Patent US4384072A successfully refreshed from Google Patents.
US4384072A
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Process for the manufacture of halogenated elastomers
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1981-09-30
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Granted: 1983-05-17
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Expires: 2001-09-30
Abstract
Abstract Continuous halogenation of olefinically unsaturated rubber is achieved in an extruder - reactor employing reactants, conditions and design features directed to maximizing mixing and contact of the rubber with the halogenating agent and neutralizing agent while simultaneously minimizing side reactions and polymer degradation. The rubber passes through five extruder-reactor zones under controlled conditions to achieve halogenation: feed, reaction, neutralization, wash and exit. The halogenated rubber, for example, halogenated butyl rubber can be vulcanized in the absence of sulfur, e.g., with zinc oxide and stearic acid, and is useful in all applications where commercially available chlorinated and brominated rubbers are presently employed.
Inventors
- 👤 Neil F. Newman
- 👤 Ronald C. Kowalski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 20:22
CPC Classifications
C; C08; C08L; C08L21/00; C08F; C08F8/00; C08F8/18; C08F8/20; C08C; C08C19/00; C08C19/12; C08F8/22; Y; Y02; Y02P; Y02P20/00; Y02P20/141; Y02P20/143
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
195 words
In a process for the continuous halogenation of olefinically unsaturated rubber of the type which comprises continuously contacting said rubber with a halogen wherein the improvement comprises: feeding said rubber to an extruder-reactor comprising (A) a feed zone, (B) a reaction zone, (C) a neutralization zone, (D) a wash zone, (E) an exit zone, and an extruder screw means transversing zones A through E inclusively, wherein: (1) said feed zone characterized by sufficient pressure and temperature to form the rubber feed into a cohesive mass and convey said mass past a restrictive dam means following said feed zone; (2) said reaction zone comprises halogenation agent injection means at an extruder-reactor position filled with said rubber, means for producing a high degree of rubber mixing, and said restrictive dam means following said feed zone; (3) said neutralization zone separated from said reaction zone by restrictive dam means and means for injecting neutralizing agents located at or immediately adjacent to the downstream end of said dam; and (4) the materials of construction for said inlet zone, reaction zone and neutralization zone selected so as to minimize reaction with said halogenating agent, corrosion and concurrent undesirable side reactions.
Claim 2
Dependent Claim
195 words
In a process for the continuous halogenation of olefinically unsaturated rubber of the type which comprises continuously contacting said rubber with a halogen wherein the improvement comprises: feeding said rubber to an extruder-reactor comprising (A) a feed zone, (B) a reaction zone, (C) a neutralization zone, (D) a wash zone, (E) an exit zone, and an extruder screw means transversing zones A through E inclusively, wherein: (1) said feed zone characterized by sufficient pressure and temperature to form the rubber feed into a cohesive mass and convey said mass past a restrictive dam means following said feed zone; (2) said reaction zone comprises halogenation agent injection means at an extruder-reactor position filled with said rubber, means for producing a high degree of rubber mixing, and said restrictive dam means following said feed zone; (3) said neutralization zone separated from said reaction zone by restrictive dam means and means for injecting neutralizing agents located at or immediately adjacent to the downstream end of said dam; and (4) the materials of construction for said inlet zone, reaction zone and neutralization zone selected so as to minimize reaction with said halogenating agent, corrosion and concurrent undesirable side reactions.
Claim 3
Dependent Claim
32 words
The process of claim 1 wherein said olefinically unsaturated rubber is selected from the group consisting of butyl rubber, EPDM rubber, styrene butadiene rubber, polyisoproprene rubber, polybutadiene rubber, and poly(butadiene-isoprene) copolymer rubber.
Claim 4
Dependent Claim
11 words
The process of claim 2 wherein said rubber is butyl rubber.
Claim 5
Dependent Claim
11 words
The process of claim 2 wherein said rubber is EPDM rubber.
Claim 6
Dependent Claim
18 words
The process of claim 1 wherein said halogen is selected from the group consisting of bromine and chlorine.
Claim 7
Dependent Claim
12 words
The process of claim 3 wherein said butyl rubber is isobutylene-isoprene copolymer.
Claim 8
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 9
Dependent Claim
21 words
The process of claim 7 wherein said diluent is selected from the group consisting of volatile hydrocarbons, chlorohydrocarbons, chlorocarbons and non-hydrocarbons.
