Patent US4548995A successfully refreshed from Google Patents.
US4548995A
Expired / Lapsed
US
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Process for the manufacture of halogenated polymers
Assignee: ExxonMobil Technology and Engineering Co
•
Filing: 1984-09-17
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Granted: 1985-10-22
•
Expires: 2004-09-17
Abstract
Abstract In a process for the continuous halogenation of polymers by contacting polymer and halogenating agent in a continuous flow device in which means are provided for disengaging reaction by-products and unreacted halogenating agent from the reaction mixture, by deforming and disrupting the halogenated polymer surface and injecting an inert gas into the halogenated polymers immediately after reaction thereby neutralizing the product. In a preferred embodiment the process is carried out in an extruder-reactor and an optional, supplementary inert gas scrubbing zone is included. The process is amenable to saturated and unsaturated polymers.
Inventors
- 👤 Ronald C. Kowalski
- 👤 William M. Davis
- 👤 Neil F. Newman
- 👤 Z. Andrew Foroulis
- 👤 Francis P. Baldwin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 10:52
CPC Classifications
C; C08; C08F; C08F8/00; C08F8/18; C08F8/20; C08C; C08C19/00; C08C19/12
Claims Analysis
Total Claims: 84
Claim 1
Independent Claim
104 words
A process for the continuous production of halogenated polymer, the process comprising contacting a cohesive polymer mass and halogenating agent in a continuous flow device comprising means for conveying said polymer through said device wherein by-product of the halogenation reaction and unreacted halogenating agent are disengaged from said halogenated polymer mass in said continuous flow device downstream of said contact between said polymer and said halogenating agent by means comprising deforming and disrupting said halogenated polymer, thereby continually generating new polymer surface and injecting an effective amount of inert gas thereby neutralizing said halogenated polymer by disengaging halogenation reaction by-products and unreacted halogenating agent.
Claim 2
Dependent Claim
104 words
A process for the continuous production of halogenated polymer, the process comprising contacting a cohesive polymer mass and halogenating agent in a continuous flow device comprising means for conveying said polymer through said device wherein by-product of the halogenation reaction and unreacted halogenating agent are disengaged from said halogenated polymer mass in said continuous flow device downstream of said contact between said polymer and said halogenating agent by means comprising deforming and disrupting said halogenated polymer, thereby continually generating new polymer surface and injecting an effective amount of inert gas thereby neutralizing said halogenated polymer by disengaging halogenation reaction by-products and unreacted halogenating agent.
Claim 3
Dependent Claim
70 words
The process of claim 1 wherein said polymer mass is subjected to deformation and disruption and wherein said polymer and said halogenating agent are present during contact as either co-continuous phases or wherein said halogenating agent is present as a continuous phase and said polymer is present as a discontinuous phase or wherein the region in which said polymer and said halogenating agent are contacted is filled with said polymer.
Claim 4
Dependent Claim
34 words
The process of claim 1 wherein said polymer is an ethylenically unsaturated polymer selected from the group consisting of butyl rubber, EPDM rubber, styrene butadiene rubber, polyisoprene rubber, polybutadiene rubber and poly(butadien-isoprene) copolymer rubber.
Claim 5
Dependent Claim
34 words
The process of claim 1 wherein said polymer is selected from the group consisting of polyisobutylene, ethylene-propylene copolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer and polyvinyl chloride.
Claim 6
Dependent Claim
11 words
The process of claim 3 wherein said rubber is butyl rubber.
Claim 7
Dependent Claim
11 words
The process of claim 3 wherein said rubber is EPDM rubber.
Claim 8
Dependent Claim
14 words
The process of claim 4 wherein said saturated polymer is linear low density polyethylene.
Claim 9
Dependent Claim
12 words
The process of claim 5 wherein said butyl rubber is isobutylene-isoprene copolymer.
Claim 10
Dependent Claim
41 words
The process of claim 1 wherein said halogenating agent is selected from the group consisting of chlorine gas, chlorine liquid, sulfuryl chloride, N-chlorosuccinimide, 1,3-dihalo-5, 5-dimethylhydantoin, iodobenzene dichloride, iodine monochloride, bromine gas, bromine liquid, bromine chloride, sodium hypobromite, sulfur bromide and N-bromosuccinimide.
Claim 11
Dependent Claim
25 words
The process of claim 1, further comprising adding a diluent to said rubber feed before, at or near the point of addition of said feed.
Claim 12
Dependent Claim
24 words
The process of claim 10 wherein said diluent is selected from the group consisting of volatile saturated hydrocarbons, chlorohydrocarbons, chlorocarbons, non-hydrocarbons, and hydrocarbon oils.
