1-AMINO-3-(OXYALKYLALKOXYSILYL)-2-PROPANOL-TERMINATED DIENE RUBBERS

Abstract

The invention concerns 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated diene rubbers, their preparation and use.

Claims

1. An 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to general formula (I), ##STR00010## wherein the polymer contains at least one carbon-carbon double bond; R.sub.1 is selected from the group consisting of (i) a —C.sub.1-C.sub.24-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.24-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (iii) a 6-24-membered aryl that is unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is either saturated or unsaturated, and which is unsubstituted, mono- or polysubstituted; (iv) a 5-24-membered heteroaryl that is unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; (v) a 3-24-membered cycloalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; and (vi) a 3-24-membered heterocycloalkyl that is saturated or unsaturated and is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; R.sub.2 is selected from the group consisting of (i) —C.sub.1-C.sub.24-alkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (ii) —C.sub.1-C.sub.24-heteroalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iii) 6-24-membered aryl, unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iv) 5-24-membered heteroaryl, unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (v) 3-24-membered cycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; and (vi) 3-24-membered heterocycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; R.sub.3 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.4 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.5 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; R.sub.6 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; wherein “mono- or polysubstituted” means substituted with one substituent in the case of “monosubstituted” or with more than one substituent in the case of “polysubstituted”, wherein the substituents independently of one another are selected from the group consisting of —F, —Cl, —Br, —I, —CN, ═O, —CF.sub.3, —CF.sub.2H, —CFH.sub.2, —CF.sub.2Cl, —CFCl.sub.2, —C.sub.1-C.sub.18-alkyl that is saturated or unsaturated, and —C.sub.1-C.sub.18-heteroalkyl that is saturated or unsaturated; and x+y=3 with 1≤x≤3 and 0≤y≤2.

2. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein the polymer is a homopolymer or a copolymer of one or more conjugated dienes.

3. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 16, wherein the the polymer is a homo- or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnecenes, ocimenes, or 1,3-hexadiene, or a combination thereof; or a copolymer of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnecenes, ocimenes, or a combination thereof with (ii) styrene, o-, m- and/or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinyl naphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, or a combination thereof.

4. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein the polymer is obtained by copolymerization of 1,3-butadiene with styrene; or isoprene with styrene.

5. (canceled)

6. (canceled)

7. (canceled)

8. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein R.sub.1 is (i) —C.sub.1-C.sub.6-alkyl, saturated or unsaturated, unsubstituted; R.sub.2 is (i) —C.sub.1-C.sub.6-alkyl, saturated or unsaturated, unsubstituted; R.sub.3 is (i) —C.sub.1-C.sub.6-alkylene-, saturated or unsaturated, unsubstituted; R.sub.4 is —C.sub.1-C.sub.6-alkylene-, saturated or unsaturated, unsubstituted; and R.sub.5 is —C.sub.1-C.sub.6-alkyl, saturated or unsaturated, unsubstituted and R.sub.6 is —C.sub.1-C.sub.6-alkyl, saturated or unsaturated, unsubstituted; x is 3 and y is 0.

9. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein the polymer is obtained by copolymerization of 1,3-butadiene with styrene; R.sub.1 is —C.sub.1-C.sub.2-alkyl, saturated or unsaturated, unsubstituted; R.sub.2 is —C.sub.1-C.sub.2-alkyl, saturated or unsaturated, unsubstituted; R.sub.3 is —C.sub.1-C.sub.2-alkylene-, saturated or unsaturated, unsubstituted; R.sub.4 is —C.sub.3-alkylene-, saturated or unsaturated, unsubstituted; R.sub.5 and R.sub.6 independently of one another are —C.sub.1-C.sub.2-alkyl, saturated or unsaturated, unsubstituted; and x+y=3 with 1≤x≤3 and 0≤y≤2.

