US4359561A — High tear strength polymers

Claim 1

Independent Claim 399 words

A continuous process for making, in the gas phase and at a level of productivity of at least 700 pounds of polymer per pound of total catalyst, heterogeneous ethylene based hydrocarbon polymers having, in film form, high Elmendorf tear strength values which comprises interpolymerizing ethylene with C a and C b monomers maintained throughout the process in the molar ratios in said gas phase of C a /C 2 of about 0.1 to 0.9 and C b /C 2 of about 0.015 to 0.2 wherein the C a monomer is selected from propylene, butene-1 and mixtures thereof and the C b monomer is one or more C 5 to C 8 alpha monoolefins which contain no branching closer than the fourth carbon atom, in a reaction zone having a pressure of about 50 to 1000 psi and a temperature of about 65° to 105° C., with an activated catalyst formed from an activator compound and a precursor compound, said activator compound having the structure Al(R").sub.c X'.sub.d H.sub.e wherein X' is Cl or OR'", R" and R'" are the same or different and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c+d+e=3, said precursor compound having the formula Mg.sub.m Ti.sub.l (OR).sub.n X.sub.p (ED).sub.q wherein ED is an electron donor compound which is an organic compound which is liquid at 25° C. at atmospheric pressure, and in which the titanium compound and magnesium compound used to form said precursor compound are partially or completely soluble, m is ≧0.5 to ≦56 n is 0, 1 or 2 p is ≧2 to ≦116 q is ≧2 to ≦85 R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I and mixtures thereof, and said precursor compound being impregnated in porous carrier material so as to provide a weight ratio of about 0.033 to 0.33 parts of precursor compound to one part of said carrier material, and said precursor compound being either completely activated in one step outside of said reaction zone in the absence of solvent, or is first partially activated outside of said reaction zone in the presence or absence of solvent and then completely activated inside of said reaction zone.

Claim 2

Dependent Claim 399 words

A continuous process for making, in the gas phase and at a level of productivity of at least 700 pounds of polymer per pound of total catalyst, heterogeneous ethylene based hydrocarbon polymers having, in film form, high Elmendorf tear strength values which comprises interpolymerizing ethylene with C a and C b monomers maintained throughout the process in the molar ratios in said gas phase of C a /C 2 of about 0.1 to 0.9 and C b /C 2 of about 0.015 to 0.2 wherein the C a monomer is selected from propylene, butene-1 and mixtures thereof and the C b monomer is one or more C 5 to C 8 alpha monoolefins which contain no branching closer than the fourth carbon atom, in a reaction zone having a pressure of about 50 to 1000 psi and a temperature of about 65° to 105° C., with an activated catalyst formed from an activator compound and a precursor compound, said activator compound having the structure Al(R").sub.c X'.sub.d H.sub.e wherein X' is Cl or OR'", R" and R'" are the same or different and are C 1 to C 14 saturated hydrocarbon radicals, d is 0 to 1.5, e is 1 or 0 and c+d+e=3, said precursor compound having the formula Mg.sub.m Ti.sub.l (OR).sub.n X.sub.p (ED).sub.q wherein ED is an electron donor compound which is an organic compound which is liquid at 25° C. at atmospheric pressure, and in which the titanium compound and magnesium compound used to form said precursor compound are partially or completely soluble, m is ≧0.5 to ≦56 n is 0, 1 or 2 p is ≧2 to ≦116 q is ≧2 to ≦85 R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical or COR' wherein R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is selected from the group consisting of Cl, Br, I and mixtures thereof, and said precursor compound being impregnated in porous carrier material so as to provide a weight ratio of about 0.033 to 0.33 parts of precursor compound to one part of said carrier material, and said precursor compound being either completely activated in one step outside of said reaction zone in the absence of solvent, or is first partially activated outside of said reaction zone in the presence or absence of solvent and then completely activated inside of said reaction zone.

Claim 3

Dependent Claim 12 words

A process as in claim 1 in which C a is propylene.

Claim 4

Dependent Claim 12 words

A process as in claim 1 in which C a is butene-1.

Claim 5

Dependent Claim 14 words

A process as in claim 2 or 3 in which C b is hexene-1.

Claim 6

Dependent Claim 57 words

A process as in claim 4 in which said C a and C b monomers are used in such amounts so as to provide said polymers which contain said monomers in a C a /C 2 molar ratio of about 0.006 to 0.09 and in a C b /C 2 molar ratio of about 0.003 to 0.07.

