Patent US3133849A successfully refreshed from Google Patents.
Patent US5401804A successfully refreshed from Google Patents.
US5401804A
Expired / Lapsed
US
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Polymerization process and toner compositions therefrom
Assignee: Xerox Corp
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Filing: 1994-01-13
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Granted: 1995-03-28
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Expires: 2014-01-13
Abstract
Abstract Disclosed is a free radical polymerization process for the preparation of a thermoplastic resin or resins comprising heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a thermoplastic resin or resins with a high monomer to polymer conversion; cooling said mixture; optionally isolating the thermoplastic resin or resins; and optionally washing and drying thermoplastic resin or resins. Related free radical processes are also disclosed for the preparation of mixtures and block copolymer thermoplastic resins. Resins prepared by the disclosed processes possesses a narrow polydispersity and a modality that is controlled by the selection of a free radical initiator and stable free radical agent addition step or steps.
Inventors
- 👤 Michael K. Georges
- 👤 Richard P. N. Veregin
- 👤 Peter M. Kazmaier
- 👤 Gordon K. Hamer
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 16:42
CPC Classifications
C; C08; C08F; C08F299/00; G; G03; G03G; G03G9/00; G03G9/08; G03G9/087; G03G9/08702; C08F2/00; C08F2/38; C08F293/00; C08F293/005; C08F4/00; C08F4/04; C08F4/28
Claims Analysis
Total Claims: 114
Claim 1
Independent Claim
100 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating at a temperature of at least 100 degrees Centigrade a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer to form said thermoplastic resin or thermoplastic resins with a high monomer to resin or resins conversion of at least about 50 weight percent and with polydispersity of from about 1 to about 2; cooling said mixture; optionally isolating said thermoplastic resin or thermoplastic resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins.
Claim 2
Dependent Claim
100 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating at a temperature of at least 100 degrees Centigrade a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer to form said thermoplastic resin or thermoplastic resins with a high monomer to resin or resins conversion of at least about 50 weight percent and with polydispersity of from about 1 to about 2; cooling said mixture; optionally isolating said thermoplastic resin or thermoplastic resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins.
Claim 3
Dependent Claim
24 words
A process in accordance with claim 1 wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade.
Claim 4
Dependent Claim
25 words
A process in accordance with claim 2 wherein the stable free radical agent to free radical initiator molar ratio is about 0.9 to about 1.6.
Claim 5
Dependent Claim
18 words
A process in accordance with claim 2 wherein the polydispersity is from about 1.1 to about about 1.4.
Claim 6
Dependent Claim
15 words
A process in accordance with claim 2 wherein the free radical initiator is benzoyl peroxide.
Claim 7
Dependent Claim
24 words
A process in accordance with claim 2 wherein the stable free radical agent is of 2,2,6,6-tetramethyl-1-piperidinyloxy and the free radical initiator is benzoyl peroxide.
Claim 8
Dependent Claim
24 words
A process in accordance with claim 1 wherein the heating is accomplished at a temperature of from about 120° to about 140 degrees Centigrade.
Claim 9
Dependent Claim
19 words
A process in accordance with claim 7 wherein the free radical initiator is benzoyl peroxide. 10,000 to about 200,000.
Claim 10
Dependent Claim
19 words
A process in accordance with claim 7 wherein the conversion is from about 50 to about 95 weight percent.
Claim 11
Dependent Claim
32 words
A process in accordance with claim 7 wherein the conversion is from about 50 to about 90 weight percent based on monomer, and the polydispersity is from about 1.1 to about 1.4.
Claim 12
Dependent Claim
14 words
A process in accordance with claim 1 wherein the polydispersity is below about 1.5.
Claim 13
Dependent Claim
15 words
A process in accordance with claim 11 wherein the free radical initiator is benzoyl peroxide.
Claim 14
Dependent Claim
17 words
A process in accordance with claim 1 wherein the polydispersity is from about 1.1 to about 1.5.
