US4157432A — Bulk sulfonation process

Claim 1

Independent Claim 116 words

A process for the bulk sulfonation of hydrocarbon polymers, characterized before sulfonation, by the presence in said polymers of sulfonatable sites selected from the group consisting of olefinic unsaturation and arylene radicals, which comprises: (a) mechanically mixing said polymers or mixtures of hydrocarbon polymers comprising said polymers with a sulfonation reagent comprising sulfuric acid or sulfur trioxide or both, in the substantial absence of a solvent for said polymers at a temperature which is between the glass transition temperature and 250° C. for amorphous polymers and between the crystalline melting point and 250° C. for crystalline or semicrystalline polymers for a time sufficient to effect sulfonation; followed by (b) recovering said sulfonated polymers and said mixtures.

Claim 2

Dependent Claim 116 words

A process for the bulk sulfonation of hydrocarbon polymers, characterized before sulfonation, by the presence in said polymers of sulfonatable sites selected from the group consisting of olefinic unsaturation and arylene radicals, which comprises: (a) mechanically mixing said polymers or mixtures of hydrocarbon polymers comprising said polymers with a sulfonation reagent comprising sulfuric acid or sulfur trioxide or both, in the substantial absence of a solvent for said polymers at a temperature which is between the glass transition temperature and 250° C. for amorphous polymers and between the crystalline melting point and 250° C. for crystalline or semicrystalline polymers for a time sufficient to effect sulfonation; followed by (b) recovering said sulfonated polymers and said mixtures.

Claim 3

Dependent Claim 166 words

Process according to claim 1 wherein said hydrocarbon polymers are selected from the group consisting of: (a) homopolymers and copolymers of one or more alkenyl hydrocarbons having the general formula Ar-C(R)═CH 2 wherein Ar is a monovalent sulfonatable aromatic radical and R is hydrogen or methyl; (b) copolymers of one or more C 4 to C 10 conjugated diolefins with one or more C 8 to C 12 vinyl aromatic hydrocarbons; (c) random copolymers of one or more C 8 to C 12 vinyl aromatic hydrocarbons comprising about 40 to 60 weight percent of said vinyl aromatic with one or more Type III C 4 to C 8 monoolefins; (d) random elastomeric copolymers of one or more C 4 to C 10 conjugated diolefins with one or more Type III C 4 to C 8 monoolefins; and (e) random interpolymers of one or more Type I C 2 to C 18 monoolefins and one or more C 6 to C 12 nonconjugated acyclic or alicyclic diolefins.

Claim 4

Dependent Claim 14 words

Process according to claim 1, wherein said sulfonation reagent is a pre-formed acetyl sulfate.

Claim 5

Dependent Claim 23 words

Process according to claim 1, wherein said sulfonation reagent is prepared in situ by the serial addition of acetic anhydride and sulfuric acid.

Claim 6

Dependent Claim 23 words

Process according to claim 1, wherein said sulfonation reagent is prepared in situ by the alternate addition of acetic anhydride and sulfuric acid.

Claim 7

Dependent Claim 25 words

Process according to claim 1, wherein said sulfonation reagent comprises a complex or coordination compound of sulfuric acid or sulfur trioxide with a Lewis base.

Claim 8

Dependent Claim 12 words

Process according to claim 1, wherein said polymer is an unmodified polystyrene.

Claim 9

Dependent Claim 12 words

Process according to claim 1, wherein said polymer is a butyl rubber.

Claim 10

Dependent Claim 30 words

Process according to claim 1, wherein said polymer is an EPDM selected from the group consisting of terpolymers of ethylene, propylene and 1,4-hexadiene, and terpolymers of ethylene, propylene and 5-ethylidene-2-norbornene.

Claim 11

Dependent Claim 63 words

Process according to claim 1, wherein said sulfonation reagent is selected from the group consisting of adducts or complexes of sulfuric acid or sulfur trioxide with diethyl ether, acetic acid, acetic anhydride, trifluoroacetic acid, trifluoroacetic anhydride, benzoic acid, benzoic anhydride, propionic acid, n-butyric acid, dioxane, tetrahydrofuran, 1,4-oxathiane, pyridine, dimethylaniline, n-ethylmorpholine, dimethylformamide, dimethyl sulfone, dimethyl sulfoxide, triethyl phosphate, hexamethyl phosphoramide and bis (β-chloroethyl ether).

Claim 12

Dependent Claim 12 words

Process according to claim 1, wherein temperature is less than 225° C.

Claim 13

Dependent Claim 22 words

The process according to claim 1 wherein said polymer contains said olefinic unsaturation and said temperature is less than about 150° C.

Claim 14

Dependent Claim 21 words

The process according to claim 1 wherein said polymer contains aromatic groups and said temperature is less than about 200° C.

