Perhalogenated co-butyl rubber

Claim 2

A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF A PERHALOGENATED BUTYL RUBBER CONSISTING OF A COPOLYMER HAVING FROM 85 TO 99.5% BY WEIGHT OF AN ISOOLEFIN HAVING FROM 4 TO 7 CARBON ATOMS, COMBINED WITH 15 TO 0.5% BY WEIGHT OF A CONJUGATED DIOLEFIN HAVING FROM 4 TO 14 CARBON ATOMS (REFERRED TO HEREINAFTER AS BUTYL RUBBER), CONTAINING IN THE LINEAR BACKBONE SUBSTANTIALLY RANDOMLY INSERTED DIOLEFIN UNITS HAVING RESIDUAL UNSATURATION AND AT LEAST TWO HALOGEN ATOMS ATTACHED THERETO.

Claim 3

The composition of claim 1, wherein the isoolefin is isobutylene and the diolefin is isoprene.

Claim 4

The composition of claim 2, having a general structure represented by:

Claim 5

The composition of claim 1, wherein the linear backbone additionally contains substantially randomly inserted diolefin units having conjugated diene unsaturation.

Claim 6

The composition of claim 2, wherein the linear backbone additionally contains substantially randomly inserted isoprene units having conjugated diene unsaturation.

Claim 7

The composition of claim 2, wherein there is combined in the copolymer from about 0.5 to about 3.0 percent by weight perhalogenated isoprene residue, substantially all of said isoprene units having at least two halogens attached thereto.

Claim 8

The composition of claim 2, wherein the halogen is chlorine.

Claim 9

The composition of claim 2, wherein the halogen is bromine.

Claim 10

The composition of claim 2 cured with sulfur or a sulfur-containing curing agent.

Claim 11

The composition of claim 2 cured with a phenolaldehyde resin.

Claim 12

The composition of claim 2, blended with from 10 to 90 weight percent of a high unsaturation rubber.

Claim 13

The composition of claim 2, covulcanized with from 10 to 90 weight percent of a high unsaturation rubber.

Claim 14

The composition of claim 11, wherein the high unsaturation rubber is natural rubber.

Claim 15

The composition of claim 11, wherein the high unsaturation rubber is SBR.

Claim 16

A process for preparing perhalogenated butyl rubber which comprises: a. contacting, in a reaction zone, a solution of halogenated butyl rubber with a suitable catalyst for a time sufficient to dehydrohalogenate said halogenated butyl rubber; b. recovering from said reaction zone the dehydrohalogenated butyl rubber, which is characterized by having conjugated diene unsaturation randomly inserted along the backbone of said butyl rubber; c. in a second reaction zone, in the absence of light, contacting a solution of said dehydrohalogenated butyl rubber with a halogen, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and d. recovering said pErhalogenated butyl rubber.

Claim 17

A process for preparing perhalogenated butyl rubber which comprises: a. contacting, in a reaction zone, a solution of halogenated butyl rubber with a suitable catalyst for a time sufficient to dehydrohalogenate said halogenated butyl rubber; b. recovering from said reaction zone the dehydrohalogenated butyl rubber, which is characterized by having conjugated diene unsaturation randomly inserted along the backbone of said butyl rubber; c. in a second reaction zone, in the absence of light, contacting a solution of said dehydrohalogenated butyl rubber with a halogen, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and d. recovering said pErhalogenated butyl rubber.

Claim 18

A process for preparing a perhalogenated copolymer consisting of from 85 to 99.5% by weight of an isoolefin having from 4 to 7 carbon atoms, combined with 15 to 0.5% by weight of a conjugated diolefin having from 4 to 14 carbon atoms, containing in the linear backbone substantially randomly inserted diolefin units having residual unsaturation, and at least 2 halogen atoms attached thereto, which comprises, A. contacting a solution of halogenated butyl rubber, in a reaction zone with: a. from about 2 X 10 3 to 2 X 10 2 moles of a soluble metal carboxylate per 100 grams of said halogenated butyl rubber, the metals being selected from the metals of Groups Ib, IIb, IVa and VIII of the Periodic Table; b. about 0 to 2 moles of a carboxylic acid per gram atom of halogen in the halogenated butyl rubber present in said reaction zone; and c. about 0.5 to 2 moles of an oxide, hydroxide or carboxylate of a metal selected from the metals of Groups Ia or IIa of the Periodic Table, per gram atom of halogen in the halogenated butyl rubber present in the reaction zone; B. recovering from the reaction zone said butyl rubber, having a reduced halogen content, which is characterized by having a conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 19