Claim 13
Dependent Claim
27 words
The process of claim 11 wherein said diluent is selected from the group consisting of pentane, hexane, methylene chloride, chloroform, carbon tetrachloride, carbon dioxide, and inert gas.
Claim 14
Dependent Claim
26 words
The process of claim 12 wherein said diluent is present in an amount less than about 50 percent by weight based on the weight of rubber.
Claim 15
Dependent Claim
21 words
The process of claim 8 wherein said halogenating agent is selected from the group consisting of bromine, chlorine and bromine chloride.
Claim 16
Dependent Claim
13 words
The process of claim 8 wherein said halogenating agent is diluted with diluent.
Claim 17
Dependent Claim
11 words
The process of claim 15 wherein said halogenating agent is chlorine.
Claim 18
Dependent Claim
24 words
The process of claim 15 wherein said diluent is a gas selected from the group consisting of nitrogen, argon, air and CO 2 .
Claim 19
Dependent Claim
43 words
The process of claim 10 wherein said halogenating agent is diluted with a diluent and wherein the total amount of diluent added to said feed and halogenating agent diluent is less than about 50 percent by weight based on the weight of polymer.
Claim 20
Dependent Claim
27 words
The process of claim 18 wherein said diluent added to said feed is selected from the group consisting of volatile saturated hydrocarbons, chlorohydrocarbons, chlorocarbons and hydrocarbon oils.
Claim 21
Dependent Claim
15 words
The process of claim 1 further comprising vent means in the inert gas injection region.
Claim 22
Dependent Claim
30 words
The process of claim 1 further comprising pressure control means in the inert gas injection region in order to explosively disengage said halogenation reaction by-products and said unreacted halogenating agent.
Claim 23
Dependent Claim
34 words
The process of claim 1 wherein said injected inert gas and said halogenated polymer are conveyed co-currently or countercurrently through said device in a neutralization zone following contact between said polymer and halogenating agent.
Claim 24
Dependent Claim
25 words
The process of claim 22 wherein said co-current conveyance of said neutralizing means is initiated at the beginning of said neutralization zone or shortly thereafter.
Claim 25
Dependent Claim
13 words
The process of claim 20 further comprising a supplementary inert gas injection step.
Claim 26
Dependent Claim
17 words
The process of claim 24 wherein said supplementary injection step is performed in a separate scrubbing zone.
Claim 27
Dependent Claim
24 words
The process of claim 20 further comprising a stabilizer addition zone wherein a degradation, oxidation or dehydrohalogenation stabilizer is added to said halogenated polymer.
Claim 28
Dependent Claim
21 words
The process of claim 24 wherein a degradation, oxidation or dehydrohalogenation stabilizer is added following said supplementary inert gas injections step.
Claim 29
Dependent Claim
11 words
The process of claim 1 further comprising a final exit zone.
Claim 30
Dependent Claim
28 words
The process of claim 28 wherein the temperature of said halogenated rubber is adjusted for delivery from said exit zone at a temperature lower than about 130° C.
Claim 31
Dependent Claim
18 words
The process of claim 28 wherein a degradation, oxidation or dehydrohalogenation stabilizer is added to said exit zone.
Claim 32
Dependent Claim
20 words
The process of claim 24 further comprising filter means to effect the separation of undispersed materials from said halogenated polymer.
Claim 33
Dependent Claim
12 words
The process of claim 20 wherein said vent means are under vacuum.
Claim 34
Dependent Claim
14 words
The process of claim 1 wherein said contact occurs in a vented reaction zone.
Claim 35
Dependent Claim
34 words
The process of claim 1 wherein said continuous flow device is selected from the group consisting of a kneader, a single- or multiple screw extruder and a continuous mixer, and a cavity transfer mixer.
Claim 36
Dependent Claim
15 words
The process of claim 1 wherein said means for conveying said polymer is screw means.
Claim 37
Dependent Claim
33 words
The process of claim 1 wherein said deformation and disruption generates a degree of mixing of said halogenated polymer and inert gas such that the scale of segregation is less than 50 microns.
Claim 38
Dependent Claim
139 words
A process for the continuous production of halogenated polymer, the process comprising reacting said polymer and a halogenating agent in an extruder-reactor, said extruder-reactor comprising zones (A), (B) and (C) and conveying means traversing said zones; zone A, feed zone, in which conditions of temperature and pressure are sufficient to generate a cohesive polymer mass; zone (B), reaction zone, in which said halogenating agent and said polymer are contacted, resulting in a product mixture comprising halogenated polymer, reaction by-products and unreacted halogenating agent; and zone (C), neutralization zone, wherein reaction by-products and unreacted halogenating agent are disengaged from said halogenated polymer mass by means comprising deforming and disrupting said halogenated polymer, thereby continually generating new polymer surface and injecting an effective amount of inert gas thereby neutralizing said halogenated polymer by disengaging halogenation reaction by-products and unreacted halogenating agent.
