US4960593A
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Process for preparing thermally stable olefinic polymers
Assignee: Himont Inc
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Filing: 1989-03-31
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Granted: 1990-10-02
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Expires: 2009-03-31
Abstract
Abstract Thermally stable olefin polymers are obtained by addition, before or during polymerization, or after polymerization is substantially complete, but before quenching the catalyst, which terminates the polymerization reaction, of stabilizers of the HALS type ("Hindered Amine Light Stabilizer") of monomeric or oligomeric type, containing in the molecule one or more substituted piperidyl groups having formula: ##STR1## wherein R1 are the same or different from each other and are C 1 -C 4 alkyl radicals, tetramethylpiperidyl radicals, or the alkyl radicals, together with the piperidyl carbon atom to which they are bonded, form a C 5 -C 9 cycloalkyl radical; R 2 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals, C 7 -C 18 aralkyl radicals, or said alkyl radicals together with the piperidyl carbon atom to which they are bonded, are a C 5 -C 10 cycloalkyl radical; R 3 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals or C 7 -C 18 aralkyl radicals; R 4 is hydrogen, a C 1 -C 8 alkyl radical or a benzyl radical; Z is hydrogen or an organic radical. Suitable organic radicals include C 1 -C 18 alkyl; C 1 -C 12 alkylene; C 3 -C 12 alkenyl; C 3 -C 5 alkenyl; C 7 -C 18 aralkyl; C 2 -C 4 acyl; C 2 -C 18 alkanoyl; C 3 -C 18 alkoxyalkyl; C 3 -C 18 alkenoyl; oxyl; cyanomethyl, and xylylenyl radicals; a radical having valence from 1 to 4 and containing from 1 to 4 hydroxyl groups and, optionally, containing ether, ester, or heterocyclic groups, all the valences of this radical being bonded to the nitrogen of the piperidyl rings; a bivalent radical containing one or more ester or amide groups, and a radical ##STR2## wherein R 5 and R 6 are hydrocarbyl radicals. Preferably Z is a C 1 -C 12 alkyl, C 3 -C 8 alkenyl, C 7 -C 11 aralkyl, or a bivalent radical containing one or more ester groups wherein the two valences of said radicals are bonded to piperidyl rings.
Inventors
- 👤 Franco Sevini
- 👤 Luciano Noristi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 16:17
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
355 words
A process for the manufacture of thermally stable, alpha-olefin polymers, which polymers are obtained by means of catalysts prepared by reaction of an aluminum alkyl compound with a solid component selected from a product comprising a titanium compound and a magnesium dihalide in active form, and a product comprising a tetravalent titanium compound supported onto a trivalent titanium halide having a surface area greater than 50 m 2/ g, which process consists in adding before or during polymerization or after polymerization is substantially complete, but before quenching the catalyst, a stabilizer containing in the molecule one or more substituted piperidyl groups having the following general formula: wherein R1 are the same or different from each other and are C 1 -C 4 alkyl radicals, tetramethylpiperidyl radicals, or the alkyl radicals, together with the piperidyl carbon atom to which they are bonded, form a C 5 -C 9 cycloalkyl radical; R 2 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals, C 7 -C 18 aralkyl radicals, or said alkyl radicals together with the piperidyl carbon atom to which they are bonded, are a C 5 -C 10 cycloalkyl radical; R 3 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals or C 7 -C 18 aralkyl radicals; R 4 is hydrogen, a C 1 -C 8 alkyl radical or a benzyl radical; Z is hydrogen or C 1 -C 18 alkyl; C 1 -C 12 alkylene; C 3 -C 12 alkenyl; C 3 -C 5 alkynyl; C 7 -C 18 aralkyl; C 2 -C 4 acyl; C 2 -C 18 alkanoyl; C 3 -C 18 alkoxyalkyl; C 3 -C 18 alkenoyl; oxyl; cyanomethyl, and xylylenyl radicals; a radical having valence from 1 to 4 and containing from 1 to 4 hydroxyl groups and, optionally, containing ether, ester, or heterocyclic groups, all the valences of this radical being bonded to the nitrogen of the piperidyl rings; a bivalent radical containing one or more ester or amide groups, and a radical ##STR78## wherein R 5 and R 6 are hydrocarbyl radicals.