Claim 7

Dependent Claim 36 words

A process as in claim 5 in which said C a and C b monomers are used in such amounts as to provide said polymers which have a Branch Chain Factor of about 0.2 to 0.8.

Claim 8

Dependent Claim 18 words

A process as in claim 6 in which said polymer has a density of about 0.91 to 0.94.

Claim 9

Dependent Claim 37 words

A process as in claim 7 in which said polymer has a melt index of about 0.5 to 5.0, a melt flow ratio of about 22 to 36 and a bulk density of about 14 to 31.

Claim 10

Dependent Claim 12 words

A process as in claim 5 in which C a is propylene.

Claim 11

Dependent Claim 12 words

A process as in claim 5 in which C a is butene-1.

Claim 12

Dependent Claim 12 words

A process as in claim 8 in which C a is propylene.

Claim 13

Dependent Claim 12 words

A process as in claim 8 in which C a is butene-1.

Claim 14

Dependent Claim 23 words

A process as in claim 1 in which said carrier material is selected from the group consisting of oxides of silicon and/or aluminum.

Claim 15

Dependent Claim 13 words

A process as in claim 13 in which said carrier material is silica.

Claim 16

Dependent Claim 27 words

A process as in claim 1 in which m is ≧1.5 to ≦5, n is 0, p is ≧6 to ≦14 and q is ≧4 to ≦11.

Claim 17

Dependent Claim 11 words

A process as in claim 15 in which X is Cl.

Claim 18

Dependent Claim 33 words

A process as in claim 16 in which said electron donor is selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones.

Claim 19

Dependent Claim 13 words

A process as in claim 17 in which said electron donor is tetrahydrofuran.

Claim 20

Dependent Claim 27 words

A process as in claim 1 in which said precursor compound is completely activated in the absence of solvent prior to feeding it to said reaction zone.

Claim 21

Dependent Claim 29 words

A process as in claim 19 in which ≧10 to ≦400 mols of said activator compound per mol of Ti in said precursor compound are used in said activation.

Claim 22

Dependent Claim 30 words

A process as in claim 20 in which about 10 to 100 mols of said activator compound per mol of Ti in said precursor compound are used in said activation.

Claim 23

Dependent Claim 116 words

A process as in claim 1 in which (a) said precursor compound is partially activated, prior to feeding it to said reaction zone, with >0 to ≦10 mols of said activator compound per mol of Ti in said precursor compound in the presence or absence of solvent for said precursor compound, (b) where said precursor compound is thus partially activated in the presence of said solvent said solvent is removed therefrom by drying at a temperature between 20° and 80° C., and (c) the resulting partially activated precursor compound is fed to said reaction zone and completely activated therein with ≧10 to ≦400 mols of said activator compound per mol of Ti in said precursor compound.

Claim 24

Dependent Claim 31 words

A process as in claim 22 in which said partial activation is conducted with about 4 to 8 mols of said activator compound per mol of Ti in said precursor compound.

Claim 25

Dependent Claim 31 words

A process as in claim 23 in which said complete activation is conducted with about 15 to 60 mols of said activator compound per mol of Ti in said precursor compound.

Claim 26

Dependent Claim 56 words

A process as in claim 1 in which unreacted monomer is removed from said reaction zone, passed through heat exchanger means external of said reaction zone to remove heat of reaction therefrom, and recycled to said reaction zone while maintaining the temperature of said recycled monomer above the dew point of the mixture of monomers therein.

Claim 27

Dependent Claim 28 words

A process as in claim 25 in which the temperature of said mixture of monomers is maintained at least about 3° to 10° C. above said dew point.

Claim 28

Dependent Claim 29 words

A process as in claim 26 in which said polymers are made at a level of productivity of at least 1000 pounds of polymer per pound of total catalyst.

Claim 29

Dependent Claim 28 words

A process as in claim 27 in which said polymers are made at a level of productivity of at least 2800 pounds of polymer per pound of catalyst.

Claim 30

Dependent Claim 15 words

A process as in claim 1 which is conducted in a fluid bed reaction process.

Claim 31

Dependent Claim 33 words

A process as in claim 29 which is conducted at a mass gas flow rate through the fluidized bed used in said process of about 1.5 to about 10 times G mf .

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1985-11-15	1986-05-17	1986-11-16	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1989-11-15	1990-05-17	1990-11-16	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1993-11-15	1994-05-17	1994-11-16	$7700.00	Window Closed / Lapsed

High tear strength polymers

Abstract

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