Claim 15

Dependent Claim 187 words

A process for the bulk sulfonation of hydrocarbon polymers, characterized before sulfonation, by the presence in said polymers of sulfonatable sites selected from the group consisting of olefinic unsaturation and arylene radicals, which comprises: (a) mechanically mixing said polymers or mixtures of hydrocarbon polymers comprising said polymers with a sulfonation reagent comprising sulfuric acid or sulfur trioxide or both, in the substantial absence of a solvent for said polymers at a temperature which is between the glass transition temperature and 250° C. for amorphous polymers and between the crystalline melting point and 250° C. for crystalline or semicrystalline polymers for a time sufficient to effect sulfonation; followed by (b) neutralization with a basic material selected from the group consisting of ammonia, mono and polyamines and basic compounds in which the cation is an element selected from the group consisting of Groups I-A, I-B, II-A and II-B of the Periodic Table of Elements, aluminum, antimony, and lead; and the anion is selected from the group consisting of oxides, hydroxides, C 1 to C 5 alkoxides, carbonates and fatty acids; followed by (c) recovering of the neutralized sulfonated polymer.

Claim 16

Dependent Claim 187 words

A process for the bulk sulfonation of hydrocarbon polymers, characterized before sulfonation, by the presence in said polymers of sulfonatable sites selected from the group consisting of olefinic unsaturation and arylene radicals, which comprises: (a) mechanically mixing said polymers or mixtures of hydrocarbon polymers comprising said polymers with a sulfonation reagent comprising sulfuric acid or sulfur trioxide or both, in the substantial absence of a solvent for said polymers at a temperature which is between the glass transition temperature and 250° C. for amorphous polymers and between the crystalline melting point and 250° C. for crystalline or semicrystalline polymers for a time sufficient to effect sulfonation; followed by (b) neutralization with a basic material selected from the group consisting of ammonia, mono and polyamines and basic compounds in which the cation is an element selected from the group consisting of Groups I-A, I-B, II-A and II-B of the Periodic Table of Elements, aluminum, antimony, and lead; and the anion is selected from the group consisting of oxides, hydroxides, C 1 to C 5 alkoxides, carbonates and fatty acids; followed by (c) recovering of the neutralized sulfonated polymer.

Claim 17

Dependent Claim 166 words

Process according to claim 14, wherein said hydrocarbon polymers are selected from the group consisting of: (a) homopolymers and copolymers of one or more alkenyl hydrocarbons having the general formula Ar-C(R)═CH 2 wherein Ar is a monovalent sulfonatable aromatic radical and R is hydrogen or methyl; (b) copolymers of one or more C 4 to C 10 conjugated diolefins with one or more C 8 to C 12 vinyl aromatic hydrocarbons; (c) random copolymers of one or more C 8 to C 12 vinyl aromatic hydrocarbons comprising about 40 to 60 weight percent of said vinyl aromatic with one or more Type III C 4 to C 8 monoolefins; (d) random elastomeric copolymers of one or more C 4 to C 10 conjugated diolefins with one or more Type III C 4 to C 8 monoolefins; and (e) random interpolymers of one or more Type I C 2 to C 18 monoolefins and one or more C 6 to C 12 nonconjugated acyclic or alicyclic diolefins.

Claim 18

Dependent Claim 14 words

Process according to claim 14, wherein said sulfonation reagent is a pre-formed acetyl sulfate.

Claim 19

Dependent Claim 23 words

Process according to claim 14, wherein said sulfonation reagent is prepared in situ by the serial addition of acetic anhydride and sulfuric acid.

Claim 20

Dependent Claim 23 words

Process according to claim 14, wherein said sulfonation reagent is prepared in situ by the alternate addition of acetic anhydride and sulfuric acid.

Claim 21

Dependent Claim 25 words

Process according to claim 14, wherein said sulfonation reagent comprises a complex or coordination compound of sulfuric acid or sulfur trioxide with a Lewis base.

Claim 22

Dependent Claim 12 words

Process according to claim 14, wherein said polymer is an unmodified polystyrene.

Claim 23

Dependent Claim 12 words

Process according to claim 14, wherein said polymer is a butyl rubber.

Claim 24

Dependent Claim 30 words

Process according to claim 14, wherein said polymer is an EPDM selected from the group consisting of terpolymers of ethylene, propylene and 1,4-hexadiene; and terpolymers of ethylene, propylene and 5-ethylidene-2-norbornene.

Claim 25

Dependent Claim 64 words

Process according to claim 14, wherein said sulfonation reagent is selected from the group consisting of adducts or complexes of sulfuric acid or sulfur trioxide with diethyl ether, acetic acid, acetic anhydride, trifluoroacetic acid, trifluoroacetic anhydride, benzoic acid, benzoic anhydride, propionic acid, n-butyric acid, dioxane, tetrahydrofuran, 1,4-oxathiane, pyridine, dimethylaniline, n-ethylmorpholine, dimethyl formamide, dimethyl sulfone, dimethyl sulfoxide, triethyl phosphate hexamethyl phosphoramide and bis (β-chloroethyl ether).

Claim 26

Dependent Claim 25 words

Process according to claim 14, wherein said basic material is selected from the group consisting of zinc oxide, zinc stearate, magnesium oxide and magnesium hydroxide.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1982-06-04	1982-12-04	1983-06-05	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1986-06-04	1986-12-04	1987-06-05	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1990-06-04	1990-12-04	1991-06-05	$7700.00	Window Closed / Lapsed

Bulk sulfonation process

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