O)OCH 2  CH 2  CH 2  C +  NC 5  H 4  N(CH 3 ) 2  Cl - ,   CH 3  O(C 2  H 4  O) 2  C(O)NHC 6  H 5  (CH 3 )NHC(O)OCH 2  CH 2  CH 2  C +  NC 5  H 4  N(CH 3 ) 2  Cl - ,   CH 3  O(C 2  H 4  O) n  CH 2  CHRCH 2  C +  NC 5  H 4  N(CH 3 ) 2  Cl -   wherein n=0-3, R=H or CH 3 ,   CH 3  O(C 2  H 4  O) n  CH 2  C(C 2  H 5 )(C 4  H 9 )CH 2   +  NC 5  H 4  N(CH 3 ) 2  Cl - ,   CH 3  O(C 2  H 4  O) n  CH 2  C(CH 3 ) 2  CH 2   +  NC 5  H 4  N(CH 3 ) 2  Cl - ,   CH 3  O(C 2  H 4  O) n  CH 2  C(C 2  H 5 )(C 4  H 9 )CH 2   +  NC 5  H 4  N-cyclo-(C 2  H 4 ) 2  CHCH 3  Cl - ,   CH 3  O(C 2  H 4  O) n  CH 2  C(CH 3 ) 2  CH 2   +  NC 5  H 4  N-cyclo-(C 2  H 4 ) 2  CHCH 3  Cl - .   
     
     
       5. The method according to claim 1 wherein he mixture of step A further comprises an effective amount of a protic solvent. 
     
     
       6. The method according to claim 5 wherein the effective amount of to protic solvent is 0.1 to 20 parts of protic solvent per 100 parts of polyepichlorohydrin polymer. 
     
     
       7. The method according to claim 1 wherein the mixture prepared in step (A) further comprises an effective amount of solvent of diluent. 
     
     
       8. The method according to claim 7 wherein the effective amount of solvent or diluent is 15 to 30 parts per 100 parts polyepichlorohydrin polymer. 
     
     
       9. The method according to claim 7 wherein the solvent or diluent is selected from the group consisting of tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane and CH 3  O(C 2  H 4  O) n  CH 5  where n is a number from 1 to 7.