Patent US3862265A successfully refreshed from Google Patents.
US3862265A
Expired / Lapsed
US
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Polymers with improved properties and process therefor
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1972-04-03
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Granted: 1975-01-21
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Expires: 1992-04-03
Abstract
Abstract Modified polymers, praticularly polyolefins having improved flow and in some instances improved adhesion properties over that of a polymeric, e.g. polyolefin, base stock used as a starting material, are produced by a controlled reaction often involving degradation in an extruder, in which an initiator is injected under conditions of either maximum distribution or intensive mixing wherein appreciable rheological, i.e., molecular weight distribution, changes in said base polymer occur. In some embodiments monomers are also grafted to said base stock, during said degradation process. In such instances, exceptional, novel, grafted polymers with high melt flow properties and other useful properties are obtained.
Inventors
- 👤 Robert A Steinkamp
- 👤 Thomas J Grail
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 13:06
CPC Classifications
C; C08; C08F; C08F255/00; B; B29; B29B; B29B7/00; B29B7/30; B29B7/34; B29B7/38; B29B7/40; B29B7/42; B29B7/421; B29B7/428; B29B7/429; B29B7/58; B29B7/72; B29B7/726; B29B7/80; B29B7/82; B29B7/823; B29B7/826; B29B7/84; B29B7/845; B29B7/86; B29B7/88; B29B7/90; B29C; B29C48/00; B29C48/022; B29C48/25; B29C48/285; B29C48/29; B29C48/36; B29C48/395; C08F8/00; C08F8/50; B29C48/03; B29C48/07; B29C48/08; B29C48/297; B29K; B29K2105/00; B29K2105/0005
Claims Analysis
Total Claims: 81
Claim 1
Independent Claim
13 words
A process according to claim 1 wherein said polymer is a thermoplastic polymer.
Claim 2
Dependent Claim
26 words
output grove means on the surface of said cylinder or cone means at the output end of said segment, terminating before reaching said input end; and
Claim 3
Dependent Claim
17 words
thin-film barrier means intermediate said grove, said barrier means not contacting the interior wall of said barrel.
Claim 4
Dependent Claim
16 words
A process according to claim 2 wherein said polymer is a C2 to C8 olefin polymer.
Claim 5
Dependent Claim
16 words
A process according to claim 3 wherein said polymer is either high or low density polyethylene.
Claim 6
Dependent Claim
11 words
A process according to claim 3 wherein said polymer is polypropylene.
Claim 7
Dependent Claim
25 words
A process according to claim 3 wherein said polymer is chosen from the group consisting of polymethyl pentene, isotactic polypropylene, polyallomers, polybutylene and mixtures thereof.
Claim 8
Dependent Claim
12 words
A process according to claim 1 wherein said polymer is an elastomer.
Claim 9
Dependent Claim
18 words
A process according to claim 7 wherein said elastomer is an ethylene-propylene copolymer or an ethylene-propylene diene terpolymer.
Claim 10
Dependent Claim
23 words
A process according to claim 1 wherein said monomer is unsaturated and has carboxylic acid functionality or a derivative of said acid functionality.
Claim 11
Dependent Claim
17 words
A process according to claim 1 wherein said monomer is acrylic acid or one of its derivatives.
Claim 12
Dependent Claim
17 words
A process according to claim 1 wherein said monomer is maleic anhydride or one of its derivatives.
Claim 13
Dependent Claim
31 words
A process according to claim 9 wherein the modified polymer resulting from the process is subsequently modified by subsequent reactions chosen from the group consisting of esterification, neutralization, amidization and imidization.
Claim 14
Dependent Claim
19 words
A process according to claim 1 wherein said free-radical initiator is introduced in the absence of free-radical reactive monomers.
Claim 15
Dependent Claim
19 words
A process according to claim 1 wherein said free-radical initiator is introduced in the presence of free-radical ractive monomers.