10. A method for manufacturing a 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to general formula (I), ##STR00011## comprising the following steps: (a) providing a polymer containing at least one carbon-carbon double bond; (b) providing a cyclic urea derivative of the general formula (II) ##STR00012## (c) providing a glycidoxyalkylsilane of the general formula (III) ##STR00013## (d) adding the cyclic urea derivative of the general formula (II) to the polymer as a first functionalization reagent to form a functionalized polymer intermediate; and (e) subsequently adding the glycidoxyalkylsilane of the general formula (III) to the functionalized polymer intermediate as a second functionalization reagent to form the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to general formula (I); wherein R.sub.1 is selected from the group consisting of (i) a —C.sub.1-C.sub.24-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.24-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (iii) a 6-24-membered aryl that is unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is either saturated or unsaturated, and which is unsubstituted, mono- or polysubstituted; (iv) a 5-24-membered heteroaryl that is unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; (v) a 3-24-membered cycloalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; and (vi) a 3-24-membered heterocycloalkyl that is saturated or unsaturated and is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; R.sub.2 is selected from the group consisting of (i) —C.sub.1-C.sub.24-alkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (ii) —C.sub.1-C.sub.24-heteroalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iii) 6-24-membered aryl, unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iv) 5-24-membered heteroaryl, unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (v) 3-24-membered cycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; and (vi) 3-24-membered heterocycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; R.sub.3 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.4 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.5 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; R.sub.6 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; wherein “mono- or polysubstituted” means substituted with one substituent in the case of “monosubstituted” or with more than one substituent in the case of “polysubstituted”, wherein the substituents independently of one another are selected from the group consisting of —F, —Cl, —Br, —I, —CN, ═O, —CF.sub.3, —CF.sub.2H, —CFH.sub.2, —CF.sub.2Cl, —CFCl.sub.2, a —C.sub.1-C.sub.18-alkyl that is saturated or unsaturated, or a —C.sub.1-C.sub.18-heteroalkyl that is saturated or unsaturated; and x+y=3 with 1≤x≤3 and 0≤y≤2.

11. The method according to claim 10, wherein step (a) is performed by an anionic solution polymerization, or a polymerization using a coordination catalyst.

12. The method according to claim 10, wherein step (a) is performed in the presence of a solvent; and an initiator.

13. (canceled)

14. The method according to claim 10, which comprises at least one of additional (f) to (i) of adding (f) a coupling reagent before, together with or after addition of the cyclic urea derivative of the general formula (III); (g) an antioxidant after the cyclic urea derivative of the general formula (III) and the cyclic carboxylic anhydride of the general formula (IV) have been added; (h) an extender oil; (i) a filler; (j) a rubber or a rubber additive.

15. (canceled)

16. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein the polymer is a diene rubber.

17. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to claim 1, wherein the polymer is a copolymer of one or more conjugated dienes with one or more vinylaromatic monomers.

18. The method of claim 10, wherein the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer is a diene rubber.

19. The method of claim 10, wherein the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer is a homopolymer or a copolymer of one or more conjugated dienes.

20. The method of claim 10, wherein the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer is a copolymer of one or more conjugated dienes with one or more vinylaromatic monomers

21. The method of claim 10, wherein the polymer is a homo- or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnecenes, ocimenes, 1,3-hexadiene or a combination thereof; or a -copolymer of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnecenes, ocimenes, or a combination thereof with (ii) styrene, o-, m- and/or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene or a combination thereof.

22. The method of claim 10, wherein the polymer is a copolymer of 1,3-butadiene with styrene or isoprene with styrene.

23. The method of claim 10, wherein R.sub.1 is (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted R.sub.2 is a (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted R.sub.3 is a (i) —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted R.sub.4 is a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted R.sub.5 is a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted and R.sub.6 is a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted; x is 3 and y is 0.

