US4163832A — Polythioethers formed by anionic ring opening of …

Claim 1

Independent Claim 63 words

A process for preparing a thiol terminated stereoregular polythioether compound having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting at least one unsymmetrical episulfide with a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols, and mixtures thereof in the presence of a catalyst selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N'-tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine, and triethylenediamine.

Claim 2

Dependent Claim 63 words

A process for preparing a thiol terminated stereoregular polythioether compound having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting at least one unsymmetrical episulfide with a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols, and mixtures thereof in the presence of a catalyst selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N'-tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine, and triethylenediamine.

Claim 3

Dependent Claim 31 words

The process of claim 1 wherein the sulfur compound has the general formula R m (SH) m wherein R is an organic radical and m is the valence of said radical.

Claim 4

Dependent Claim 33 words

The process of claim 2 wherein R is a hydrocarbyl radical or substituted hydrocarbyl radical of about C 1 to about C 30 carbon atoms and m is about 1 to about 10.

Claim 5

Dependent Claim 24 words

The process of claim 3 wherein R is a C 1 to C 10 aliphatic hydrocarbon radical and m is about 1 to 4.

Claim 6

Dependent Claim 28 words

The process of claim 1 wherein the organic thiol is a C 1 to C 30 hydrocarbyl dithiol or a C 1 to C 30 substituted hydrocarbyl dithiol.

Claim 7

Dependent Claim 18 words

The process of claim 5 wherein the organic thiol is a C 2 to C 6 alkylene dithiol.

Claim 8

Dependent Claim 28 words

The process of claim 1 wherein the organic thiol is a C 1 to C 30 hydrocarbyl monothiol or a C 1 to C 30 substituted hydrocarbyl monothiol.

Claim 9

Dependent Claim 28 words

The process of claim 1 wherein the organic thiol is a C 1 to C 30 hydrocarbyl monothiol or a C 1 to C 30 substituted hydrocarbyl trithiol.

Claim 10

Dependent Claim 26 words

The process of claim 1 wherein the episulfide has the general formula: ##STR60## wherein R', R" and R'" are hydrogen, hydrocarbyl radicals or substituted hydrocarbyl radicals.

Claim 11

Dependent Claim 11 words

The process of claim 1 wherein the episulfide is propylene sulfide.

Claim 12

Dependent Claim 17 words

The process of claim 1 wherein at least two different episulfides are reacted with said sulfur compound.

Claim 13

Dependent Claim 10 words

The process of claim 1 wherein the catalyst is trimethylamine.

Claim 14

Dependent Claim 21 words

The process of claim 1 wherein the process is conducted at a temperature ranging from about 25° to about 40° C.

Claim 15

Dependent Claim 47 words

A process for preparing stereoregular diterminal-thioether dithiol compounds having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting at least one unsymmetrical episulfide with hydrogen sulfide in the presence of a catalyst selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N'-tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine and triethylenediamine.

Claim 16

Dependent Claim 47 words

A process for preparing stereoregular diterminal-thioether dithiol compounds having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting at least one unsymmetrical episulfide with hydrogen sulfide in the presence of a catalyst selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N'-tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine and triethylenediamine.

Claim 17

Dependent Claim 10 words

The process of claim 14 wherein the catalyst is trimethylamine.

Claim 18

Dependent Claim 21 words

The process of claim 14 wherein the process is conducted at a temperature ranging from about 25° to about 40° C.

Claim 19

Dependent Claim 104 words

A process for preparing secondary and tertiary thiol terminated stereoregular polythioether compounds having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols and mixtures thereof with at least one unsymmetrical episulfide of the formula: ##STR61## wherein R', R" and R'" are selected from the group consisting of hydrogen, hydrocarbyl radicals and substituted hydrocarbyl radicals with the proviso that R', R" and R'" are not the same and if R" is hydrogen, R'" must also be a hydrogen, wherein said reaction is conducted in the presence of a catalyst comprising trimethylamine.

Claim 20

Dependent Claim 104 words

A process for preparing secondary and tertiary thiol terminated stereoregular polythioether compounds having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols and mixtures thereof with at least one unsymmetrical episulfide of the formula: ##STR61## wherein R', R" and R'" are selected from the group consisting of hydrogen, hydrocarbyl radicals and substituted hydrocarbyl radicals with the proviso that R', R" and R'" are not the same and if R" is hydrogen, R'" must also be a hydrogen, wherein said reaction is conducted in the presence of a catalyst comprising trimethylamine.