Claim 16
Dependent Claim
29 words
A process according to claim 1 wherein the initial portion of said reaction zone is at a relatively low pressure as compared to the rest of said reaction zone.
Claim 17
Dependent Claim
18 words
A process according to claim 1 wherein said polymer is a blend of a plastic and an elastomer.
Claim 18
Dependent Claim
28 words
A process according to claim 1 wherein said monomer is chosen from the group consisting of acrylic acid, glycidyl acrylate and maleic anhydride, and said polymer is polypropylene.
Claim 19
Dependent Claim
30 words
A process according to claim 1 wherein said monomer is chosen from the group consisting of acrylic acid, glycidyl acrylate and maleic anhydride, and said polymer is an ethylene-containing polymer.
Claim 20
Dependent Claim
198 words
A process for modifying the rheological or chemical-rheological properties of a polymer which is normally solid at room temperature, which comprises in combination the steps of: a. introducing said polymer into an extruder with a moving positive displacement screw of varying root cross-sectional area to define a reaction zone; b. generating an above-atmospheric pressure within said extruder as said polymer is conveyed therethrough; c. applying sufficient heat in addition to working said polymer, to convert it into its fluid form; d. conveying said fluid polymer through the initial portion of said reaction zone whereby said fluid polymer is forced into a relatively thin, as compared to the portion of said extruder just prior to said initial portion of said reaction zone, fluid film under high shear; e. introducing into said initial portion of said reaction zone while said polymer is in a thin-film, high-shear state sufficient of a material selected from the group consisting of: i. a monomer or monomers; ii. a free-radical initiator; iii. a combination of the foregoing; to measurably change either the rheological or chemical properties or both of said properties; and f. conveying the resultant modified polymer through the remainder of the extrusion process.
Claim 21
Dependent Claim
37 words
A method according to claim 19 wherein said initial portion of said reaction zone is characterized by a relatively large screw root cross-sectional area as compared to the screw root cross-sectional area immediately preceding said reaction zone.
Claim 22
Dependent Claim
16 words
A process according to claim 19 wherein said polymer is a C2 to C8 olefin polymer.
Claim 23
Dependent Claim
16 words
A process according to claim 21 wherein said polymer is either high or low density polyethylene.
Claim 24
Dependent Claim
11 words
A process according to claim 21 wherein said polymer is polypropylene.
Claim 25
Dependent Claim
25 words
A process according to claim 21 wherein said polymer is chosen from the group consisting of polymethyl pentene, isotactic polypropylene, polyallomers, polybutylene and mixtures thereof.
Claim 26
Dependent Claim
12 words
A process according to claim 19 wherein said polymer is an elastomer.
Claim 27
Dependent Claim
18 words
A process according to claim 25 wherein said elastomer is an ethylene-propylene copolymer or an ethylene-propylene diene terpolymer.
Claim 28
Dependent Claim
22 words
A process according to claim 19 wherein said monomer is unsaturated and has carboxylic functionality or a derivative of said acid functionality.
Claim 29
Dependent Claim
17 words
A process according to claim 19 wherein said monomer is acrylic acid or one of its derivatives.
Claim 30
Dependent Claim
20 words
A process according to claim 19 wherein said monomer is glycidyl acrylate or maleic anhydride or one of its derivatives.
Claim 31
Dependent Claim
31 words
A process according to claim 27 wherein the modified polymer resulting from the process is subsequently modified by subsequent reactions chosen from the group consisting of esterification, neutralization, amidization and imidization.
Claim 32
Dependent Claim
19 words
A process according to claim 19 wherein said free-radical initiator is introduced in the absence of free-radical reactive monomers.
Claim 33
Dependent Claim
19 words
A process according to claim 19 wherein said free-radical initiator is introduced in the presence of free-radical reactive monomers.
Claim 34
Dependent Claim
18 words
A process according to claim 19 wherein said polymer is a blend of a plastic and an elastomer.