Claim 2
Dependent Claim
355 words
A process for the manufacture of thermally stable, alpha-olefin polymers, which polymers are obtained by means of catalysts prepared by reaction of an aluminum alkyl compound with a solid component selected from a product comprising a titanium compound and a magnesium dihalide in active form, and a product comprising a tetravalent titanium compound supported onto a trivalent titanium halide having a surface area greater than 50 m 2/ g, which process consists in adding before or during polymerization or after polymerization is substantially complete, but before quenching the catalyst, a stabilizer containing in the molecule one or more substituted piperidyl groups having the following general formula: wherein R1 are the same or different from each other and are C 1 -C 4 alkyl radicals, tetramethylpiperidyl radicals, or the alkyl radicals, together with the piperidyl carbon atom to which they are bonded, form a C 5 -C 9 cycloalkyl radical; R 2 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals, C 7 -C 18 aralkyl radicals, or said alkyl radicals together with the piperidyl carbon atom to which they are bonded, are a C 5 -C 10 cycloalkyl radical; R 3 are the same or different from each other and are hydrogen, C 1 -C 18 alkyl radicals or C 7 -C 18 aralkyl radicals; R 4 is hydrogen, a C 1 -C 8 alkyl radical or a benzyl radical; Z is hydrogen or C 1 -C 18 alkyl; C 1 -C 12 alkylene; C 3 -C 12 alkenyl; C 3 -C 5 alkynyl; C 7 -C 18 aralkyl; C 2 -C 4 acyl; C 2 -C 18 alkanoyl; C 3 -C 18 alkoxyalkyl; C 3 -C 18 alkenoyl; oxyl; cyanomethyl, and xylylenyl radicals; a radical having valence from 1 to 4 and containing from 1 to 4 hydroxyl groups and, optionally, containing ether, ester, or heterocyclic groups, all the valences of this radical being bonded to the nitrogen of the piperidyl rings; a bivalent radical containing one or more ester or amide groups, and a radical ##STR78## wherein R 5 and R 6 are hydrocarbyl radicals.
Claim 3
Dependent Claim
52 words
A process according to claim 1, wherein Z in the general formula I is a C 1 -C 12 alkyl, C 3 -C 8 alkenyl, C 7 -C 11 aralkyl, or a bivalent radical containing one or more ester groups wherein the two valences of said radical are bonded to piperidyl rings.
Claim 4
Dependent Claim
80 words
A process according to claim 1, wherein the stabilizer has formula: ##STR79## wherein n is a whole number from 2 to 100; R 1 , R 2 , R 3 , R 4 and Z have the same meaning as in claim 1; X is a bivalent organic radical; Y is a direct chemical bond, or a bivalent aliphatic, cycloaliphatic, aromatic or heterocyclic organic radical containing N or O, S, P atoms in the chain or in the heterocyclic ring.
Claim 5
Dependent Claim
43 words
A process according to claim 3 wherein the stabilizer has formula: ##STR80## wherein: n is a whole number from 2 to 20; Z is hydrogen and R is ##STR81## or ##STR82## radical; wherein R 5 is a C 1 -C 10 alkyl radical.
Claim 6
Dependent Claim
28 words
A process according to claim 4 wherein R 5 in formula XXIV of the stabilizer is a --C(CH 3 ) 2 --CH 2 --C(CH 3 ) 3 radical.
Claim 7
Dependent Claim
41 words
A process according to claim 3 wherein the stabilizer has formula: ##STR83## wherein n is a whole number comprised from 2 to 20, Z is hydrogen and Y is a direct chemical bond or a radical --CH 2 --CH 2 --.
Claim 8
Dependent Claim
121 words
A process according to claim 1, wherein the stabilizer has formula: ##STR84## wherein n is a whole number from 2 to 100; R 1 , R 2 , R 3 , R 4 have the same meaning as in claim 1; Z is a C 1 -C 12 alkylene radical or a bivalent radical containing one or more ester or amide groups; W is a direct chemical bond or a bivalent organic radical, --N--R radical (wherein R is hydrogen or a C 1 -C 18 alkyl radical), or --O --; Y is a direct chemical bond, or a bivalent aliphatic, cycloaliphatic, aromatic or heterocyclic organic radical containing N, or O, S, P atoms in the chain or in the heterocyclic ring.
