US4368302A — Polymerization process and products therefrom

Claim 1

Independent Claim 237 words

A process for polymerising ethylene or a mixture of ethylene with up to 40 wt % (based on total monomer) of other 1-olefinic monomer comprising (a) supporting chromium oxide, or a compound calcinable thereto, on a refractory oxide support material, (b) adding one or more tetravalent titanium compounds selected from (1) TiO 2 , (2) TiOCl 2 , (3) titanium acetyl acetonate compounds, (4) alkanolamine titanates and (5) compounds having the general formula Ti(OR) m X n , wherein m+n is 4, m is zero or an integer from 1 to 4, R is an organic hydrocarbon group and when the titanium compound contains more than one R or Y group the groups may be the same of different (c) heating the product under such conditions that an active polymerisation catalyst is formed, (d) and contacting the monomer with the active polymerisation catalyst in the presence of (6) one or more organometallic compounds having the general formular MR 2 p Y q-p wherein M is a metal of groups 1A, 2A, 2B or 3A of the Periodic Table (Mendeleef), R 2 is a hydrocarbon group containing 1 to 10 carbon atoms, Y is hydrogen or halogen, q is the valency of M, p is an integer from 1 to q inclusive and when the organometallic compound contains more than one R 2 or Y group they may be the same or different, and (7) a polyene modifier.

Claim 2

Dependent Claim 237 words

A process for polymerising ethylene or a mixture of ethylene with up to 40 wt % (based on total monomer) of other 1-olefinic monomer comprising (a) supporting chromium oxide, or a compound calcinable thereto, on a refractory oxide support material, (b) adding one or more tetravalent titanium compounds selected from (1) TiO 2 , (2) TiOCl 2 , (3) titanium acetyl acetonate compounds, (4) alkanolamine titanates and (5) compounds having the general formula Ti(OR) m X n , wherein m+n is 4, m is zero or an integer from 1 to 4, R is an organic hydrocarbon group and when the titanium compound contains more than one R or Y group the groups may be the same of different (c) heating the product under such conditions that an active polymerisation catalyst is formed, (d) and contacting the monomer with the active polymerisation catalyst in the presence of (6) one or more organometallic compounds having the general formular MR 2 p Y q-p wherein M is a metal of groups 1A, 2A, 2B or 3A of the Periodic Table (Mendeleef), R 2 is a hydrocarbon group containing 1 to 10 carbon atoms, Y is hydrogen or halogen, q is the valency of M, p is an integer from 1 to q inclusive and when the organometallic compound contains more than one R 2 or Y group they may be the same or different, and (7) a polyene modifier.

Claim 3

Dependent Claim 15 words

A process as claimed in claim 1 wherein the refractory oxide support material is silica.

Claim 4

Dependent Claim 30 words

A process as claimed in claim 1 wherein the titanium compound has the general formula (RO) 4 Ti wherein R represents an alkyl group containing 1 to 6 carbon atoms.

Claim 5

Dependent Claim 26 words

A process as claimed in claim 1 wherein the heating in step (c) is carried out at a temperature in the range 400° to 900° C.

Claim 6

Dependent Claim 15 words

A process as claimed in claim 1 wherein the organometallic compound is an aluminium trialkyl.

Claim 7

Dependent Claim 17 words

A process as claimed in claim 1 wherein the organometallic compound is triethyl aluminium or triisobutyl aluminium.

Claim 8

Dependent Claim 51 words

A process as claimed in claim 1 wherein the polymerisation is carried out by contacting the monomer with a suspension or a fluidised bed of the catalyst particles in a fluid medium under conditions such tha the polymeric 1-olefin forms as solid particles suspended in or fluidised in the fluid medium.

Claim 9

Dependent Claim 22 words

A process as claimed in claim 1 wherein the polyene modifier is a C 1 to C 20 conjugated or non-conjugated polyene.

Claim 10

Dependent Claim 21 words

A process as claimed in claim 1 wherein the polyene is butadiene, isoprene, 1,5-hexadiene, 1,4-hexadiene, myrcene, cyclopentadiene, dicyclopentadiene or ethylidene norbornene.

Claim 11

Dependent Claim 28 words

A process as claimed in claim 1 wherein the quantity of polyene employed lies in the range 0.1 to 50 parts by weight per unit weight of catalyst.