Claim 35
Dependent Claim
28 words
A process according to claim 19 wherein said monomer is chosen from the group consisting of acrylic acid, glycidyl acrylate and maleic anhydride, and said polymer is polypropylene.
Claim 36
Dependent Claim
30 words
A process according to claim 19 wherein said monomer is chosen from the group consisting of acrylic acid, glycidyl acrylate and maleic anhydride, and said polymer is an ethylene-containing polymer.
Claim 37
Dependent Claim
68 words
A grafted polymeric composition, prepared from a base polymer, comprising from 0.02 to 20 weight percent of grafted compound and having a melt flow rate of from 3 to 1,000 and at least 50% higher than said base polymer and a die swell of at least 0.05 unit less than that of said base polymer wherein said grafted composition has been prepared by the process of claim 1.
Claim 38
Dependent Claim
34 words
A composition according to claim 36 wherein said base polymer is polystyrene or a C3 to C10 polyolefin and said grafted portion of said polymer is derived from unsaturated carboxylic acids or their derivatives.
Claim 39
Dependent Claim
12 words
A composition according to claim 36 wherein said base polymer is plastic.
Claim 40
Dependent Claim
12 words
A composition according to claim 36 wherein said base polymer is elastomeric.
Claim 41
Dependent Claim
18 words
A composition according to claim 36 wherein said base polymer is a blend of elastomeric and plastic polymers.
Claim 42
Dependent Claim
18 words
A composition according to claim 37 wherein said unsaturated carboxylic acid is acrylic acid or a derivative thereof.
Claim 43
Dependent Claim
21 words
A composition according to claim 37 wherein said unsaturated carboxylic acid or a derivative thereof is glycidyl acrylate or maleic anhydride.
Claim 44
Dependent Claim
27 words
A composition according to claim 38 wherein said grafted compound is selected from the group consisting of acrylic acid, glycidyl acrylate, maleic anhydride or a derivative thereof.
Claim 45
Dependent Claim
27 words
A composition according to claim 39 wherein said grafted compound is selected from the group consisting of acrylic acid, glycidyl acrylate, maleic anhydride or a derivative thereof.
Claim 46
Dependent Claim
92 words
A reactor apparatus which comprises in combination: a. a hollow extruder barrel with exterior, interior, beginning, middle and final portions; b. an extruder screw means having a root of varying cross-sectional area operably mounted within said barrel to advance material through said barrel; c. a reaction chamber in the middle portion of said barrel having an initial portion, said initial portion of said chamber being characterized by a decreased cross-sectional area of said screw root; and d. orifice means communicating between said initial chamber portion and said exterior portion of said barrel.
Claim 47
Dependent Claim
45 words
A reactor apparatus according to claim 45 wherein said final portion of the reaction chamber has a root cross-sectional area only slightly smaller than the internal cross-sectional area of said barrel, whereby gaseous materials within said chamber are prevented from easily escaping from said chamber.
Claim 48
Dependent Claim
98 words
A reactor apparatus which comprises in combination: a. a hollow extruder barrel with exterior, interior, beginning, middle and final portions; b. extruder screw means having a root of varying cross-sectional area operably mounted within said barrel to advance material through said barrel; c. a high-shear, thin film reaction chamber in the middle of said barrel having an initial portion defined by an increased cross-sectional thin film forming means screw root to shearingly engage said material between said barrel and said segment; and d. orifice means communicating between said initial chamber portion and said exterior portion of said barrel.
Claim 49
Dependent Claim
47 words
A reactor apparatus according to claim 47 wherein said reaction chamber has a final portion defined by a root cross-sectional area only slightly smaller than said interior cross-sectional area of said barrel, whereby gaseous materials formed in said chamber are prevented from easily escaping from said chamber.
