Patent US3689595A successfully refreshed from Google Patents.
US3689595A
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US
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High impact polypropylenes
Assignee: Phillips Petroleum Co
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Filing: 1970-04-28
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Granted: 1972-09-05
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Expires: 1990-04-28
Abstract
Abstract A high impact polypropylene having an improved low brittleness temperature and an increased Izod impact strength is produced by blending together (1) a mixed copolymer, produced by first forming blocks of propylene homopolymer in presence of which there is then polymerized unreacted propylene and added ethylene by continuing the polymerization reaction thus resulting in said mixed copolymer with (2) a resinous radial block copolymer obtained by sequentially polymerizing a monovinyl-substituted aromatic hydrocarbon and a conjugated diene, and subsequently treating polymer thus obtained with a polyfunctional treating agent to obtain said copolymer which is radial with respect to long branches which radiate from a nucleus formed by the polyfunctional compound. The mixed copolymer can be produced by either batch or continuous operation. When produced by continuous operation, it is improved as a high-impact resin by addition of the radial copolymer, which lowers brittleness temperature and increases Izod impact. The batch produced mixed copolymer, the properties of which are already attractive can be further improved with respect to reduction of brittleness temperature and increase of Izod impact by adding thereto the radial resin. An increase in flexural modulus of the mixed copolymer, for example, as produced by continuous operation, can be obtained by blending it with polypropylene as produced by a usual method. Mixed copolymer is also blended with the radial copolymer and with polypropylene to obtain an improved high impact polypropylene polymer. The radial block copolymer can also be polymodal.
Inventors
- 👤 J S Gwinn
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 18:37
CPC Classifications
C; C08; C08L; C08L23/00; C08L23/02; C08L23/10; C08F; C08F297/00; C08F297/06; C08F297/08; C08F297/083; C08L53/00; C08L2205/00; C08L2205/02; C08L2205/03; C08L23/14; C08L2308/00; C08L53/02; Y; Y10; Y10S; Y10S525/00; Y10S525/901; Y10S525/94
Claims Analysis
Total Claims: 10
Claim 1
Independent Claim
25 words
A composition according to claim 1 containing also a minor proportion of solid polypropylene based on said mixed copolymer whereby said properties are further improved.
Claim 2
Dependent Claim
682 words
A composition according to claim 1 wherein the mixed propylene-ethylene block copolymer is produced by a two-step polymerization process comprising a step in which propylene as the sole monomer is polymerized in the presence of liquid propylene in the absence of additional liquid diluent at a temperature within the range of 80* to 150* F. and a step in which ethylene is polymerized in the presence of liquid propylene in the absence of additional liquid diluent at a temperature within the range of -50* to 75* F., the step which is carried out second being performed in the presence of the polymer produced in the first, using a catalyst formed by mixing materials comprising a. a compound having the formula RnMXm, wherein R is selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, X is selected from the group consisting of hydrogen and a halogen, M is selected from the group consisting of aluminum, gallium, indium, and thallium, n is from 1 to 3, inclusive, m is from 0 to 2, inclusive, and the sum of m and n is equal to the the valence of the metal M, and b. a halide of a metal selected from the group consisting of metals of Groups IV-A, IV-B, V-B, VI-B, and VIII and the resinous, radial block copolymer is produced by a. contacting under polymerization conditions at a temperature up to about 250* F. a monovinyl-substituted aromatic hydrocarbon monomer containing from about eight to 18 carbon atoms per molecule with an organolithium polymerization initiator containing from about one to 20 carbon atoms per molecule wherein said monovinyl-substituted aromatic hydrocarbon monomer is employed in an amount to provide from about 40 to 100 weight percent of the total monovinyl-substituted aromatic hydrocarbon employed in preparing said copolymer wherein said initiator is employed in an amount to provide from about 0.01 to 0.2 parts by weight of initiator per 100 parts by weight of said monomer and continuing said contacting for a period of time sufficient to polymerize essentially all of said monovinyl-substituted aromatic hydrocarbon monomer; b. charging to the polymerization reaction product of step (a), in one or more increments, any remaining monovinyl-substituted aromatic hydrocarbon monomer representing from about 0 to 60 weight percent of said total monovinyl-substituted aromatic hydrocarbon monomer employed in preparing said copolymer, wherein for each incremental charge of monovinyl-substituted aromatic hydrocarbon monomer additional said organolithium initiator is provided in an amount from about 0.1 to 1.5 parts by weight of said initiator per 100 parts by weight of said incremental charge of monomer, wherein after each monomer and initiator charged a sufficient contacting time is allowed to permit essential complete polymerization of the newly added monomer, wherein the amount of initiator