Claim 12

Dependent Claim 106 words

A process for polymerizing ethylene or a mixture of ethylene with up to 40 wt.% (based on total monomer) of other 1-olefinic monomer as defined in claim 1 wherein the concentration of tetravalent titanium compound in the product resulting from step (b) is in the range of from about 0.05 to 20 wt.%, the quantity of organometallic compound employed in step (d) is from about 0.1 to 100 wt.% based on the total weight of the catalyst, and the quantity of polyene modifier employed in step (d) is in the range of from about 0.1 to 50 parts by weight per unit weight of the catalyst.

Claim 13

Dependent Claim 213 words

A catalyst for polymerising 1-olefins prepared by (a) supporting chromium oxide, or a compound calcinable thereto, on a refractory oxide support material, (b) adding one or more tetravalent titanium compounds selected from (1) TiO 2 , (2) TiOCl 2 , (3) titanium acetyl acetonate compounds, (4) alkanolamine titanates and (5) compounds having the general formula Ti(OR) m X n , wherein m+n is 4, m is zero or an integer from 1 to 4, R is an organic hydrocarbon group and when the titanium compound contains more than one R or X group the groups may be the same or different, (c) heating the product under such conditions that an active polymerisation catalyst is formed, (d) and adding to the active polymerisation catalyst (6) one or more organometallic compounds having the general formula MR 2 p Y q-p wherein M is a metal of groups 1A, 2A, 2B or 3A of the Periodic Table (Mendeleef), R 2 is a hydrocarbon group containing 1 to 10 carbon atoms, Y is hydrogen or halogen, q is the valency of M, p is an integer from 1 to q inclusive and when the organometallic compound contains more than one R 2 or Y group they may be the same or different, and (7) a polyene modifier.

Claim 14

Dependent Claim 213 words

A catalyst for polymerising 1-olefins prepared by (a) supporting chromium oxide, or a compound calcinable thereto, on a refractory oxide support material, (b) adding one or more tetravalent titanium compounds selected from (1) TiO 2 , (2) TiOCl 2 , (3) titanium acetyl acetonate compounds, (4) alkanolamine titanates and (5) compounds having the general formula Ti(OR) m X n , wherein m+n is 4, m is zero or an integer from 1 to 4, R is an organic hydrocarbon group and when the titanium compound contains more than one R or X group the groups may be the same or different, (c) heating the product under such conditions that an active polymerisation catalyst is formed, (d) and adding to the active polymerisation catalyst (6) one or more organometallic compounds having the general formula MR 2 p Y q-p wherein M is a metal of groups 1A, 2A, 2B or 3A of the Periodic Table (Mendeleef), R 2 is a hydrocarbon group containing 1 to 10 carbon atoms, Y is hydrogen or halogen, q is the valency of M, p is an integer from 1 to q inclusive and when the organometallic compound contains more than one R 2 or Y group they may be the same or different, and (7) a polyene modifier.

Claim 15

Dependent Claim 82 words

A catalyst as defined in claim 12, wherein the concentration of tetravalent titanium compound resulting from step (b) is in the range of from about 0.05 to 20 wt.%, the quantity of organometallic compound employed in step (d) is from about 0.1 to 100 wt.% based on the total weight of the catalyst, and the quantity of polyene modifier employed in step (d) is in the range of from about 0.1 to 50 parts by weight per unit weight of the catalyst.

Claim 16

Dependent Claim 54 words

A catalyst as defined in claim 13 wherein the metal of said organometallic compound is lithium, sodium, beryllium, magnesium, calcium, zinc, cadmium, boron, aluminum or gallium and the organo- portion of said compound is one or more alkyl groups, and said polyene modifier is a C 1 to C 20 conjugated or non-conjugated diene.

Claim 17

Dependent Claim 32 words

A catalyst as defined in claim 13 wherein said organometallic compound is dibutyl magnesium, triethyl boron, triethyl aluminum, and said polyene is butadiene, isoprene, 1,5-hexadiene, 1,4-hexadiene, myrcene, cyclopentadiene, dicyclopentadiene, or ethylidene norbornene.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-01-10	1986-07-12	1987-01-11	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-01-10	1990-07-12	1991-01-11	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-01-10	1994-07-12	1995-01-11	$7700.00	Window Closed / Lapsed

Polymerization process and products therefrom

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