Claim 50
Dependent Claim
44 words
A reactor apparatus according to claim 47 wherein said thin-film forming means is a cylinder or cone segment means having an output end and an input end longitudinally mounted in said barrel to shearingly engage a fluid between said barrel and said cylinder comprising:
Claim 51
Dependent Claim
18 words
A composition according to claim 42 wherein said unsaturated carboxylic acid or a derivative thereof is glycidyl acrylate.
Claim 52
Dependent Claim
29 words
The composition of claim 36 which has an MFR of from 11 to 250 and said MFR being at least 150% higher than the MFR of said base polymer.
Claim 53
Dependent Claim
31 words
A composition according to claim 36 having an MFR of 21 to 100 and a die swell of at least 0.1 of a unit less than that of the base polymer.
Claim 54
Dependent Claim
24 words
A composition according to claim 52 having a die swell of at least 0.15 of a unit less than that of the base polymer.
Claim 55
Dependent Claim
14 words
A composition according to claim 51 in which the grafted monomer is glycidyl acrylate.
Claim 56
Dependent Claim
18 words
A composition according to claim 36 wherein said polyolefin is polypropylene and said grafted monomer is glycidyl acrylate.
Claim 57
Dependent Claim
17 words
A composition according to claim 36 wherein said polyolefin is polypropylene and said monomer is acrylic acid.
Claim 58
Dependent Claim
104 words
A grafted C3 to C10 polyolefin comprising from 0.02 to 20 weight percent of a grafted component and having a melt-flow rate (MFR) of from 3 to 1,000 wherein said grafted polyolefin has been prepared by free radical attack on a base polymer in the presence of a monomer or a graftable reactive compound, wherein said base polymer has an MFR of from 0.3 to 0.9 and the MFR of said grafted polyolefin is at least 1,000% more than the MFR of said base polymer and the die swell of said grafted polyolefin is at least 0.05 less than that of said base polyolefin.
Claim 59
Dependent Claim
104 words
A grafted C3 to C10 polyolefin comprising from 0.02 to 20 weight percent of a grafted component and having a melt-flow rate (MFR) of from 5 to 1,000 wherein said grafted polyolefin has been prepared by free radical attack on a base polymer in the presence of a monomer or a graftable reactive compound, wherein said base polymer has an MFR of from 0.91 to 5.0 and the MFR of said grafted polyolefin is at least 700% more than the MFR of said base polymer and the die swell of said grafted polyolefin is at least 0.10 less than that of said base polyolefin.
Claim 60
Dependent Claim
104 words
A grafted C3 to C10 polyolefin comprising from 0.02 to 20 weight percent of a grafted component and having a melt-flow rate (MFR) of from 20 to 300 wherein said grafted polyolefin has been prepared by free radical attack on a base polymer in the presence of a minor or a graftable reactive compound, wherein said base polymer has an MFR of from 5.01 to 10 and the MFR of said grafted polyolefin is at least 400% more than the MFR of said base polymer and the die swell of said grafted polyolefin is at least 0.10 less than that of said base polyolefin.
Claim 61
Dependent Claim
104 words
A grafted C3 to C10 polyolefin comprising from 0.02 to 20 weight percent of a grafted component and having a melt-flow rate (MFR) of from 20 to 300 wherein said grafted polyolefin has been prepared by free radical attack on a base polymer in the presence of a monomer or a graftable reactive compound, wherein said base polymer has an MFR of from 10.1 to 150 and the MFR of said grafted polyolefin is at least 100% more than the MFR of said base polymer and the die swell of said grafted polyolefin is at least 0.10 less than that of said base polyolefin.
Claim 62
Dependent Claim
104 words
A grafted C3 to C10 polyolefin comprising from 0.02 to 20 weight percent of a grafted component and having a melt-flow rate (MFR) of from 5 to 300 wherein said grafted polyolefin has been prepared by free radical attack on a base polymer in the presence of a monomer or a graftable reactive compound, wherein said base polymer has an MFR of from 0.91 to 5.0 and the MFR of said grafted polyolefin is at least 900% more than the MFR of said base polymer and the die swell of said grafted polyolefin is at least 0.15 less than that of said base polyolefin.