Claim 15
Dependent Claim
15 words
A process in accordance with claim 13 wherein the free radical initiator is benzoyl peroxide.
Claim 16
Dependent Claim
25 words
A process in accordance with claim 13 wherein the stable free radical agent to free radical initiator molar ratio is about 0.9 to about 1.6.
Claim 17
Dependent Claim
15 words
A process in accordance with claim 1 wherein the polydispersity is from 1.1 to 1.3.
Claim 18
Dependent Claim
25 words
A process in accordance with claim 16 wherein the stable free radical agent to free radical initiator molar ratio is about 0.9 to about 1.6.
Claim 19
Dependent Claim
30 words
A process in accordance with claim 1 wherein the conversion is at least about 92 weight percent based on monomer and wherein the monomer is a vinyl substituted aromatic compound.
Claim 20
Dependent Claim
38 words
A process in accordance with claim 1 wherein the conversion is at least about 86 weight percent based on monomer and wherein the monomer selected is a mixture of a vinyl substituted aromatic and a conjugated diene compound.
Claim 21
Dependent Claim
45 words
A process in accordance with claim 1 wherein the conversion is from about 50 to about 90 weight percent, the polydispersity is from about 1.1 to about 1.5, and the heating is accomplished at a temperature of from about 120° to about 1.60 degrees Centigrade.
Claim 22
Dependent Claim
22 words
A process in accordance with claim 1 wherein the free radical initiator and the stable free radical are added as separate components.
Claim 23
Dependent Claim
15 words
A process in accordance with claim 21 wherein the free radical initiator is benzoyl peroxide.
Claim 24
Dependent Claim
24 words
A process in accordance with claim 21 wherein the stable free radical agent is of 2,2,6,6-tetramethyl-1-piperidinyloxy and the free radical initiator is benzoyl peroxide.
Claim 25
Dependent Claim
27 words
A process in accordance with claim 21 wherein the stable free radical agent to free radical initiator molar ratio is from about 0.9 g to about 2.5.
Claim 26
Dependent Claim
22 words
A process in accordance with claim 21 wherein the stable free radical agent to free radical initiator molar ratio is about 1.3.
Claim 27
Dependent Claim
15 words
A process in accordance with claim 1 wherein the free radical initiator is benzoyl peroxide.
Claim 28
Dependent Claim
21 words
A process in accordance with claim 1 wherein the stable free radical agent is comprised of a nitroxide stable free radical.
Claim 29
Dependent Claim
33 words
A process in accordance with claim 1 wherein the stable free radical agent is comprised of 8 nitroxide stable free radical selected from the group of consisting of 2,2,5,5-tetramethyl-1-pyrrolidinyloxy, 2,2,6,6-tetramethyl-1-piperidinyloxy, and mixtures thereof.
Claim 30
Dependent Claim
24 words
A process in accordance with claim 1 wherein the stable free radical agent is of 2,2,6,6-tetramethy-1-piperidinyloxy and the free radical initiator is benzoyl peroxide.
Claim 31
Dependent Claim
26 words
A process in accordance with claim 29 wherein the stable free radical agent to free radical initiator molar ratio is from about 0.9 to about 2.5.
Claim 32
Dependent Claim
22 words
A process in accordance with claim 29 wherein the stable free radical agent to free radical initiator molar ratio is about 1.3.
Claim 33
Dependent Claim
26 words
A process in accordance with claim 1 wherein the stable free radical agent to free radical initiator molar ratio is from about 0.9 to about 2.5.
Claim 34
Dependent Claim
26 words
A process in accordance with claim 1 wherein the stable free radical agent to free radical initiator molar ratio is from about 0.9 to about 1.6.
Claim 35
Dependent Claim
22 words
A process in accordance with claim 1 wherein the stable free radical agent to free radical initiator molar ratio is about 1.3.
Claim 36
Dependent Claim
20 words
A process in accordance with claim 1 wherein the polymerizable monomer is a mixture of styrene and an acrylate ester.