Claim 39
Dependent Claim
139 words
A process for the continuous production of halogenated polymer, the process comprising reacting said polymer and a halogenating agent in an extruder-reactor, said extruder-reactor comprising zones (A), (B) and (C) and conveying means traversing said zones; zone A, feed zone, in which conditions of temperature and pressure are sufficient to generate a cohesive polymer mass; zone (B), reaction zone, in which said halogenating agent and said polymer are contacted, resulting in a product mixture comprising halogenated polymer, reaction by-products and unreacted halogenating agent; and zone (C), neutralization zone, wherein reaction by-products and unreacted halogenating agent are disengaged from said halogenated polymer mass by means comprising deforming and disrupting said halogenated polymer, thereby continually generating new polymer surface and injecting an effective amount of inert gas thereby neutralizing said halogenated polymer by disengaging halogenation reaction by-products and unreacted halogenating agent.
Claim 40
Dependent Claim
26 words
The process of claim 37 further comprising first flow restriction means between zones A and B, and second flow restriction means between zones B and C.
Claim 41
Dependent Claim
14 words
The process of claim 32 wherein a vacuum is applied to said vent means.
Claim 42
Dependent Claim
33 words
The process of claim 37 wherein said deformation and disruption generates a degree of mixing of said halogenated polymer and inert gas such that the scale of segregation is less than 50 microns.
Claim 43
Dependent Claim
39 words
The process of claim 38 wherein said restriction means following said feed zone is selected from the group consisting of a reverse flighted screw section, a filled screw section, a shallow flighted screw section, and an unflighted screw section.
Claim 44
Dependent Claim
19 words
The process of claim 41 wherein said restriction means is about 0.5 to about 8 screw diameters in length.
Claim 45
Dependent Claim
17 words
The process of claim 38 wherein said restriction means following said feed zone comprises said reaction zone.
Claim 46
Dependent Claim
58 words
The process of claim 37 wherein said means for producing said deformation is selected from the group consisting of a reverse flighted screw section, a multiple reverse flighted screw section, a pin section, a series of very short alternating reverse and forward screw sections, multiple flight screw section, interrupted flight section, a cavity transfer mixer, and combinations thereof.
Claim 47
Dependent Claim
43 words
The process of claim 38 wherein said restriction means separating said neutralization zone from said reaction zone is selected from the group consisting of a reverse flighted screw section, a filled screw section, a shallow flighted screw section, and an unflighted screw section.
Claim 48
Dependent Claim
44 words
The process of claim 38 wherein each of said restriction means is an unflighted screw section with a diameter of from 5 to 25 percent larger than the root diameter of the upstream screw section, but not greater than the upstream screw flight diameter.
Claim 49
Dependent Claim
12 words
The process of claim 37 wherein said conveying means is screw means.
Claim 50
Dependent Claim
20 words
The process of claim 47 wherein said screw means is selected from the group consisting of single and multiple screws.
Claim 51
Dependent Claim
30 words
The process of claim 47 wherein said shear forces are generated in said reaction zone by operating said screw means at a rotation rate of from 50 to 600 RPM.
Claim 52
Dependent Claim
47 words
The process of claim 37 wherein the material used in the construction of one or more of said zones is selected from the group consisting of alloys comprising nickel, cobalt, molybdenum, chromium and iron as major alloying elements, and steel coated with inert polymer, ceramic or titanium.
Claim 53
Dependent Claim
23 words
The process of claim 37 wherein the polymer in the feed zone is subjected to a pressure of up to about 600 psig.
Claim 54
Dependent Claim
22 words
The process of claim 38 wherein said inert gas is injected at or adjacent the downstream end of said second restriction means.
Claim 55
Dependent Claim
28 words
The process of claim 37 wherein said inert gas is injected into said neutralization zone so as to flow countercurrent to the flow of said halogenated product mixture.
Claim 56
Dependent Claim
13 words
The process of claim 37 further comprising a supplementary inert gas injection step.
Claim 57
Dependent Claim
30 words
The process of claim 54 wherein said supplementary injection step is performed in a separate scrubbing zone (D) which follows said neutralization zone, prior to delivering said halogenated polymer product.
Claim 58
Dependent Claim
12 words
The process of claim 37 further comprising a final exit zone (E).
Claim 59
Dependent Claim
22 words
The process of claim 37 further comprising stabilizer addition wherein a degradation, oxidation or dehydrohalogenation stabilizer is added to said halogenated polymer.