Claim 21

Dependent Claim 21 words

The process of claim 17 wherein the process is conducted at a temperature ranging from about 25° to about 40° C.

Claim 22

Dependent Claim 13 words

The process of claim 17 wherein the unsymmetrical episulfide is a mono-substituted episulfide.

Claim 23

Dependent Claim 24 words

The process of claim 19 wherein R" and R'" are hydrogen and R' is a C 1 to C 6 alkyl or cycloalkyl radical.

Claim 24

Dependent Claim 28 words

A process for preparing stereoregular polythioether dithiols having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting propylene sulfide with ethane dithiol in the presence of trimethylamine.

Claim 25

Dependent Claim 28 words

A process for preparing stereoregular polythioether dithiols having 3 to 20,000 recurring alkylene sulfide groups which comprises reacting propylene sulfide with ethane dithiol in the presence of trimethylamine.

Claim 26

Dependent Claim 176 words

A secondary or tertiary polythioether thiol block copolymer having the general formula: ##STR62## wherein R is a C 1 to C 200 ,000 hydrocarbon radical or a C 1 to C 200 ,000 hydrocarbon radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, dialkylamino groups; R' is a C 1 to C 200 ,000 hydrocarbyl or C 1 to C 200 ,000 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthio, carbohydrocarbyloxy, acyl, alkylene sulfide and alkylene oxide groups; R" and R'" are each independently selected from the group consisting of hydrogen, C 1 to C 30 hydrocarbyl radicals with the proviso that if R" is hydrogen, R'" must also be hydrogen; R"" is selected from the group consisting of hydrogen and C 1 to C 4 aliphatic hydrocarbyl radical; p is an integer of 1 to about 1,000; n is an integer of 1 to about 50,000; r is an integer of 1 to about 10; m is an integer of 1 to about 500; X is a tertiary organoamine; and t is an integer of 0-10.

Claim 27

Dependent Claim 176 words

A secondary or tertiary polythioether thiol block copolymer having the general formula: ##STR62## wherein R is a C 1 to C 200 ,000 hydrocarbon radical or a C 1 to C 200 ,000 hydrocarbon radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, dialkylamino groups; R' is a C 1 to C 200 ,000 hydrocarbyl or C 1 to C 200 ,000 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthio, carbohydrocarbyloxy, acyl, alkylene sulfide and alkylene oxide groups; R" and R'" are each independently selected from the group consisting of hydrogen, C 1 to C 30 hydrocarbyl radicals with the proviso that if R" is hydrogen, R'" must also be hydrogen; R"" is selected from the group consisting of hydrogen and C 1 to C 4 aliphatic hydrocarbyl radical; p is an integer of 1 to about 1,000; n is an integer of 1 to about 50,000; r is an integer of 1 to about 10; m is an integer of 1 to about 500; X is a tertiary organoamine; and t is an integer of 0-10.

Claim 28

Dependent Claim 46 words

The product of claim 22 wherein R has a maximum of 1000 carbon atoms; m is an integer of about 1 to about 10; R' is a C 1 to C 4 hydrocarbon radical; R" and R'" are hydrogen; and t is an integer of 0-3.

Claim 29

Dependent Claim 83 words

The product of claim 22 wherein R is a C 1 to C 30 aliphatic hydrocarbon radical; R' is a C 1 to C 4 hydrocarbyl radical selected from the group consisting of alkyl, allyl, and propargyl; R', R"" are hydrogen; m is an integer of 2 or 3; p is an integer of 1 to about 1000; n is an integer of about 2 to about 3000; r is an integer of 2 to 3; and t is an integer of 0-3.

Claim 30

Dependent Claim 65 words

The product of claim 22 wherein R is a C 2 to C 12 hydrocarbyl radical; R' is methyl; R", R'" and R"" are hydrogen; X is trimethylamine; m is an integer of 2 or 3; n is an integer of about 1 to about 20,000; p is an integer of about 1 to about 1000 and t is an integer of 0 to 3.