A process for preparing a perhalogenated copolymer consisting of from 85 to 99.5% by weight of an isoolefin having from 4 to 7 carbon atoms, combined with 15 to 0.5% by weight of a conjugated diolefin having from 4 to 14 carbon atoms, containing in the linear backbone substantially randomly inserted diolefin units having residual unsaturation, and at least 2 halogen atoms attached thereto, which comprises, A. contacting a solution of halogenated butyl rubber, in a reaction zone with: a. from about 2 X 10 3 to 2 X 10 2 moles of a soluble metal carboxylate per 100 grams of said halogenated butyl rubber, the metals being selected from the metals of Groups Ib, IIb, IVa and VIII of the Periodic Table; b. about 0 to 2 moles of a carboxylic acid per gram atom of halogen in the halogenated butyl rubber present in said reaction zone; and c. about 0.5 to 2 moles of an oxide, hydroxide or carboxylate of a metal selected from the metals of Groups Ia or IIa of the Periodic Table, per gram atom of halogen in the halogenated butyl rubber present in the reaction zone; B. recovering from the reaction zone said butyl rubber, having a reduced halogen content, which is characterized by having a conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 20

The process of claim 16, wherein the butyl rubber is a copolymer consisting of from 85 to 99.5% by weight isobutylene, combined with 15 to 0.5% by weight isoprene, having a number average molecular weight of from about 5,000 to 500,000.

Claim 21

The process of claim 16, wherein the soluble metal carboxylate is a zinc carboxylate.

Claim 22

The process of claim 16, wherein the soluble metal carboxylate is zinc naphthenate.

Claim 23

The process of claim 16, wherein the metal of the Group Ia or IIa oxide, hydroxide or carboxylate is calcium.

Claim 24

The process of claim 16, wherein the metal of the Group Ia or IIa oxide, hydroxide or carboxylate is magnesium.

Claim 25

The process of claim 16, wherein the halogenated butyl rubber is dehydrohalogenated by contacting said halogenated butyl rubber with: a. zinc naphthenate; b. naphthenic acid; and c. calcium oxide.

Claim 26

The process of claim 16, wherein the dehydrohalogenation is conducted at a temperature of between about 75* and 200*C., for a period of time to at least partially dehydrohalogenate said halogenated butyl rubber.

Claim 27

The process of claim 16, wherein the carboxylic acid is an aliphatic or naphthenic acid having from 4 to 20 carbon atoms.

Claim 28

The process of claim 16, wherein the halogenating agent is gaseous chlorine.

Claim 29

The process of claim 16, wherein the halogenating agent is bromine.

Claim 30

The process of claim 16, wherein the halogenating agent is chlorine or bromine in a solution of the same solvent as the dehydrohalogenated butyl rubber.

Claim 31

The process of claim 16, wherein the halogenating agent is in excess of the stoichiometric amount required for perhalogenation of the dehydrohalogenated butyl rubber.

Claim 32

A process for preparing perhalogenated butyl rubber which comprises: A. contacting a solution of halogenated butyl rubber, in a reaction zone, with a metal salt of a strong acid wherein said metal is selected from the metals of Group IIa or IIb of the Periodic Table, the mole ratio of rubber to metal salt being from 0.1 to 0.5, at a temperature of from 100* to 220*C., for a time sufficient to dehydrohalogenate said halogenated butyl rubber, and said metal salt being other than a Friedel-Crafts catalyst; B. recovering from the reaction zone, said butyl rubber having a reduced halogen content, which is characterized by having conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 33

A process for preparing perhalogenated butyl rubber which comprises: A. contacting a solution of halogenated butyl rubber, in a reaction zone, with a metal salt of a strong acid wherein said metal is selected from the metals of Group IIa or IIb of the Periodic Table, the mole ratio of rubber to metal salt being from 0.1 to 0.5, at a temperature of from 100* to 220*C., for a time sufficient to dehydrohalogenate said halogenated butyl rubber, and said metal salt being other than a Friedel-Crafts catalyst; B. recovering from the reaction zone, said butyl rubber having a reduced halogen content, which is characterized by having conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20* to 75*C., at a feed level of 0.2 to 1.1 moles of elemental halogen per mole of conjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 34

The process of claim 29 wherein the solution of halogenated butyl rubber is contacted with a hydrocarbon insoluble metal salt of a strong acid wherein said metal is selected from the metals of Group IIa or IIb of the Periodic Table, at a temperature of about 130* to about 180*C., the mole ratio of rubber to metal salt being from about 0.2 to about 0.5.