Claim 37
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerizable monomer is styrene.
Claim 38
Dependent Claim
25 words
A process in accordance with claim 1 wherein the weight average molecular weight of the resin or resins is from about 10,000 to about 200,000.
Claim 39
Dependent Claim
23 words
A process in accordance with claim 1 wherein the weight average molecular weight of the resin is from about 10,000 to about 200,000.
Claim 40
Dependent Claim
23 words
A process in accordance with claim 38 wherein the number average molecular weight of the resin is from about 9,000 to about 100,000.
Claim 41
Dependent Claim
23 words
A process in accordance with claim 1 wherein the number average molecular weight of the resin is from about 9,000 to about 100,000.
Claim 42
Dependent Claim
41 words
A process in accordance with claim 1 further comprising adding an organic sulfonic or organic carboxylic acid during heating of said mixture thereby increasing the rate of formation of said thermoplastic resin or thermoplastic resins from said polymerization of said monomer.
Claim 43
Dependent Claim
15 words
A process in accordance with claim 41 wherein the organic sulfonic acid is camphorsulfonic acid.
Claim 44
Dependent Claim
22 words
A process in accordance with claim 42 wherein the molar ratio of stable free radical to acid is from 1.5:1 to 5:1.
Claim 45
Dependent Claim
15 words
A process in accordance with claim 41 wherein the organic carboxylic add is benzoic acid.
Claim 46
Dependent Claim
33 words
A process in accordance with claim 41 wherein the sulfonic or carboxylic acid is selected from the group consisting of acetic, propanoic, butanoic, p-chlorobenzoic, benzene sulfonic, naphthalene sulfonic, dodecyl sulfonic, arid mixtures thereof.
Claim 47
Dependent Claim
24 words
A process in accordance with claim 41 wherein the molar ratio of stable free radical to acid is from about 1:1 to about 11:1.
Claim 48
Dependent Claim
19 words
A process in accordance with claim 1 wherein the conversion is from about 50 to about 95 weight percent.
Claim 49
Dependent Claim
25 words
A process in accordance with claim 1 wherein the heating is accomplished for a period of time of from about 1 to about 60 hours.
Claim 50
Dependent Claim
25 words
A process in accordance with claim 1 wherein the heating is accomplished for a period of time of from about 1 to about 10 hours.
Claim 51
Dependent Claim
19 words
A process in accordance with claim 1 wherein the polymerizable monomer is a mixture of styrene and a diene.
Claim 52
Dependent Claim
27 words
A process in accordance with claim 1 wherein the ratio of monomer to stable free radical to free radical initiator is from about 100:2.0:1.0 to about 10,000:2.5:1.0.
Claim 53
Dependent Claim
30 words
A process in accordance with claim 1 further comprising adding a protic acid during heating of said mixture thereby increasing the rate of conversion of monomer to the thermoplastic resin.
Claim 54
Dependent Claim
18 words
A process in accordance with claim 1 wherein said at least one polymerizable monomer is a single monomer.
Claim 55
Dependent Claim
20 words
A process in accordance with claim 1 wherein said at least one polymerizable monomer comprises from two to three monomers.
Claim 56
Dependent Claim
122 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin or thermoplastic resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of from about 100° to about 160 degrees Centigrade, the monomer to polymer conversion is at least about 50 weight percent based on monomer, the resin or resins polydispersity is from about 1.1 to about 1.5.
Claim 57
Dependent Claim
122 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin or thermoplastic resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of from about 100° to about 160 degrees Centigrade, the monomer to polymer conversion is at least about 50 weight percent based on monomer, the resin or resins polydispersity is from about 1.1 to about 1.5.
Claim 58
Dependent Claim
15 words
A process in accordance with claim 55 wherein the free radical initiator is benzoyl peroxide.
Claim 59
Dependent Claim
15 words
A process in accordance with claim 55 wherein the stable free radical agent is 2,2,6,6-tetramethyl-1-piperidinyloxy.