24. The method of claim 10, wherein the polymer is obtainable by copolymerization of 1,3-butadiene with styrene; R.sub.1 is a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; R.sub.2 is a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; R.sub.3 is a —C.sub.1-C.sub.2-alkylene- that is saturated or unsaturated and that is unsubstituted; R.sub.4 is a —C.sub.3-alkylene- that is saturated or unsaturated and that is unsubstituted; R.sub.5 and R.sub.6 are independently of one another a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; and x+y=3 with 1≤x≤3 and 0≤y≤2.

25. The method of claim 10, wherein wherein step (a) is performed by a polymerization using a coordination catalyst, wherein the coordination catalyst is selected from a Ziegler-Natta catalyst or a monometallic catalyst system.

26. A molded article prepared from a vulcanizable composition comprising a polymer, wherein the preparation comprises vulcanization of the vulcanizable composition and wherein the polymer is an 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymer according to general formula (I), ##STR00014## wherein the polymer contains at least one carbon-carbon double bond wherein R.sub.1 is selected from the group consisting of (i) a —C.sub.1-C.sub.24-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.24-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (iii) a 6-24-membered aryl that is unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is either saturated or unsaturated, and which is unsubstituted, mono- or polysubstituted; (iv) a 5-24-membered heteroaryl that is unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; (v) a 3-24-membered cycloalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; and (vi) a 3-24-membered heterocycloalkyl that is saturated or unsaturated and is unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through a —C.sub.1-C.sub.6-alkylene- or a —C.sub.1-C.sub.6-heteroalkylene-, which in each case is saturated or unsaturated and which is unsubstituted, mono- or polysubstituted; R.sub.2 is selected from the group consisting of (i) —C.sub.1-C.sub.24-alkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (ii) —C.sub.1-C.sub.24-heteroalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iii) 6-24-membered aryl, unsubstituted, mono- or polysubstituted, wherein said 6-24-membered aryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (iv) 5-24-membered heteroaryl, unsubstituted, mono- or polysubstituted; wherein said 5-24-membered heteroaryl is optionally connected through —C.sub.1-C.sub.6-alkylene- or -C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; (v) 3-24-membered cycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered cycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; and (vi) 3-24-membered heterocycloalkyl, saturated or unsaturated, unsubstituted, mono- or polysubstituted; wherein said 3-24-membered heterocycloalkyl is optionally connected through —C.sub.1-C.sub.6-alkylene- or —C.sub.1-C.sub.6-heteroalkylene-, in each case saturated or unsaturated, unsubstituted, mono- or polysubstituted; R.sub.3 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.4 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkylene- that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered arylene that is unsubstituted, mono- or polysubstituted; R.sub.5 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; R.sub.6 is selected from the group consisting of (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; (ii) a —C.sub.1-C.sub.6-heteroalkyl that is saturated or unsaturated and that is unsubstituted, mono- or polysubstituted; and (iii) a 6-14-membered aryl that is unsubstituted, mono- or polysubstituted; wherein “mono- or polysubstituted” means substituted with one substituent in the case of “monosubstituted” or with more than one substituent in the case of “polysubstituted”, wherein the substituents independently of one another are selected from the group consisting of —F, —Cl, —Br, —I, —CN, ═O, —CF.sub.3, —CF.sub.2H, —CFH.sub.2, —CF.sub.2Cl, —CFCl.sub.2, -C.sub.1-C.sub.18-alkyl that is saturated or unsaturated, or —C.sub.1-C.sub.18-heteroalkyl that is saturated or unsaturated; and x+y=3 with 1≤x≤3 and 0≤y≤2.

27. The molded article of claim 26, wherein the polymer is a homo- or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnecenes, ocimenes, 1,3-hexadiene or a combination thereof; or a copolymer of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnecenes, ocimenes, or a combination thereof with (ii) styrene, o-, m- and/or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene or a combination thereof.

28. The molded article of claim 26, wherein the polymer is a copolymer of 1,3-butadiene and styrene or a copolymer of isoprene and styrene.

