Connected branch copolymers, methods for their production, and copying materials including same

Claim 2

A capped connected branch copolymer comprising: (A) a core segment having a valence of v, wherein v is an integer, and having correspondingly v terminal bonds connected to: (B) v polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about two, one of said terminal bonds being connected to said core segment, and each of said branched polymer segments being connected via its remaining (t-1) terminal bonds to: (C) a set of linear polymer segments, with an average of t-1 linear polymer segments per set, to provide a group of about v (t-1) linear polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within said group, the capped connected branch copolymer having a group of terminal linear polymer segments bearing groups capable of effecting hydrogen bonding; and (D) a set of cap segments connected to terminals of the terminal linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 4 carbon atoms, there being on average at least about 0.5 of said alkylene oxide residues for each terminal of the terminal linear polymer segments not connected to the branched polymer segments.

Claim 3

A capped connected branch copolymer according to claim 1 comprising only the elements carbon, hydrogen, oxygen, nitrogen, phosphorus and silicon.

Claim 4

A capped connected branch copolymer according to claim 2 comprising only the elements carbon, hydrogen, oxygen and nitrogen.

Claim 5

A capped connected branch copolymer according to claim 1 wherein the core, branched and linear segments provide separate hydrophobic and hydrophilic portions of the polymer.

Claim 6

A capped connected branch copolymer according to claim 1 wherein the core segment has a linear or star structure.

Claim 7

A capped connected branch copolymer according to claim 5 having a divalent linear core segment connecting two polyvalent, non-crosslinked, branched polymer segments, which are in turn connected to two sets of linear polymer segments.

Claim 8

A capped connected branch copolymer according to claim 6 wherein the linear core segment comprises a polysiloxane, polyoxyalkylene, polyphosphazine, polyalkylene, polyester, polyamide, polyurethane, or an alkyl ether.

Claim 9

A capped connected branch copolymer according to claim 5 wherein the star core segment comprises a polyether derived from reacting an alkylene oxide with glycerol, pentaerythritol, dipentaerythritol, or trimethylolpropane.

Claim 10

A capped connected branch copolymer according to claim 5 wherein the liner core segment comprises an oxyalkylene homopolymer, or a random or block copolymer of an oxyalkylene.

Claim 11

A capped connected branch copolymer according to claim 9 wherein the linear core segment further comprises a glycidyl polyether derived from methyl glycidyl ether.

Claim 12

A capped connected branch copolymer according to claim 9 wherein the core segment comprises an ethylene oxide/propylene oxide random copolymer or an ethylene oxide homopolymer.

Claim 13

A capped connected branch copolymer according to claim 9 wherein the core segment has an average molecular weight in the range of about 4000 to about 16,000.

Claim 14

A capped connected branch copolymer according to claim 1 wherein at least one branched polymer segment comprises a polyether or polyimine.

Claim 15

A capped connected branch copolymer according to claim 1 wherein at least one branched polymer segment comprises residues of a monomer of the formula: ##STR10## wherein X is nitrogen, oxygen, or sulfur; Y is alkyl, alkylamine or hydroxyalkyl; R is hydrogen or lower alkyl; R 1 and R 3 are each hydrogen, alkyl, aryl or aralkyl; R 2 is (1) an alkyl, aryl or aralkyl group which may be connected to R 1 to form a cyclic ring or (2) hydrogen when n is 0, or (3) a covalent bond when n is 1; R 4 is hydrogen or lower alkyl; m is (1) 0 when W is oxygen or sulfur or (2) 1 when X is nitrogen; n is 0 or 1 provided that n is 1 when X is oxygen or sulfur.

Claim 16

A capped connected branch copolymer according to claim 13 wherein at least one branched polymer segment comprises a glycidyl polyether.

Claim 17

A capped connected branch copolymer according to claim 15 wherein the glycidyl polyether is derived from glycidol.

Claim 18

A capped connected branch copolymer according to claim 1 wherein at least one branched polymer segment comprises a polyimine derived from aziridine.

Claim 19

A capped connected branch copolymer according to claim 1 wherein at least one branched polymer segment has a reduced branching density due to the presence of linear polymer segments within the branched polymer segment.

Claim 20

A capped connected branch copolymer according to claim 1 wherein the terminal groups capable of effecting hydrogen bonding comprise carboxylic acid groups, esters, salts or amides of carboxylic acid groups, amino groups, phosphate groups, esters, salts or amides of phosphate groups, hydroxyl groups, or residues of any of such groups remaining after attachment of the cap segments to the terminal linear polymer segments via the terminal groups.