Claim 31

Dependent Claim 135 words

A secondary polythioether polythiol block copolymer having the general formula: ##STR63## wherein R is a C 1 to C 1000 hydrocarbon radical, a C 1 to C 1000 hydrocarbon radical substituted with oxyethers, thioethers or esters; R' is selected from the group consisting of a C 1 to C 30 hydrocarbon radical; a C 1 to C 30 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthiol, carbohydrocarbyloxy, acyl, alkylene sulfide, and alkylene oxide groups; R"" is hydrogen or C 1 to C 4 aliphatic hydrocarbyl radical; m is an integer of 1 to about 50; n is an integer of 1 to about 50,000; p is an integer of 1 to about 1,000; r is an integer of 1 to about 10; X is a tertiary organoamine; and t is an integer of 0 to 3.

Claim 32

Dependent Claim 135 words

A secondary polythioether polythiol block copolymer having the general formula: ##STR63## wherein R is a C 1 to C 1000 hydrocarbon radical, a C 1 to C 1000 hydrocarbon radical substituted with oxyethers, thioethers or esters; R' is selected from the group consisting of a C 1 to C 30 hydrocarbon radical; a C 1 to C 30 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthiol, carbohydrocarbyloxy, acyl, alkylene sulfide, and alkylene oxide groups; R"" is hydrogen or C 1 to C 4 aliphatic hydrocarbyl radical; m is an integer of 1 to about 50; n is an integer of 1 to about 50,000; p is an integer of 1 to about 1,000; r is an integer of 1 to about 10; X is a tertiary organoamine; and t is an integer of 0 to 3.

Claim 33

Dependent Claim 9 words

The product of claim 26 wherein R"" is hydrogen.

Claim 34

Dependent Claim 9 words

The product of claim 26 wherein p is 1.

Claim 35

Dependent Claim 6 words

The vulcanized product of claim 26.

Claim 36

Dependent Claim 73 words

A secondary polythioether dithiol block copolymer of the formula: ##STR64## wherein R is a C 1 to C 200 ,000 divalent hydrocarbon radical or a C 1 to C 200 ,000 hydrocarbon radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, dialkylamino groups; p is an integer of 1 to about 1000; n is an integer of 1 to about 50,000; X is trimethylamine and t is an integer of 0 to 3.

Claim 37

Dependent Claim 73 words

A secondary polythioether dithiol block copolymer of the formula: ##STR64## wherein R is a C 1 to C 200 ,000 divalent hydrocarbon radical or a C 1 to C 200 ,000 hydrocarbon radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, dialkylamino groups; p is an integer of 1 to about 1000; n is an integer of 1 to about 50,000; X is trimethylamine and t is an integer of 0 to 3.

Claim 38

Dependent Claim 6 words

The vulcanized product of claim 30.

Claim 39

Dependent Claim 17 words

The block copolymer of claim 30 wherein R is a divalent C 1 -C 30 hydrocarbon radical.

Claim 40

Dependent Claim 24 words

The block copolymer of claim 30 wherein R is a divalent aliphatic hydrocarbon radical having 1 to 6 carbon atoms and t is 0.

Claim 41

Dependent Claim 21 words

The block copolymer of claim 30 wherein n is an integer of about 2 to about 3000 and t is 0.

Claim 42

Dependent Claim 58 words

A process for preparing secondary and tertiary thiol terminated stereoregular polythioether block copolymers having 3 to 20,000 recurring alkylene sulfide groups and at least two different episulfides which comprises selectively reacting said episulfides with a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols and mixtures thereof in the presence of a catalyst comprising trimethylamine.

Claim 43

Dependent Claim 58 words

A process for preparing secondary and tertiary thiol terminated stereoregular polythioether block copolymers having 3 to 20,000 recurring alkylene sulfide groups and at least two different episulfides which comprises selectively reacting said episulfides with a sulfur compound selected from the group consisting of hydrogen sulfide, organic thiols and mixtures thereof in the presence of a catalyst comprising trimethylamine.

Claim 44

Dependent Claim 40 words

The process of claim 35 wherein the reaction is carried out sequentially by first adding a first episulfide to the reaction mixture; allowing the reaction to go substantially to completion; and then adding the second episulfide to the reaction mixture.

Claim 45

Dependent Claim 14 words

The process of claim 36 wherein the episulfides are ethylene episulfide and propylene episulfide.