Claim 60
Dependent Claim
113 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin or resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of at least about 100° C., the conversion is from about 50 to about 95 weight percent, and the polydispersity is from about 1.1 to about 1.5.
Claim 61
Dependent Claim
113 words
A free radical polymerization process for the preparation of a thermoplastic resin or thermoplastic resins comprising: heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or thermoplastic resins with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin or resins; and optionally washing and drying said thermoplastic resin or thermoplastic resins, and wherein the heating is accomplished at a temperature of at least about 100° C., the conversion is from about 50 to about 95 weight percent, and the polydispersity is from about 1.1 to about 1.5.
Claim 62
Dependent Claim
13 words
A process in accordance with claim 58 wherein the peroxide is benzoyl peroxide.
Claim 63
Dependent Claim
29 words
A process in accordance with claim 58 wherein the temperature is from about 120° to about 160 degrees Centigrade, and the polydispersity is from about 1.1 to about 1.4.
Claim 64
Dependent Claim
20 words
A process in accordance with claim 60 wherein the stable free radical is 2,2,6,6-tetramethyl-1-piperidinyloxy and the initiator is benzoyl peroxide.
Claim 65
Dependent Claim
14 words
A process in accordance with claim 58 wherein the stable free radical is 2,2,6,6-tetramethyl-1-piperidinyloxy.
Claim 66
Dependent Claim
119 words
A free radical polymerization process for the preparation of a thermoplastic resin comprising: heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin; and optionally washing and drying said thermoplastic resin, and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from 50 to 95 weight percent, the polydispersity is from about 1.1 to about 1.5 and wherein the heating is accomplished for a period of from about 1 to about 60 hours.
Claim 67
Dependent Claim
119 words
A free radical polymerization process for the preparation of a thermoplastic resin comprising: heating a mixture of a peroxide free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said thermoplastic resin; and optionally washing and drying said thermoplastic resin, and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from 50 to 95 weight percent, the polydispersity is from about 1.1 to about 1.5 and wherein the heating is accomplished for a period of from about 1 to about 60 hours.
Claim 68
Dependent Claim
100 words
A free radical polymerization process for the preparation of a thermoplastic resin or resins comprising: heating a water suspension mixture of a peroxide free radical initiator, a nitroxide stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or resins with a monomer to polymer conversion in excess of about 50 weight percent; cooling said mixture; optionally isolating said thermoplastic resin or resins; and optionally washing and drying said thermoplastic resin or resins and wherein said thermoplastic resin possesses a narrow polydispersity of from about 1.0 to about 2.0 and a modality of 1.
Claim 69
Dependent Claim
100 words
A free radical polymerization process for the preparation of a thermoplastic resin or resins comprising: heating a water suspension mixture of a peroxide free radical initiator, a nitroxide stable free radical agent, and at least one polymerizable monomer compound to form said thermoplastic resin or resins with a monomer to polymer conversion in excess of about 50 weight percent; cooling said mixture; optionally isolating said thermoplastic resin or resins; and optionally washing and drying said thermoplastic resin or resins and wherein said thermoplastic resin possesses a narrow polydispersity of from about 1.0 to about 2.0 and a modality of 1.
Claim 70
Dependent Claim
27 words
A process in accordance with claim 64 wherein the stable free radical agent to free radical initiator molar ratio SFR:INIT is from about 0.2 to about 2.5.
Claim 71
Dependent Claim
34 words
A process in accordance with claim 64 wherein monomer to polymer conversion is of from about 50 to about weight percent based on monomer and said narrow polydispersity is about 1.1 to about 1.6.
Claim 72
Dependent Claim
38 words
A process in accordance with claim 64 wherein said narrow polydispersity is from about 1.1 to about 1.4 and wherein the conversion from monomer to polymers is from about 50 to about 100 weight percent based on monomer.