Claim 60
Dependent Claim
28 words
The process of claim 56 wherein the temperature of said halogenated polymer is adjusted for delivery from said exit zone at a temperature lower than about 130° C.
Claim 61
Dependent Claim
21 words
The process of claim 54 wherein a degradation, oxidation or dehydrohalogenation stabilizer is added in said supplementary inert gas injection step.
Claim 62
Dependent Claim
18 words
The process of claim 56 wherein a degradation, oxidation, or dehydrohalogenation stabilizer is added to said exit zone.
Claim 63
Dependent Claim
23 words
The process of claim 55 wherein said extruder-reactor further comprises filter means to effect the separation of undispersed materials from said halogenated polymer.
Claim 64
Dependent Claim
77 words
The process of claim 37 wherein said polymer mass is subjected to deformation and disruption in said reaction zone and wherein said polymer and said halogenating agent form co-continuous phases within said reaction zone or are present during contact as either co-continuous phases or wherein said halogenating agent is present as a continuous phase and said polymer is present as a discontinuous phase or wherein said halogenating agent is injected at a position filled with said polymer.
Claim 65
Dependent Claim
33 words
The process of claim 62 wherein said polymer is an ethylenically unsaturated polymer selected from the group consisting of butyl rubber, EPDM rubber, styrene butadiene rubber, polyisoprene rubber, polybutadiene rubber and poly(butadiene-isoprene)copolymer rubber.
Claim 66
Dependent Claim
37 words
The process of claim 37 wherein said polymer is selected from the group of saturated polymers consisting of polyisobutylene, ethylene-propylene copolymer, high density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer and polyvinyl chloride.
Claim 67
Dependent Claim
11 words
The process of claim 63 wherein said rubber is butyl rubber.
Claim 68
Dependent Claim
11 words
The process of claim 63 wherein said rubber is EPDM rubber.
Claim 69
Dependent Claim
14 words
The process of claim 64 wherein said saturated polymer is linear low density polyethylene.
Claim 70
Dependent Claim
12 words
The process of claim 65 wherein said butyl rubber is isobutylene-isoprene copolymer.
Claim 71
Dependent Claim
40 words
The process of claim 37 wherein said halogenating agent is selected from the group consisting of chlorine gas, chlorine liquid, sulfuryl chloride, N-chlorosuccinimide, 1,3-dihalo-5,5-dimethylhydantoin, iodobenzene dichloride, iodine monochloride, bromine gas, bromine liquid, bromine chloride, sodium hypobromite, sulfur bromide and N-bromosuccinimide.
Claim 72
Dependent Claim
25 words
The process of claim 37 further comprising adding a diluent to said rubber feed before, at or near the point of addition of said feed.
Claim 73
Dependent Claim
24 words
The process of claim 70 wherein said diluent is selected from the group consisting of volatile saturated hydrocarbons, chlorohydrocarbons, chlorocarbons, non-hydrocarbons and hydrocarbon oils.
Claim 74
Dependent Claim
27 words
The process of claim 71 wherein said diluent is selected from the group consisting of pentane, hexane, methylene chloride, chloroform, carbon tetrachloride, carbon dioxide, and inert gas.
Claim 75
Dependent Claim
26 words
The process of claim 72 wherein said diluent is present in an amount less than about 50 percent by weight based on the weight of rubber.
Claim 76
Dependent Claim
21 words
The process of claim 69 wherein said halogenating agent is selected from the group consisting of bromine, chlorine and bromine chloride.
Claim 77
Dependent Claim
13 words
The process of claim 69 wherein said halogenating agent is diluted with diluent.
Claim 78
Dependent Claim
11 words
The process of claim 75 wherein said halogenating agent is chlorine.
Claim 79
Dependent Claim
24 words
The process of claim 75 wherein said diluent is a gas selected from the group consisting of nitrogen, argon, air and CO 2 .
Claim 80
Dependent Claim
44 words
The process of claim 70 wherein said halogenating agent is diluted with a diluent and wherein the total amount of diluent added to said feed and halogenating agent diluent is less than about 50 percent by weight based on the weight of butyl rubber.
Claim 81
Dependent Claim
27 words
The process of claim 70 wherein said diluent added to said feed is selected from the group consisting of volatile saturated hydrocarbons, chlorohydrocarbons, chlorocarbons and hydrocarbon oils.
Claim 82
Dependent Claim
18 words
The process of claim 68 wherein the temperature in said reaction zone is less than about 170° C.
Claim 83
Dependent Claim
13 words
The process of claim 37 further comprising vent means in said neutralization zone.
Claim 84
Dependent Claim
32 words
The process of claim 81 wherein said conveying means comprises screw means wherein said screw means is configured so as to avoid restricting the exiting flow of inert gas and disengaged materials.
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