employed per 100 parts by weight of each incremental monomer charge of step (b) exceeds the amount of initiator employed in step (a) by at least 0.1 part of initiator per 100 parts of monomer by weight and wherein the total amount of said monovinyl-substituted aromatic hydrocarbon monomer employed in steps (a) and (b) comprises from about 70 to 95 weight percent of the total weight of said branched block copolymer based upon the total weight of all of the monomer employed; c. charging, to the polymerization reaction product of steps (a) and (b), a conjugated diene monomer containing from about four to 12 carbon atoms per molecule and polymerizing to essential completion said diene monomer in the presence of said reaction product to form a block copolymer, and wherein the amount of said diene monomer comprises from about 30 to 5 weight percent of the total weight of said branched block copolymer based upon the total weight of all of the monomers employed; and d. charging to the polymerization reaction product of step (c) a polyfunctional treating agent capable of reacting with terminal lithium atoms on a preformed polymer to form a branched polymer wherein saId polyfunctional treating agent is employed in an amount to provide from about 0.05 to 2 equivalents of said polyfunctional treating agent per gram atom of lithium employed in said polymerization process.
Claim 3
Dependent Claim
659 words
A composition according to claim 1 wherein the mixed propylene-ethylene block copolymer is produced by polymerizing ethylene in the presence of liquid propylene in the absence of additional liquid diluent at a temperature within the range of -50* to 75* F., using a catalyst formed by mixing materials comprising a. a compound having the formula RnMXm, wherein R is selected from the group consisting of alkyl, cycloalkyl and aryl radicals, X is selected from the group consisting of hydrogen and a halogen, M is selected from the group consisting of aluminum, gallium, indium and thallium, n is from 1 to 3, inclusive, m is from 0 to 2, inclusive, and the sum of m and n is equal to the valence of the metal M, and b. a halide of a metal selected from the group consisting of metal of Groups IV-A, IV-B, V-B, VI-B and VIII removing unpolymerized ethylene from the reaction mixture, and polymerizing in the presence of liquid propylene at least a portion of the remaining propylene at a temperature within the range of 80* to 150* F. in the presence of the polymer produced in the first step and said resinous, radial block copolymer is produced by a. contacting, under polymerization conditions at a temperature up to about 250* F., a monovinyl-substituted aromatic hydrocarbon monomer, containing from about eight to 18 carbon atoms per molecule, with an organolithium polymerization initiator containing from about one to 20 carbon atoms per molecule, wherein said monovinyl-substituted aromatic hydrocarbon monomer is employed in an amount to provide from about 40 to 90 weight percent of the total monovinyl-substituted aromatic hydrocarbon employed in preparing said copolymer, wherein said initiator is employed in an amount to provide from about 0.01 to 0.2 parts by weight of initiator per 100 parts by weight of said monomer and continuing said contacting for a period of time sufficient to polymerize essentially all of said monovinyl-substituted aromatic hydrocarbon monomer; b. charging to the polymerization reaction product of step (a), in one or more increments, the remaining monovinyl-substituted aromatic hydrocarbon monomer representing from about 10 to 60 weight percent of said total monovinyl-substituted aromatic hydrocarbon monomer employed in preparing said copolymer, wherein for each incremental charge of monovinyl-substituted aromatic hydrocarbon monomer additional said organolithium initiator is provided in an amount from about 0.1 to 1.5 parts by weight of said initiator per 100 parts by weight of said incremental charge of monomer, wherein after each monomer and initiator charged a sufficient contacting time is allowed to permit essential complete polymerization of the newly added monomer, wherein the amount of initiator employed per 100 parts by weight of each incremental monomer charge of step (b) exceeds the amount of initiator employed in step (a) by at least 0.1 part of initiator per 100 parts of monomer by weight and wherein the total amount of said monovinyl-substituted aromatic hydrocarbon monomer employed in steps (a) and (b) comprises from about 70 to 95 weight percent of the total weight of said branched block copolymer based upon the total weight of all of the monomers employed; c. charging to the polymerization reaction product of step (b) a conjugated diene monomer containing from about four to 12 carbon atoms per molecule and polymerizing to essential completion said diene monomer in the presence of said reaction product to form a block copolymer, and wherein tHe amount of said diene monomer comprises from about 30 to 5 weight percent of the total weight of said branched block copolymer based upon the total weight of all of the monomers employed; and d. charging to the polymerization reaction product of step (c) a polyfunctional treating agent capable of reacting with terminal lithium atoms on a preformed polymer to form a branched polymer wherein said polyfunctional treating agent is employed in an amount to provide from about 0.05 to 2 equivalents of said polyfunctional treating agent per gram atom of lithium employed in said polymerization process.