Claim 73
Dependent Claim
119 words
A free radical polymerization process for the preparation of resin comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said resin; and optionally washing and drying said resin, and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, the polydispersity is from about 1.1 to about 1.4, and the free radical initiator and stable free radical agent are added into the mixture as separate components.
Claim 74
Dependent Claim
119 words
A free radical polymerization process for the preparation of resin comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; optionally isolating said resin; and optionally washing and drying said resin, and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, the polydispersity is from about 1.1 to about 1.4, and the free radical initiator and stable free radical agent are added into the mixture as separate components.
Claim 75
Dependent Claim
15 words
A process in accordance with claim 68 wherein the free radical initiator is benzoyl peroxide.
Claim 76
Dependent Claim
15 words
A process in accordance with claim 68 wherein the stable free radical agent is 2,2,6,6-tetramethyl-1-piperidinyloxy.
Claim 77
Dependent Claim
23 words
A process in accordance with claim 68 wherein the free radical initiator is benzoyl peroxide and the stable free radical agent is 2,2,6,6-tetramethyl-1-piperidinyloxy.
Claim 78
Dependent Claim
102 words
A free radical polymerization process for the preparation of a resin comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; isolating said resin, and optionally washing and drying said resin and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, and the polydispersity is from about 1.1 to about 1.4.
Claim 79
Dependent Claim
102 words
A free radical polymerization process for the preparation of a resin comprising: heating a mixture of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form said resin with a high monomer to polymer conversion and with excellent polydispersities; cooling said mixture; isolating said resin, and optionally washing and drying said resin and wherein the heating is accomplished at a temperature of from about 120° to about 160 degrees Centigrade, the conversion is from about 50 to about 95 weight percent based on monomer, and the polydispersity is from about 1.1 to about 1.4.
Claim 80
Dependent Claim
15 words
A process in accordance with claim 72 wherein the stable free radical agent is 2,2,6,6-tetramethyl-1-piperidinyloxy.
Claim 81
Dependent Claim
62 words
A process for the preparation of resin which comprises heating at a temperature of from about 100° to about 160° C. a mixture of free radical initiator, stable free radical agent, and at least one monomer component, which resin has a polydispersity of from about 1.1 to about 2, and the monomer to resin conversion is at least about 50 weight percent.
Claim 82
Dependent Claim
62 words
A process for the preparation of resin which comprises heating at a temperature of from about 100° to about 160° C. a mixture of free radical initiator, stable free radical agent, and at least one monomer component, which resin has a polydispersity of from about 1.1 to about 2, and the monomer to resin conversion is at least about 50 weight percent.
Claim 83
Dependent Claim
42 words
A process in accordance with claim 74 wherein the heating is from about 120° to about 160° C., the polydispersity is from about 1.1 to about 1.4, and the conversion is from about 50 to about 95 weight percent based on monomer.
Claim 84
Dependent Claim
35 words
A process in accordance with claim 74 wherein the heating is from about 120° to about 140° C., the polydispersity is from 1.1 to 1.4, and the conversion exceeds 65 weight percent based on monomer.
Claim 85
Dependent Claim
23 words
A process in accordance with claim 74 wherein the stable free radical agent and the free radical initiator are added as separate components.
Claim 86
Dependent Claim
23 words
A process in accordance with claim 74 wherein the stable free radical agent is 2,2,6,6-tetramethyl-1-piperidinyloxy and the free radical initiator is benzoyl peroxide.
Claim 87
Dependent Claim
24 words
A process in accordance with claim 74 wherein the stable free radical agent to initiator molar ratio is from about 0.9 to about 1.6.
Claim 88
Dependent Claim
19 words
A process in accordance with claim 74 wherein said at least one monomer component is a single monomer component.
Claim 89
Dependent Claim
15 words
A process in accordance with claim 74 wherein the mixture is cooled by heating termination.
Claim 90
Dependent Claim
16 words
A process in accord with claim 74 wherein the mixture is cooled to about 25° C.