Claim 35

The process of claim 30, wherein the catalyst is a metal salt of a strong acid selected from the group consisting of phosphate, sulfate, chloride and nitrate, of a metal selected from the metals of Groups IIa and IIb of the Periodic Table.

Claim 36

The process of claim 30, wherein the Group IIa metal is calcium.

Claim 37

The process of claim 30, wherein the Group IIb metal is zinc.

Claim 38

The process of claim 30, wherein the metal salt of a strong acid is tricalcium orthophosphate.

Claim 39

The process of claim 30, wherein the halogenating agent is gaseous chlorine.

Claim 40

The process of claim 30, wherein the halogenating agent is bromine.

Claim 41

The process of claim 30, wherein the halogenating agent is chlorine or bromine in a solution of the same solvent as the dehydrohalogenated butyl rubber.

Claim 42

The process of claim 30, wherein the halogenating agent is in excess of the stoichiometric amount required for perhalogenation of the dehydrohalogenated butyl rubber.

Claim 43

The process of claim 29 wherein the butyl rubber having a reduced halogen content is halogenated in the presence of light.

Claim 44

The process of claim 15 wherein the dehydrohalogenated butyl rubber is contacted with a halogen in the presence of light.

Claim 45

The process of claim 16, wherein the butyl rubber having a reduced halogen content, is contacted with a halogen in the presence of light.

Claim 46

A process for preparing perhalogenated butyl rubber which comprises: A. contacting a solution of halogenated butyl rubber, in a reaction zone, with a Friedel-Crafts catalyst and a metal oxide, hydroxide or carboxylate of a metal selected from the metals of Group Ia and IIa and wherein the Friedel-Crafts catalyst is a metal salt of a strong acid wherein said metal is selected from the metals of Group IIa or IIb of the Periodic Table of the Elements, the mole ratio of rubber to metal salt being about 0.1 to about 0.5, at a temperature of about 100*C. to about 220*C. for a time sufficient to dehydrogenate said halogenated butyl rubber; B. recovering from the reaction zone, said butyl rubber having a reduced halogen content, which is characterized by having conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20 to 75*C., at a feed level of 0.2 to 1.1 miles of elemental halogen per mole of coNjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 47

A process for preparing perhalogenated butyl rubber which comprises: A. contacting a solution of halogenated butyl rubber, in a reaction zone, with a Friedel-Crafts catalyst and a metal oxide, hydroxide or carboxylate of a metal selected from the metals of Group Ia and IIa and wherein the Friedel-Crafts catalyst is a metal salt of a strong acid wherein said metal is selected from the metals of Group IIa or IIb of the Periodic Table of the Elements, the mole ratio of rubber to metal salt being about 0.1 to about 0.5, at a temperature of about 100*C. to about 220*C. for a time sufficient to dehydrogenate said halogenated butyl rubber; B. recovering from the reaction zone, said butyl rubber having a reduced halogen content, which is characterized by having conjugated diene unsaturation randomly inserted along the isoolefin backbone of said butyl rubber; C. contacting a solution of said butyl rubber having a reduced halogen content, in a reaction zone, in the absence of light, with a halogenating agent, at a temperature of from -20 to 75*C., at a feed level of 0.2 to 1.1 miles of elemental halogen per mole of coNjugated diene moiety present in the dehydrohalogenated butyl rubber solution; and D. recovering said perhalogenated butyl rubber.

Claim 48

The process of claim 42 wherein the metal of the metal oxide, hydroxide or carboxylate is calcium.

Claim 49

The process of claim 42 wherein the metal of the metal oxide, hydroxide or carboxylate is magnesium.

Claim 50

The process of claim 42 wherein the halogenating agent is gaseous chlorine.

Claim 51

The process of claim 42 wherein the halogenating agent is bromine.

Claim 52

The process of claim 42 wherein the halogenating agent is chlorine or bromine in a solution of the same solvent as the dehydrohalogenating butyl rubber.

Claim 53

The process of claim 42 wherein the halogenating agent is in excess of the stoichiometric amount required for perhalogenation of the dehydrohalogenated butyl rubber.

Claim 54

The process of claim 42 wherein the butyl rubber having a reduced halogen content is halogenated in the presence of light.

Claim 55

The process of claim 42 wherein the dehydrohalogenated butyl rubber is contacted with halogen in the presence of light.