Claim 4
Independent Claim
183 words
A method for improving the low brittleness temperature and impact resistance properties of a mixed propylene-ethylene block copolymer containing at least 75 weight percent of polypropylene, said mixed propylene-ethylene copolymer being produced in a two-step process yielding a solid in which in one-step propylene is homopolymerized and in the other step ethylene is copolymerized with propylene, which comprises blending it together with an amount of a solid polymodal, resinous, branched block copolymer prepared by treatment of a resinous block polymer comprising from about 70 to 95 weight percent polymerized monovinyl-substituted aromatic hydrocarbon monomer containing from about 8 to 18 carbon atoms per molecule and from about 30 to 5 weight percent polymerized conjugated diene monomer containing from about four to 12 carbon atoms per molecule; said polymer having a melt flow in the range of about 0.5 to 20.0 as determined by ASTM D-1238-65T, condition G with a polyfunctional treating agent to add branches to said resinous polymer, thus forming therewith said radial block copolymer, effective to appreciably improve at least one one of its properties such as Izod impact or brittleness temperature.
Claim 5
Dependent Claim
150 words
A method according to claim 5 wherein the mixed propylene-ethylene block copolymer contains at least about 75 weight percent of propylene obtained by homopolymerization and from about 10 to about 25 percent of propylene-ethylene copolymer obtained by copolymerization of an ethylene-propylene mixture, the total mixed copolymer containing from about 5 to about 15 weight percent ethylene and the remainder being propylene and wherein the polymodal, resinous, branched block copolymer contains from about 70 to 95 weight percent polymerized monovinyl-substituted aromatic hydrocarbon monomer containing from about eight to 18 carbon atoms per molecule and from about 30 to 5 weight percent polymerized conjugated diene monomer containing from about four to 12 carbon atoms per molecule, said polymodal, resinous, branched block copolymer being formed by first forming segments by multiple additions of monovinyl-substituted aromatic hydrocarbon monomer and initiator, subsequently adding conjugated diene to form polymer and then adding a polyfunctional treating agent.
Claim 6
Dependent Claim
18 words
A composition according to claim 2 wherein the mixed propylene-ethylene block copolymer results from a continuous production thereof.
Claim 7
Dependent Claim
38 words
A composition according to claim 1 wherein the blend contains at least about 65 percent of the mixed copolymer, the remainder being at least the resinous, radial block copolymer present in a minimum of at least 2 percent.
Claim 8
Dependent Claim
48 words
A composition according to claim 1 wherein the blend contains at least about 70 weight percent of the mixed copolymer, the remainder being composed of the resinous, radial block copolymer and polypropylene and the radial ingredient is present in a content of about 5 to about 10 percent.
Claim 9
Dependent Claim
12 words
A composition according to claim 8 wherein the radial copolymer is polymodal.
Claim 10
Dependent Claim
12 words
A composition according to claim 1 wherein the radial copolymer is polymodal.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1975-09-05 | 1976-03-06 | 1976-09-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1979-09-05 | 1980-03-06 | 1980-09-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1983-09-05 | 1984-03-06 | 1984-09-05 | $7700.00 | Window Closed / Lapsed |