Claim 46

Dependent Claim 21 words

The process of claim 35 wherein the reactions are carried out at temperatures ranging from about 25° to about 40° C.

Claim 47

Dependent Claim 131 words

A polythioether thiol compound having the general formula: ##STR65## wherein R is a C 1 to C 200 ,000 hydrocarbyl radical or a C 1 to C 200 ,000 hydrocarbyl radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, and dialkylamino groups; R' is a C 1 to C 200 ,000 hydrocarbyl or C 1 to C 200 ,000 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthio, carbohydrocarbloxy, acyl, alkylene sulfide and alkylene oxide groups; R" and R'" are hydrogen or C 1 to C 30 hydrocarbyl radicals with the proviso that if R" is hydrogen, R'" is also hydrogen; X is a tertiary organoamine n is an integer of 3 to about 1,000; m is an integer of 1 to about 10; and t is an integer of 0 to 3.

Claim 48

Dependent Claim 131 words

A polythioether thiol compound having the general formula: ##STR65## wherein R is a C 1 to C 200 ,000 hydrocarbyl radical or a C 1 to C 200 ,000 hydrocarbyl radical substituted with oxyethers, thioethers, esters, halogenated aromatic groups, and dialkylamino groups; R' is a C 1 to C 200 ,000 hydrocarbyl or C 1 to C 200 ,000 hydrocarbyl radical substituted with hydroxy, hydrocarbyloxy, hydrocarbylthio, carbohydrocarbloxy, acyl, alkylene sulfide and alkylene oxide groups; R" and R'" are hydrogen or C 1 to C 30 hydrocarbyl radicals with the proviso that if R" is hydrogen, R'" is also hydrogen; X is a tertiary organoamine n is an integer of 3 to about 1,000; m is an integer of 1 to about 10; and t is an integer of 0 to 3.

Claim 49

Dependent Claim 48 words

The thioether thiol of claim 39 wherein R has a maximum of 1000 carbon atoms; R' is a C 1 to C 4 hydrocarbyl radical; R" and R'" are hydrogen; n is an integer of 2 to about 3,000; and m is an integer of 1 to 4.

Claim 50

Dependent Claim 6 words

The vulcanized product of claim 39.

Claim 51

Dependent Claim 10 words

The thioether thiol of claim 40 wherein m is 1.

Claim 52

Dependent Claim 10 words

The thioether thiol of claim 40 wherein m is 2.

Claim 53

Dependent Claim 10 words

The thioether thiol of claim 40 wherein m is 3.

Claim 54

Dependent Claim 68 words

Stereoregular polythioether thiol adducts having 3 to 20,000 recurring alkylene sulfide groups formed by a tertiary amine base catalyzed reaction of propylene sulfide and an organic thiol selected from the group consisting of methanethiol, ethanethiol, benzenethiol, 3,4-dichlorobenzenethiol, 4-cyanobenzenethiol, 4-nitrobenzenethiol, 4-methylthiobenzenethiol, 3-chloropropanethiol, 3-hydroxypropanethiol, 3-cyanopropanethiol, ethanedithiol, trimethylene dithiol and tetramethylenedithiol, wherein said tertiary amine catalyst is selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N',tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine and triethylenediamine.

Claim 55

Dependent Claim 68 words

Stereoregular polythioether thiol adducts having 3 to 20,000 recurring alkylene sulfide groups formed by a tertiary amine base catalyzed reaction of propylene sulfide and an organic thiol selected from the group consisting of methanethiol, ethanethiol, benzenethiol, 3,4-dichlorobenzenethiol, 4-cyanobenzenethiol, 4-nitrobenzenethiol, 4-methylthiobenzenethiol, 3-chloropropanethiol, 3-hydroxypropanethiol, 3-cyanopropanethiol, ethanedithiol, trimethylene dithiol and tetramethylenedithiol, wherein said tertiary amine catalyst is selected from the group consisting of trimethylamine, tetramethyl azabicyclooctane, N,N,N',N',tetramethyl-ethylenediamine, trans-2,5-dimethyl piperazine and triethylenediamine.

Claim 56

Dependent Claim 38 words

Stereoregular polythioether adducts having 3 to 20,000 recurring alkylene sulfide groups formed by the trimethylamine base catalyzed reaction of propylene sulfide and an organic thiol selected from the group consisting of methanethiol, ethanethiol, ethanedithiol, trimethylene dithiol and tetramethylenedithiol.