Claim 91
Dependent Claim
14 words
A process in accordance with claim 74 wherein the resin is isolated by filtration.
Claim 92
Dependent Claim
231 words
A polymerization process for the preparation of thermoplastic resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same monomer components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture; heating said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from substantially only said second monomer; cooling said third mixture; optionally isolating said mixture of thermoplastic product resins from said third mixture; and optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a polydispersity of about 1 to about 2.
Claim 93
Dependent Claim
231 words
A polymerization process for the preparation of thermoplastic resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same monomer components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture; heating said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from substantially only said second monomer; cooling said third mixture; optionally isolating said mixture of thermoplastic product resins from said third mixture; and optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a polydispersity of about 1 to about 2.
Claim 94
Dependent Claim
18 words
A process in accordance with claim 84, wherein said mixture of thermoplastic resins possesses a modality of 2.
Claim 95
Dependent Claim
17 words
A process in accordance with claim 84 wherein said mixture of thermoplastic resins has a bimodal distribution.
Claim 96
Dependent Claim
23 words
A process in accordance with claim 84 wherein said heating is for a period of from about 1 hour to about 30 hours.
Claim 97
Dependent Claim
27 words
A process in accordance with claim 84 wherein the stable free radical agent to free radical initiator molar ratio SFR:INIT is from about 0.2 to about 2.5.
Claim 98
Dependent Claim
34 words
A process in accordance with claim 84 wherein monomer to polymer conversion is of from about 50 to about weight percent based on monomer and said narrow polydispersity is about 1.0 to about 2.0.
Claim 99
Dependent Claim
29 words
A process in accordance with claim 84 wherein said free radical initiator has a half life of from about 5 seconds to about 10 minutes at above 100° C.
Claim 100
Dependent Claim
278 words
A free radical polymerization process for the preparation of thermoplastic resin comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture; heating for a period of from about 1 to about 60 hours said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from said second monomer; cooling said third mixture; optionally isolating said mixture of thermoplastic product resins from said third mixture; and optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a narrow polydispersity obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent and which polydispersity is from about 1.1 to about 1.5; and wherein heating is accomplished at a temperature of from about 100° to about 160 degrees Centigrade.
Claim 101
Dependent Claim
278 words
A free radical polymerization process for the preparation of thermoplastic resin comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; adding to said first intermediate product resin a second mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture contains the same components as said polymerizable monomer compound of said first mixture, and said free radical initiator and said stable free radical agent of said second mixture are the same or different from said free radical initiator and said stable free radical agent of said first mixture, and wherein there is formed a combined mixture; heating for a period of from about 1 to about 60 hours said combined mixture to form a third mixture comprised of a mixture of thermoplastic resins comprised of a first product resin formed from said first intermediate product resin and added said second monomer and a second product resin formed from said second monomer; cooling said third mixture; optionally isolating said mixture of thermoplastic product resins from said third mixture; and optionally washing and drying said mixture of thermoplastic resins and wherein said first product resin and said second product resin each possess a narrow polydispersity obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent and which polydispersity is from about 1.1 to about 1.5; and wherein heating is accomplished at a temperature of from about 100° to about 160 degrees Centigrade.
Claim 102
Dependent Claim
19 words
A process in accordance with claim 91 wherein the temperature is from about 120° to about 160 degrees Centigrade.
Claim 103
Dependent Claim
179 words
A polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture containing said block copolymer thermoplastic resin; optionally isolating said block copolymer thermoplastic resin from said third mixture; and optionally washing and drying said block copolymer thermoplastic resin wherein said block copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2.
Claim 104
Dependent Claim
179 words
A polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture containing said block copolymer thermoplastic resin; optionally isolating said block copolymer thermoplastic resin from said third mixture; and optionally washing and drying said block copolymer thermoplastic resin wherein said block copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2.
Claim 105
Dependent Claim
16 words
A process in accordance with claim 93, wherein said block copolymer possesses a modality of 1.