29. The molded article of claim 26, wherein R.sub.1 is (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted R.sub.2 is a (i) a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted R.sub.3 is a (i) —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted R.sub.4 is a —C.sub.1-C.sub.6-alkylene- that is saturated or unsaturated and that is unsubstituted R.sub.5 is a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted and R.sub.6 is a —C.sub.1-C.sub.6-alkyl that is saturated or unsaturated and that is unsubstituted; x is 3 and y is 0.

30. The molded article of claim 26, wherein the polymer is a copolymer of 1,3-butadiene and styrene; R.sub.1 is a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; R.sub.2 is a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; R.sub.3 is a —C.sub.1-C.sub.2-alkylene- that is saturated or unsaturated and that is unsubstituted; R.sub.4 is a —C.sub.3-alkylene- that is saturated or unsaturated and that is unsubstituted; R.sub.5 and R.sub.6 are independently of one another a —C.sub.1-C.sub.2-alkyl that is saturated or unsaturated and that is unsubstituted; and x+y=3 with 1≤x≤3 and 0≤y≤2.

31. The molded article of claim 26, which is selected from cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings, damping elements.

32. The molded article of claim 26, which is selected from a tire.

Description

EXAMPLES

[0157] The number-average molecular weight Mn, the polydispersity Mw/Mn and the degree of coupling of the styrene-butadiene rubbers were determined using GPC (PS calibration).

[0158] The Mooney viscosity ML(1+4)100° C. was measured according to DIN 52523/52524.

[0159] The vinyl and styrene content was determined by FTIR spectroscopy on rubber films.

[0160] The glass transition temperature Tg was determined using DSC from the 2nd heating curve at a heating rate of 20 K/min.

[0161] The loss factors tan δ were measured at 0° C. and tan δ at 60° C. to determine the temperature-dependent dynamic-mechanical properties. An Eplexor device (Eplexor 500 N) from Gabo was used for this purpose. The measurements were carried out in accordance with DIN 53513 at 10 Hz on Ares strips in the temperature range from −100° C. to 100° C. The Eplexor 500 N was used for this purpose. To determine the strain-dependent dynamic-mechanical properties, ΔG′ was determined as the difference between the shear modulus at 0.5% strain and the shear modulus at 15% strain as well as the maximum loss factor tan δmax. These measurements were determined according to DIN53513-1990 on an MTS elastomer test system on cylinder specimens (20×6 mm) with 2 mm compression at a temperature of 60° C. and a measuring frequency of 10 Hz in the strain range from 0.1% to 40%.

[0162] The rebound elasticity was determined at 23° C. and 60° C. according to DIN 53512.

Styrene-Butadiene Copolymers

Example 1

Synthesis of Styrene-Butadiene Copolymer, Non-Functionalized (Comparative Example)

[0163] An inert 20L reactor was filled with 8.5 kg hexane, 6.6 mmol 2,2-bis(2-tetrahydrofuryl)-propane and 12.1 mmol n-butyllithium (as a 23% solution by weight in hexane) and the contents heated to 40° C. The heating circuit was then closed and 1185 g of 1,3-butadiene and 315 g of styrene were added simultaneously. It was polymerized under stirring for 35 minutes whereas the reactor contents reached a peak temperature of 61° C. 12.1 mmol n-octanol was then added to stop the anionic polymer chain ends. The rubber solution was drained, stabilized by adding 3 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol) and the solvent removed by stripping with steam. The rubber crumbs were dried at 65° C. for 16 h in a vacuum drying oven.

[0164] The number-average molecular weight Mn, the molecular weight distribution Mw/Mn, the degree of coupling (all from the GPC measurement with PS calibration), the Mooney viscosity ML1+4@100° C., the vinyl and styrene content (from the FTIR measurement, data in % by weight, based on the total polymer), as well as the glass transition temperature Tg (from the DSC measurement) were determined on the dried rubber crumbs. The values are listed in Table 1.