Claim 57

Dependent Claim 38 words

Stereoregular polythioether adducts having 3 to 20,000 recurring alkylene sulfide groups formed by the trimethylamine base catalyzed reaction of propylene sulfide and an organic thiol selected from the group consisting of methanethiol, ethanethiol, ethanedithiol, trimethylene dithiol and tetramethylenedithiol.

Claim 58

Dependent Claim 36 words

Stereoregular polythioether thiol adducts having 3 to 20,000 recurring alkylene sulfide groups formed by the trimethylamine base catalyzed reaction of propylene sulfide and an organic dithiol selected from the group consisting of ethanedithiol, trimethylenedithiol and tetramethylenedithiol.

Claim 59

Dependent Claim 36 words

Stereoregular polythioether thiol adducts having 3 to 20,000 recurring alkylene sulfide groups formed by the trimethylamine base catalyzed reaction of propylene sulfide and an organic dithiol selected from the group consisting of ethanedithiol, trimethylenedithiol and tetramethylenedithiol.

Claim 60

Dependent Claim 26 words

The polythiol of the formula: ##STR66## wherein m is an integer of 1 to about 50 and n is an integer from 2 to about 3000.

Claim 61

Dependent Claim 26 words

The polythiol of the formula: ##STR66## wherein m is an integer of 1 to about 50 and n is an integer from 2 to about 3000.

Claim 62

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR67## wherein n is an integer of 2 to about 3,000.

Claim 63

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR67## wherein n is an integer of 2 to about 3,000.

Claim 64

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR68## wherein n is an integer of 2 to about 3,000.

Claim 65

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR68## wherein n is an integer of 2 to about 3,000.

Claim 66

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR69## wherein n is an integer of 2 to about 3,000.

Claim 67

Dependent Claim 18 words

The polythioether thiol adduct of the formula: ##STR69## wherein n is an integer of 2 to about 3,000.

Claim 68

Dependent Claim 28 words

The polythioether thiol adduct of the formula: ##STR70## wherein m is an integer of 1 to about 50 and n is an integer of 2 to about 3,000.

Claim 69

Dependent Claim 28 words

The polythioether thiol adduct of the formula: ##STR70## wherein m is an integer of 1 to about 50 and n is an integer of 2 to about 3,000.

Claim 70

Dependent Claim 28 words

The polythioether thiol adduct of the formula: ##STR71## wherein m is an integer of 1 to about 50 and n is an integer of 2 to about 3,000.

Claim 71

Dependent Claim 28 words

The polythioether thiol adduct of the formula: ##STR71## wherein m is an integer of 1 to about 50 and n is an integer of 2 to about 3,000.

Claim 72

Dependent Claim 16 words

A polythioether thiol of the formula: ##STR72## wherein n is an integer of 3 to 1000.

Claim 73

Dependent Claim 16 words

A polythioether thiol of the formula: ##STR72## wherein n is an integer of 3 to 1000.

Claim 74

Dependent Claim 43 words

A polythioether dithiol hydrocarbyl diisocyanate polyadduct compound of the general formula: ##STR73## wherein n is an integer of 3 to 1000 and m is an integer of 1 to about 10, R is a C 1 to C 200 ,000 divalent hydrocarbon radical.

Claim 75

Dependent Claim 43 words

A polythioether dithiol hydrocarbyl diisocyanate polyadduct compound of the general formula: ##STR73## wherein n is an integer of 3 to 1000 and m is an integer of 1 to about 10, R is a C 1 to C 200 ,000 divalent hydrocarbon radical.

Claim 76

Dependent Claim 31 words

A polythioether dithiol ethylene bis-acrylate polyadduct compound of the general formula: ##STR74## wherein n is an integer of 3 to 1000 and m is an integer of 1 to about 10.

Claim 77

Dependent Claim 31 words

A polythioether dithiol ethylene bis-acrylate polyadduct compound of the general formula: ##STR74## wherein n is an integer of 3 to 1000 and m is an integer of 1 to about 10.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1982-08-06	1983-02-05	1983-08-07	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1986-08-06	1987-02-05	1987-08-07	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1990-08-06	1991-02-05	1991-08-07	$7700.00	Window Closed / Lapsed

Polythioethers formed by anionic ring opening of episulfides

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