High tensile strength amorphous 1-butene/propylene copolymers

• US 5,302,675 A
• Filed: 09/08/1992
• Issued: 04/12/1994
• Est. Priority Date: 09/08/1992
• Status: Expired due to Term

• Current Assignee: Rextac Llc
• Original Assignee: Rexene Corp. (Huntsman Corporation)
• Inventors: Allen, George C., Sustic, Andres
• Primary Examiner(s): Smith, Edward J.
• Application Number:
  US07/941,916
• Time in Patent Office: 581 Days
• Field of Search: 526/125, 526/348.6
• US Class Current: 526/125.3
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/16 Syndiotactic
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/6465 containing silicium
• CPC Class Codes: C08F 4/6555 and magnesium or compounds thereof

Abstract

A process for the production of propylene/1-butene copolymers comprising:

reacting propylene and 1-butene monomers in the presence of a catalyst system comprising:

(a) a solid supported catalyst component is prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0.

(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50:1 and about 500:1.

(c) an alkoxy silane component of the formula R_n Si(OR'"'"')_4-n where n=1-3, R=aryl or alkyl and R'"'"'=C_1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1.

said copolymer being characterized by a propylene content of 25 to 50 wt%, a 1-butene content of 75 to 50 wt% and a tensile strength of at least 300 psig.

Claims

1. A process for the production of an amorphous propylene/1-butene copolymers comprising:

reacting propylene and 1-butene monomers in the presence of a catalyst system comprising;

(a) a solid supported catalyst component is prepared by the method comprising;

(i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8;

0.5 to about 8;

3 in the absence of added electron donor; and

(ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8;

0.1 to about 8;

1.0.

(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50;

1 and about 500;

1.

(c) an alkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20;

1 to about 45;

1;

said amorphous copolymer being characterized by a propylene content of 25 to 50 wt% and 1-butene content of 75 to 50 wt%.

2. The process of claim 1 wherein the propylene and 1-butene monomers are polymerized at a temperature of from 130°

F. to 150°

F.

3. The process of claim 1 wherein the propylene and 1-butene monomers are polymerized at pressure from 250 psig to 350 psig.

4. The process of claim 1 wherein the alkoxy silane is selected from the group of alkoxy silanes of the formula R_n Si(OR'"'"')_4-n where n=1-3, R=aryl or alkyl and R'"'"'=C_1-3 alkyl.

5. The process of claim 1 wherein the alkoxy silane is selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.

6. The process of claim 1 wherein the alkoxy silane is selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl dimethoxy silane and methyl triethoxy silane.

7. The process of claim 1 wherein the copolymer is characterized by a tensile strength of at least 300 psig.

8. A process for the production of an amorphous propylene/1butene copolymers comprising:

reacting propylene and 1-butene monomers in the presence of a catalyst system comprising;

(a) a solid supported catalyst component is prepared by the method comprising;

(i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8;

0.5 to about 8;

3 in the absence of added electron donor; and

(ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8;

0.1 to about 8;

1.0.

(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50;

1 and about 500;

1.

(c) an alkoxy silane component of the formula R_n Si(OR'"'"')_4-n where n=1-3, R=aryl or alkyl and R'"'"'=C_1-3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20;

1 to about 45;

1;

said amorphous copolymer being characterized by a propylene content of 25 to 50 wt%, a 1-butene content of 75 to 50 wt% and a tensile strength of at least 300 psig.

9. The process of claim 8 wherein the propylene and 1-butene monomers are polymerized at a temperature of from 130°

F. to 150°

F.

10. The process of claim 8 wherein the propylene and 1-butene monomers are polymerized at pressure from 250 psig to 350 psig.

11. The process of claim 8 wherein the alkoxy silane is selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.

12. The process of claim 8 wherein the alkoxy silane is selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl dimethoxy silane and methyl triethoxy silane.

13. A copolymer comprising:

from 25 to 50 wt% propylene and from 75 to 50 wt% 1-butene characterized by a tensile strength of greater than 300 psig;

said copolymer containing no heptane insolubles and being further characterized by having no detectable heat of fusion.

14. The copolymer of claim 14 wherein the copolymer is produced by the process comprising:

reacting propylene and 1-butene monomers in the presence of a catalyst system comprising;

(a) a solid supported catalyst component is prepared by the method comprising;

(i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8;

0.5 to about 8;

3 in the absence of added electron donor; and

(ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8;

0.1 to about 8;

1.0.

(b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al/Ti ratio is between about 50;

1 and about 500;

1.

(c) an alkoxy silane component in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from 20;

1 to about 45;

1.

15. The copolymer of claim 14 wherein the copolymer is produced by polymerizing propylene and 1-butene monomers are polymerized at a temperature of from 130°

F. to 150°

F.

16. The copolymer of claim 14 wherein the copolymer is produced by polymerizing and 1-butene monomers are polymerized at pressure from 250 psig to 350 psig.

17. The copolymer of claim 14 wherein the copolymer is produced with an alkoxy silane selected from the group of alkoxy silanes of the formula R_n Si(OR'"'"')_4-n where n=1-3, R=aryl or alkyl and R'"'"'=C_1-3.

18. The copolymer of claim 14 wherein the copolymer is produced with an alkoxy silane selected from the group consisting of cyclohexyl methyl dimethoxy silane and phenyl triethoxy silane.

19. The copolymer of claim 14 wherein the copolymer is produced with an alkoxy silane selected from the group consisting of dimethyl diethoxy silane, dodecyl triethoxy silane, methyl phenyl diethoxy silane, dimethyl diisopropenoxy silane, methyl octyl dimethoxy silane and methyl triethoxy silane.