Block copolymer, method of making the same, diamine precursors of the same method, method of making such diamines and end products comprising the block copolymer

Claim 2

Organopolysiloxane-polyurea block copolymer characterized by the following recurring unit: where: Z    is a divalent radical selected from phenylene, alkylene, aralkylene and cycloalkylene; Y    is an alkylene radical of 1 to 10 carbon atoms; R    is at least 50% methyl with the balance of the 100% of all R radicals being monovalent alkyl or substituted alkyl radical having from 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical; D    is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; B    is a divalent radical selected from alkylene, aralkylene, cycloalkylene, phenylene, polyethylene oxide polytetramethylene oxide, polycaprolactone, and mixtures thereof; A    is difunctional moiety selected from -O- or - - where G is hydrogen, an alkyl radical of 1 to 10 carbon atoms, phenyl, or an alkylene radical which completes a ring structure including B to form a heterocycle; n    is a number which is 50 or larger; and m    is a number which can be zero to about 25.

Claim 3

The block copolymer of claim 1 further characterized by Z being selected from the group consisting of hexamethylene, methylene, bis-(phenylene), tetramethylene, isophorone, cyclohexylene, and methylene dicyclohexylene.

Claim 4

The block copolymer of claim 1 further characterized by R being methyl.

Claim 5

Method of making organopolysiloxane-polyurea block copolymer, said method characterized by polymerizing: (1) a diamine having a molecular weight of at least 5,000 and the formula: where: R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group; Y is an alkylene radical of 1 to 10 carbon atoms; D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; n is a number which is 50 or larger; and (2) at least one a diisocyanate having the formula OCN-Z-NCO where: Z is a divalent radical selected from the group consisting of hexamethylene, methylene bis-(phenylene), tetramethylene, isophorone, cyclohexylene, and methylene dicyclohexyl; the molar ratio of diamine to diisocyanate being maintained in the range of about 1:0.95 to 1:1.05; and (3) up to 95 weight percent chain extender selected from diamines, dihydroxy compounds or mixtures thereof.

Claim 6

Method of making organopolysiloxane-polyurea block copolymer, said method characterized by polymerizing: (1) a diamine having a molecular weight of at least 5,000 and the formula: where: R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group; Y is an alkylene radical of 1 to 10 carbon atoms; D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; n is a number which is 50 or larger; and (2) at least one a diisocyanate having the formula OCN-Z-NCO where: Z is a divalent radical selected from the group consisting of hexamethylene, methylene bis-(phenylene), tetramethylene, isophorone, cyclohexylene, and methylene dicyclohexyl; the molar ratio of diamine to diisocyanate being maintained in the range of about 1:0.95 to 1:1.05; and (3) up to 95 weight percent chain extender selected from diamines, dihydroxy compounds or mixtures thereof.

Claim 7

The method of claim 4 further characterized by said diisocyanate being a phenylene diisocyanate selected from toluene diisocyanate and p- phenylene diisocyanate.

Claim 8

The method of claim 4 further characterized by said diisocyanate being hexamethylene diisocyanate.

Claim 9

The method of claim 4 further characterized by said diisocyanate being an aralkylene diisocyanate selected from methylene bis phenyl isocyanate and tetramethylxylene diisocyanate.

Claim 10

The method of claim 4 further characterized by said diisocyanate being a cycloalkylene diisocyanate selected from isophorone diisocyanate and methylene dicyclohexyl diisocyanate.

Claim 11

Organopolysiloxane diamine characterized by having a molecular weight of at least 5000 and the general formula: where: R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group; Y is an alkylene radical of 1 to 10 carbon atoms; D is hydrogen, an alkyl radical of 1 to 10 carbon atoms of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle, or phenyl; n is a number of 50 or larger.

Claim 12

Organopolysiloxane diamine characterized by having a molecular weight of at least 5000 and the general formula: where: R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical group; Y is an alkylene radical of 1 to 10 carbon atoms; D is hydrogen, an alkyl radical of 1 to 10 carbon atoms of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle, or phenyl; n is a number of 50 or larger.

Claim 13

Method of making the organopolysiloxane diamine of claim 9 characterized by: (1) combining under reaction conditions: (a) amine functional end blocker of the general formula where: Y is an alkylene radical of 1 to 10 carbon atoms; and R is at least 50% methyl with the balance of 100% of all R radicals being a monovalent alkyl or substituted alkyl radical having from 2 to 12 carbon atoms, a vinylene radical phenyl radical, or substituted phenyl radical; D is hydrogen, an alkyl group of 1 to 10 carbon atoms or an alkylene radical of 1 to 10 carbon atoms which completes a ring structure including Y to form a heterocyclic ring, or phenyl; (b) sufficient cyclic siloxane to react with said amine functional end blocker to form a lower molecular weight organopolysiloxane diamine having a molecular weight less than about 2,000 and general formula where: R, Y are D as defined above; and X is a number in the range of about 4 to 40; (c) a catalytic amount of tetramethyl ammonium 3-aminopropyl dimethyl silanolate; (2) continuing the reaction until substantially all of said amine functional end blocker is consumed; and (3) adding additional cyclic siloxane until the organopolysiloxane diamine of claim 9 is obtained.

Claim 14

The method of claim 10 further characterized by said catalytic amount being less than bout 0.05% by weight of said organopolysiloxane diamine of claim 9 is obtained.

Claim 15

The method of claim 10 further characterized by said catalytic amount being from about 0.005 to about 0.03 weight percent of said organopolysiloxane diamine of claim 9 is obtained.

Claim 16

The method of claim 10 further characterized by said reaction conditions comprising a reaction temperature range of about 80°C to about 90°C, a reaction time of about 5 to 7 hours, and dropwise addition addition of said additional cyclic siloxane.

Claim 17

A pressure-sensitive adhesive composition characterized by including the block copolymer of claim 1.

Claim 18

A compound characterized by having a molecular structure represented by the formula: where D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; Y is an alkylene radical of 1 to 10 carbon atoms; R is at least 50% methyl with the balance of 100% of all R radials being a monovalent alkyl or substituted alkyl radical having from 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical; and M⁺ is the cation K⁺, Li⁺ or N(CH₃)₄⁺.

Claim 19

A compound characterized by having a molecular structure represented by the formula: where D is hydrogen, an alkyl radical of 1 to 10 carbon atoms or an alkylene radical which completes a ring structure including Y to form a heterocycle or phenyl; Y is an alkylene radical of 1 to 10 carbon atoms; R is at least 50% methyl with the balance of 100% of all R radials being a monovalent alkyl or substituted alkyl radical having from 2 to 12 carbon atoms, a vinylene radical, phenyl radical, or substituted phenyl radical; and M⁺ is the cation K⁺, Li⁺ or N(CH₃)₄⁺.

Claim 20

A release agent comprising the copolymer of claim 1.

Claim 21

The release agent of claim 16 wherein the copolymer comprises from about 15% to about 70% hard segments.

Claim 22

A pressure-sensitive adhesive material comprising a backing member having a front side and a back side, a pressure-sensitive adhesive mass on the front side and a low adhesion backsize on the back side of the backing member comprising the release agent of claim 16.

Claim 23

A pressure-sensitive adhesive material comprising a backing member having a front side and a back side, a pressure-sensitive adhesive mass on the front side and a low adhesion backsize on the back side of the backing member comprising the release agent of claim 16.