Example 2

Functionalization of Styrene-Butadiene Copolymer by Reaction with 1,3-dimethyl-2-imidazolidinone (Comparative Example)

[0165] The procedure was the same as in example 1. Instead of n-octanol, however, the amount of the functionalization reagent 1,3-dimethyl-2-imidazoli¬dinone (1) equimolar to n-butyllithium was added and the reactor content then stirred for a further 5 minutes. The rubber solution was then drained, stabilized by adding 3 g Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol) and the solvent removed by stripping with steam. The rubber crumbs were dried at 65° C. for 16 h in a vacuum drying oven.

Example 3

Functionalization of Styrene-Butadiene Copolymer by Reaction with (3-glycidoxypropyl)trimethoxysilane (Comparative Example)

[0166] The procedure was the same as in example 2. As functionalization reagent, the amount of (3-glycidoxypropyl)trimethoxysilane (15) equimolar to n-butyl-lithium was added.

Example 4

Functionalization of Styrene-Butadiene Copolymer by Reaction with (3-glycidoxypropyl)triethoxysilane (Comparative Example)

[0167] The procedure was the same as in example 2. As functionalization reagent, the amount of (3-glycidoxypropyl)triethoxysilane (16) equimolar to n-butyl-lithium was added.

Example 5

Functionalization of Styrene-Butadiene Copolymer by Successive Reaction with 1,3-dimethyl-2-imidazolidinone and (3-glycidoxypropyl)trimethoxysilane (Inventive Example)

[0168] The procedure was the same as in example 2. For functionalization, the amount of 1,3-dimethyl-2-imidazolidinone (1) equimolar to n-butyl-lithium was added first. It was stirred for 5 minutes and then the amount of (3-glycidoxypropyl)trimethoxysilane (15) equimolar to n-butyllithium was added.

Example 6

Functionalization of Styrene-Butadiene Copolymer by Successive Reaction with 1,3-dimethyl-2-imidazolidinone and (3-glycidoxypropyl)triethoxysilane (Inventive Example)

[0169] The procedure was the same as in example 2. For functionalization, the amount of 1,3-dimethyl-2-imidazolidinone (1) equimolar to n-butyl-lithium was added first. It was stirred for 5 minutes and then the amount of 3-glycidoxypropyltriethoxysilane (16) equimolar to n-butyllithium was added.

[0170] The polymer properties of styrene-butadiene copolymers from examples 1-6 are summarized in Table 1. Table 1 shows that the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol-terminated polymers of examples 5 and 6, prepared by successive addition of the two functionalization reagents according to formula (II) and (III), have significantly reduced degrees of coupling compared to the polymers of examples 3 and 4, prepared by addition of functionalization reagents according to formula (III) without prior addition of a functionalization reagent according to formula (II).

Rubber Compounds

[0171] Tire tread rubber compounds containing the styrene-butadiene copolymers of examples 1-6 were produced. The components are listed in Table 2. The components (without sulfur and accelerator) were mixed in a 1.5 L kneader. The components sulfur and accelerator were mixed in on a roller at 40° C. The individual steps in the preparation of the mixture are listed in Table 3.

TABLE-US-00001 TABLE 1 Properties of the styrene-butadiene copolymers according to Examples 1-6 functionalization functionalization S-SBR reagent reagent degree of Vinyl- Styrene- from according to according to M.sub.n coupling ML1 + 4 content content Tg Example formula (II) formula (III) [kg/mol] M.sub.w/M.sub.n [%] [ME] [wt.-%] [wt.-%] [° C.] 1 (comparativ — — 269 1.12  0 45 49.2 20.7 −26.8 2 (comparativ (1) — 207 1.40  2 51 49.6 20.5 −27.2 3 (comparativ — (15) 308 1.38 33 67 50.4 20.2 −26.1 4 (comparativ — (16) 292 1.50 29 64 49.9 20.6 −26.3 5 (inventive) (1) (15) 248 1.41  6 74 51.8 20.2 −24.3 6 (inventive) (1) (16) 239 1.47  7 67 48.6 20.8 −27.1