Claim 63
Dependent Claim
68 words
A grafted polymeric composition, prepared from a base polymer, comprising from 0.02 to 20 weight percent of grafted compound and having a melt flow rate of from 3 to 1,000 and at least 50% higher than said base polymer and a die swell of at least 0.05 unit less than that of said base polymer, wherein said grafted composition has been prepared by the process of claim 19.
Claim 64
Dependent Claim
67 words
A grafted polymeric composition, prepared from a base polymer, comprising from 0.02 to 20 weight percent of grafted compound and having a melt flow rate of from 3 to 1,000 and at least 90 higher than said base polymer and a die swell of at least 0.05 unit less than that of said polymer, wherein said grafted composition has been prepared by the process of claim 20.
Claim 65
Dependent Claim
34 words
A composition according to claim 62 wherein said base polymer is polystyrene or a C3 to C10 polyolefin and said grafted portion of said polymer is derived from unsaturated carboxylic acids or their derivatives.
Claim 66
Dependent Claim
12 words
A composition according to claim 62 wherein said base polymer is plastic.
Claim 67
Dependent Claim
12 words
A composition according to claim 62 wherein said base polymer is elastomeric.
Claim 68
Dependent Claim
18 words
A composition according to claim 62 wherein said base polymer is a blend of elastomeric and plastic polymers.
Claim 69
Dependent Claim
18 words
A composition according to claim 62 wherein said unsaturated carboxylic acid is acrylic acid or a derivative thereof.
Claim 70
Dependent Claim
21 words
A composition according to claim 62 wherein said unsaturated carboxylic acid or a derivative thereof is glycidyl acrylate or maleic anhydride.
Claim 71
Dependent Claim
27 words
A composition according to claim 66 wherein said grafted compound iS selected from the group consisting of acrylic acid, glycidyl acrylate, maleic anhydride or a derivative thereof.
Claim 72
Dependent Claim
27 words
A composition according to claim 62 wherein said grafted compound is selected from the group consisting of acrylic acid, glycidyl acrylate, maleic anhydride or a derivative thereof.
Claim 73
Dependent Claim
14 words
A process according to claim 1 wherein said monomer is himic anhydride or acid.
Claim 74
Dependent Claim
14 words
A process according to claim 19 wherein said monomer is himic anhydride or acid.
Claim 75
Dependent Claim
20 words
A composition according to claim 64 wherein said unsaturated carboxylic acid or a derivative thereof is himic anhydride or acid.
Claim 76
Dependent Claim
29 words
The composition of claim 62 which has an MFR of from 11 to 250 and said MFR being at least 150% higher than the MFR of said base polymer.
Claim 77
Dependent Claim
31 words
A composition according to claim 62 having an MFR of 21 to 100 and a die swell of at least 0.1 of a unit less than that of the base polymer.
Claim 78
Dependent Claim
24 words
A composition according to claim 76 having a die swell of at least 0.15 of a unit less than that of the base polymer.
Claim 79
Dependent Claim
14 words
A composition according to claim 75 in which the grafted monomer is glycidyl acrylate.
Claim 80
Dependent Claim
18 words
A composition according to claim 64 wherein said polyolefin is polypropylene and said grafted monomer is glycidyl acrylate.
Claim 81
Dependent Claim
17 words
A composition according to claim 64 wherein said polyolefin is polypropylene and said monomer is acrylic acid.
References Cited (Backward Citations)
US3177270A
Cited
US3177269A
Cited
US3270090A
Cited
US3652730A
Cited
US3701751A
Cited
US3699186A
Cited
US3696069A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-01-20 | 1978-07-22 | 1979-01-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-01-20 | 1982-07-22 | 1983-01-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-01-20 | 1986-07-22 | 1987-01-21 | $7700.00 | Window Closed / Lapsed |