Claim 9
Dependent Claim
22 words
A process according to claim 7 wherein the stabilizer has formula: ##STR85## wherein n is a whole number from 2 to 20.
Claim 10
Dependent Claim
22 words
A process according to claim 7 wherein the stabilizer has formula: ##STR86## wherein n is a whole number from 2 to 20.
Claim 11
Dependent Claim
55 words
A process according to claim 1, wherein the stabilizer has formula: ##STR87## wherein n, Y, R 1 , R 2 , R 3 and R 4 have the same meaning as in claim 1; Z is a C 1 -C 12 alkylene radical or a bivalent radical containing one or more ester or amide groups.
Claim 12
Dependent Claim
22 words
A process according to claim 10 wherein the stabilizer has formula: ##STR88## wherein n is a whole number from 2 to 20.
Claim 13
Dependent Claim
48 words
A process according to claim 1, wherein the stabilizer has formula: ##STR89## wherein R 1 , R 2 , R 3 and Z have the same meaning as in claim 1; X is a bivalent radical or a bivalent radical containing one or more ester or amide groups.
Claim 14
Dependent Claim
20 words
A process according to claim 12 wherein the stabilizer has formula: ##STR90## wherein Z is hydrogen or a methyl radical.
Claim 15
Dependent Claim
16 words
A process according to claim 12 wherein the stabilizer has formula: ##STR91## wherein Z is hydrogen.
Claim 16
Dependent Claim
44 words
A process according to claim 1, wherein the stabilizer has formula: ##STR92## wherein Z R 1 and R 2 have the same meaning as in claim 1; R is an alkyl, alkenyl or phenyl radical; n is a whole number from 1 to 3.
Claim 17
Dependent Claim
25 words
A process according to claim 15 wherein the stabilizer has formula: ##STR93## wherein L is H, halogen, or a C 1 -C 4 alkyl radical.
Claim 18
Dependent Claim
74 words
A process according to claim 1, wherein the stabilizer has formula: ##STR94## wherein Q is a bivalent organic radical, such as a C 1 -C 12 alkylene or phenylene radical, or a radical having fromula ##STR95## W is a substituted piperidylamino radical; R is H, a C 1 -C 18 alkyl, or a substituted piperidyl radical. y is 1 or zero x and m are 1, 2 or 3 n is 2 or 3
Claim 19
Dependent Claim
112 words
A process according to claim 17 wherein the stabilizer has general formula: ##STR96## wherein: R 5 is hydrogen, C 1 -C 18 alkyl, or a substituted piperidyl radical; R 6 is hydrogen, a C 1 -C 18 alkyl radical or a radical --(CH 2 )n--Y wherein n is a whole number from 1 to 12, Y is a --OH or a OR group, R being as hereinafter defined, or a ##STR97## group, wherein R is a C 1 -C 18 alkyl radical, R' is a C 1 -C 2 alkyl radical, Q is a radical --CH 2 --CH 2 -- or --CH 2 --CH 2 --CH 2 -- and Z is hydrogen
Claim 20
Dependent Claim
39 words
A process according to claim 18, wherein in the stabilizer of formula XXXII R 5 is hydrogen, R 6 is an alkyl radical --C 4 H 9 , Q is a radical --CH 2 --CH 2 --CH 2 --.
Claim 21
Dependent Claim
25 words
A process according to claim 1 wherein the stabilizer is added in an amount ranging between 0.01 and 1% by weight, referred to the polymer.
Claim 22
Dependent Claim
43 words
A process according to claim 1 wherein the alpha-olefin polymers are obtained using stereospecific catalysts comprising the reaction product of an aluminum-alkyl compound with catalytic components comprising a titanium compound and an electron-donor compound, supported on a magnesium dihalide in the active form.
Claim 23
Dependent Claim
48 words
The process according to claim 1 wherein the alpha-olefin polymers are selected from the group consisting of crystalline linear high density polyethylene, low density polyethylene, polypropylene, propylene-ethylene copolymers containing prevailing amounts of propylene, high impact polypropylene, polybutene and poly(4-methyl-1-pentene); and elastomeric ethylene-propylene copolymers, optionally containing a diene monomer.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1993-10-01 | 1994-04-02 | 1994-10-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-10-01 | 1998-04-02 | 1998-10-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-10-01 | 2002-04-02 | 2002-10-02 | $7700.00 | Window Closed / Lapsed |