Claim 10
Dependent Claim
28 words
The process of claim 8 wherein said diluent is selected from the group consisting of pentane, hexane, methylene chloride, chloroform, carbon tetrachloride, carbon dioxide, inert gas and water.
Claim 11
Dependent Claim
24 words
The process of claim 9 wherein said diluent is present at less than about 50 percent by weight based on the weight of rubber.
Claim 12
Dependent Claim
40 words
The process of claim 1 wherein said halogenating agent is selected from the group consisting of chlorine gas, aqueous chlorine, sulfuryl chloride, N-Chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin iodobenzene dichloride, iodine monochloride, bromine gas, bromine liquid, bromine chloride, sodium hypobromite, sulfur bromide and N-bromosuccinimide.
Claim 13
Dependent Claim
13 words
The process of claim 11 wherein said halogenating agent is diluted with diluent.
Claim 14
Dependent Claim
11 words
The process of claim 12 wherein said halogenating agent is chlorine.
Claim 15
Dependent Claim
24 words
The process of claim 12 wherein said diluent is a gas selected from the group consisting of nitrogen, argon, air and CO 2 .
Claim 16
Dependent Claim
22 words
The process of claim 12 wherein said inert diluent is selected from the group consisting of volatile saturated hydrocarbons, chlorohydrocarbons and chlorocarbons.
Claim 17
Dependent Claim
44 words
The process of claim 7 wherein said halogenating agent is diluted with an inert diluent and wherein the total amount of said viscosity reducing diluent and halogenating agent diluent is less than about 50 percent by weight based on the weight of butyl rubber.
Claim 18
Dependent Claim
34 words
The process of claim 1 wherein an aqueous base is added to said neutralization zone, said aqueous base selected from the group consisting of hydroxide, bicarbonates and carbonates of alkali and alkaline earth metals.
Claim 19
Dependent Claim
21 words
The process of claim 1 wherein water is added to said wash zone to remove nonpolymer-bound materials from said halogenated rubber.
Claim 20
Dependent Claim
22 words
The process of claim 6 wherein said halogenated butyl rubber leaves said exit zone at a temperature lower than about 130° C.
Claim 21
Dependent Claim
18 words
The process of claim 1 wherein a degradation, oxidation or dehydrohalogenation stabilizer is added to said wash zone.
Claim 22
Dependent Claim
18 words
The process of claim 1 wherein a degradation, oxidation or dehydrohalogenation stabilizer is added to said exit zone.
Claim 23
Dependent Claim
24 words
The process of claim 18 wherein said extruder-reactor further comprises filter means to effect the separation of said nonpolymer-bound materials from said halogenated rubber.
Claim 24
Dependent Claim
40 words
The process of claim 1 wherein said restrictive dam 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 25
Dependent Claim
20 words
The process of claim 23 wherein said restrictive dam means is about 0.5 to about 8 screw diameters in length.
Claim 26
Dependent Claim
18 words
The process of claim 1 wherein said restrictive dam means following said feed zone comprises said reaction zone.
Claim 27
Dependent Claim
49 words
The process of claim 1 wherein said means for producing a high degree of rubber mixing is selected from the group consisting of a reverse flighted screw section, a multiple reverse flighted screw section, a pin section, and a series of very short alternating reverse and forward screw sections.
Claim 28
Dependent Claim
44 words
The process of claim 1 wherein said restrictive dam 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 29
Dependent Claim
18 words
The process of claim 6 wherein the temperature in said reaction zone is less than about 170° C.
Claim 30
Dependent Claim
43 words
The process of claim 23 wherein said restrictive dam 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 31
Dependent Claim
43 words
The process of claim 27 wherein said restrictive dam 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 32
Dependent Claim
12 words
The process of claim 7 wherein said diluent is a hydrocarbon oil.
Claim 33
Dependent Claim
14 words
The process of claim 1 wherein said extruder screw means is a twin screw.
Claim 34
Dependent Claim
14 words
The process of claim 1 wherein said extruder screw means is a single screw.
Claim 35
Dependent Claim
11 words
The process of claim 12 wherein said halogenating agent is bromine.
Claim 36
Dependent Claim
12 words
The process of claim 12 wherein said halogenating agent is bromine chloride.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-05-16 | 1986-11-15 | 1987-05-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-05-16 | 1990-11-15 | 1991-05-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-05-16 | 1994-11-15 | 1995-05-17 | $7700.00 | Window Closed / Lapsed |