Claim 106
Dependent Claim
23 words
A process in accordance with claim 93 wherein said heating is for a period of from about 1 hour to about 30 hours.
Claim 107
Dependent Claim
38 words
A process in accordance with claim 93 wherein said narrow polydispersity is from about 1.1 to about 1.4 and wherein the conversion from monomer to polymers is from about 50 to about 100 weight percent based on monomer.
Claim 108
Dependent Claim
224 words
A polymerization process for the preparation of a multiblock copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture; optionally isolating said third mixture; sequentially repeating the preceding steps of adding, heating and cooling, N times, to form a fourth mixture containing a multiblock copolymer thermoplastic resin or resins having N+2 blocks and wherein N is the number of times said sequence is repeated; optionally isolating said multiblock copolymer thermoplastic resin from said fourth mixture; and optionally washing and drying said multiblock copolymer thermoplastic resin and wherein said multiblock copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2 and a modality of 1.
Claim 109
Dependent Claim
224 words
A polymerization process for the preparation of a multiblock copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture; optionally isolating said third mixture; sequentially repeating the preceding steps of adding, heating and cooling, N times, to form a fourth mixture containing a multiblock copolymer thermoplastic resin or resins having N+2 blocks and wherein N is the number of times said sequence is repeated; optionally isolating said multiblock copolymer thermoplastic resin from said fourth mixture; and optionally washing and drying said multiblock copolymer thermoplastic resin and wherein said multiblock copolymer thermoplastic resin possesses a polydispersity of about 1 to about 2 and a modality of 1.
Claim 110
Dependent Claim
33 words
A process in accordance with claim 55 wherein the resin contains a terminal and covalently bound nitroxyl group arising from reaction of a nitroxyl stable free radical agent with a propagating polymeric chain.
Claim 111
Dependent Claim
15 words
A process in accordance with claim 97, wherein N is from 1 to about 20.
Claim 112
Dependent Claim
213 words
A free radical polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture; optionally isolating said block copolymer thermoplastic resin from said third mixture; and optionally washing and drying said block copolymer thermoplastic resin wherein the resin possesses a narrow polydispersity and is obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent based on monomer and which polydispersity is from about 1.1 to about 1.6 and which heating is at a temperature of from about 120° to about 160 degrees Centigrade.
Claim 113
Dependent Claim
213 words
A free radical polymerization process for the preparation of a block copolymer thermoplastic resin or resins comprising: heating a first mixture comprised of a free radical initiator, a stable free radical agent, and at least one polymerizable monomer compound to form a first intermediate product resin; optionally cooling said first mixture; optionally isolating said first intermediate product resin; adding to said first intermediate product resin a second mixture comprised of at least one polymerizable monomer compound, wherein said polymerizable monomer compound of said second mixture is different from said polymerizable monomer compound of said first mixture, to form a combined mixture; heating said combined mixture to form a third mixture comprised of a block copolymer thermoplastic resin comprised of a first product resin formed from said first intermediate product resin and added said second monomer; cooling said third mixture; optionally isolating said block copolymer thermoplastic resin from said third mixture; and optionally washing and drying said block copolymer thermoplastic resin wherein the resin possesses a narrow polydispersity and is obtained in excellent conversion, which conversion is from about 50 to about 90 weight percent based on monomer and which polydispersity is from about 1.1 to about 1.6 and which heating is at a temperature of from about 120° to about 160 degrees Centigrade.
Claim 114
Dependent Claim
21 words
A process in accordance with claim 97 wherein the multiblock copolymer thermoplastic possesses a covalently bonded and thermally lablie nitroxyl terminus.
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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) | 1998-03-27 | 1998-09-26 | 1999-03-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2002-03-27 | 2002-09-26 | 2003-03-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2006-03-27 | 2006-09-26 | 2007-03-28 | $7700.00 | Window Closed / Lapsed |