TABLE-US-00002 TABLE 2 Components of tire tread rubber compounds (Specifications in phr: parts by weight per 100 parts by weight rubber) Styrene-butadiene copolymer 70 High-cis polybutadiene (BUNA CB 24 from Arlanxeo 30 Deutschland GmbH) Silica (Ultrasil ® 7000) 90 Carbon black (Vulcan ® J/N 375) 7 TDAE oil (Vivatec 500) 36.3 Processing aid (Aflux 37) 3 Stearic acid (Edenor C 18 98-100) 1 Antioxidant (Vulkanox ® 4020/LG der Lanxess 2 Deutschland GmbH) Antioxidant (Vulkanox ® HS/LG der Lanxess 2 Deutschland GmbH) Zink oxide (Zinkweiβ Rotsiegel) 3 Light protection wax (Antilux 654) 2 Silane (Si 69 ® from Evonik) 7.2 Diphenylguanidine (Rhenogran DPG-80) 2.75 Sulfenamide (Vulkacit ® NZ/EGC from Lanxess 1.6 Deutschland GmbH) Sulphur (Mahlschwefel 90/95 Chancel) 1.6 Sulfonamide (Vulkalent ® E/C) 0.2

TABLE-US-00003 TABLE 3 Preparation Step 1:  0 seconds Addition of polymers Mixing in  30 seconds Addition of ⅔ silica, ⅔ silane, stearic acid, wax, antioxidant, carbon black a 1.5 litre  90 seconds Addition of residual silica and silane kneader 150 seconds Addition of zinc oxide 240 seconds Heat up to 150° C., hold at temperature for 3 min 420 seconds Ejection Step 2: Cut the sheet three times left and right followed by 3 revolutions at 40° C. and a Mixing on nip of 4 mm the roller Step 3: 24 hours storage at 24° C. Step 4:  0 seconds Addition of the compound from step 3 Mixing in  30 seconds Heat up to 150° C., hold at temperature for 3 min a 1.5 litre 210 seconds Ejection kneader Step 5: Addition of sulphur and accelerator, cut the sheet three times left and right Mixing on followed by 3 rounds at 40° C. and a nip of 4 mm the roller

[0172] The rubber compounds were vulcanized at 160° C. for 20 minutes. The physical properties of the corresponding vulcanizates 7-12 are listed in Table 4. The vulcanizate properties of the vulcanized rubber compound from comparison example 7 with the non-functionalized styrene-butadiene copolymer as the compound component are given an index of 100. All values greater than 100 in Table 4 indicate a corresponding percentage improvement of the respective test property.

TABLE-US-00004 TABLE 4 properties of vulcanizates vulcanizate vulcanizate vulcanizate vulcanizate vulcanizate vulcanizate Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 contains   1   2   3   4   5   6 SBR from Example Tanδ at 0° C. 100 115 114 110 115 111 Tanδ at 60° C. 100 114 116 117 118 121 Tanδ 100 111 108 114 115 118 Maximum ΔG′ 100 145 131 155 162 165 rebound 100  92  91  92 100  96 elasticity at 23° C. rebound 100 112 110 111 113 112 elasticity at 60° C.

[0173] The rebound elasticity at 60° C., the loss factor tanδ at 60° C. from the temperature-dependent dynamic-mechanical measurement as well as the tanδ maximum and the modulus difference G′ between low and high strain from the strain-dependent dynamic-mechanical measurement are indicators for the rolling resistance in the tire. The loss factor tanδ at 0° C. and the rebound elasticity at 23° C. are indicators for the wet slip resistance of the tire.

[0174] As can be seen from Table 4, all vulcanizates containing functionalized diene rubbers are characterized by improved values for the wet grip indicator tanδ at 0° C. and the rolling resistance indicators. The vulcanizates from the inventive examples 11 and 12 show the best overall picture of all property indicators.