Claim 21

A capped connected branch copolymer according to claim 19 wherein the terminal groups capable of effecting hydrogen bonding comprise ether linkages remaining after attachment of the cap segments to the terminal linear polymer segments via terminal hydroxyl groups on the terminal linear polymer segments.

Claim 22

A capped connected branch copolymer according to claim 20 wherein the terminal linear polymer segments comprise polyoxyalkylene linear polymer segments.

Claim 23

A capped connected branch copolymer according to claim 21 wherein at least one linear polymer segment further comprises a glycidyl polyether derived from methyl glycidyl ether.

Claim 24

A capped connected branch copolymer according to claim 1 wherein the average number of terminal linear polymer segments is from about 8 to about 30.

Claim 25

A capped connected branch copolymer according to claim 1 wherein the average molecular weight of each of the group of terminal linear polymer segments is from about 4000 to about 10,000.

Claim 26

A capped connected branch copolymer according to claim 1 wherein the core, branched and linear polymer segments form a copolymer of the formula: [[(C').sub.n B'].sub.x [(C).sub.m B].sub.y ].sub.z A[B(C).sub.m ].sub.y [B'(C').sub.n ].sub.x wherein A is a core segment having a valence of z+1; B and B 1 are noncrosslinked, branched polymer segments having valences of m+1 and n+1, respectively; C and C 1 are linear polymer segments having substantially similar chain lengths and composition within each group of x or y segments; m is greater than 1 and may vary between each set of linear polymer segments; n is (1) greater than 1 or (2) may be 0 when y is 0 or (2) m when y is 1 and the product of all m values when y is greater than 1; y and z are each integers greater than or equal to 0; provided that y is at least 1 when z is 0.

Claim 27

A capped connected branch copolymer according to claim 25 having a structure such that in said formula y is 0 and z is 1, the core, branched and linear polymer segments thus forming a copolymer of the formula: (C').sub.n B'- A - B'(C').sub.n wherein A, B 1 , C 1 and n are as defined in claim 25.

Claim 28

A capped connected branch copolymer according to claim 1 wherein there are on average from about 0.75 to about 3 of said alkylene oxide residues for each terminal of the linear polymer segments not connected to the branched polymer segments.

Claim 29

A capped connected branch copolymer according to claim 27 wherein there are on average from about 1 to about 2 of said alkylene oxide residues for each terminal of the linear polymer segments not connected to the branched polymer segments.

Claim 30

A capped connected branch copolymer according to claim 1 wherein the alkylene oxide residues comprise residues of an epoxyalkane containing from about 8 to about 16 carbon atoms.

Claim 31

A capped connected branch copolymer according to claim 29 wherein the alkylene oxide residues comprise residues of a 1,2-epoxy straight-chain alkane containing from about 8 to about 16 carbon atoms.

Claim 32

A capped connected branch copolymer according to claim 1 having a molecular weight in the range of about 20,000 to about 80,000.

Claim 33

A capped connected branch copolymer according to claim 1 having a transition temperature of not more than about 70° C.

Claim 34

A capped connected branch copolymer comprising: (A) a core segment comprising a linear polyether connected to: (B) two polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about 2, one of the branched polymer segments being connected, via one of its t terminal bonds, to each end of the linear core segment, and each of the branched polymer segments being connected to: (C) a set of linear polyether polymer segments, with an average of (t-1) linear polymer segments per set, to provide a group of about 2(t-1) linear polyether polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within the group, the linear polyether polymer segments comprising residues of alkylene oxide monomers containing not more than about 5 carbon atoms; and (D) a set of cap segments connected to terminals of the linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 8 carbon atoms, there being on average at least about 0.75 of said alkylene oxide residues for each terminal of the linear polymer segments not connected to the branched polymer segments.

Claim 35

A capped connected branch copolymer comprising: (A) a core segment comprising a linear polyether connected to: (B) two polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about 2, one of the branched polymer segments being connected, via one of its t terminal bonds, to each end of the linear core segment, and each of the branched polymer segments being connected to: (C) a set of linear polyether polymer segments, with an average of (t-1) linear polymer segments per set, to provide a group of about 2(t-1) linear polyether polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within the group, the linear polyether polymer segments comprising residues of alkylene oxide monomers containing not more than about 5 carbon atoms; and (D) a set of cap segments connected to terminals of the linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 8 carbon atoms, there being on average at least about 0.75 of said alkylene oxide residues for each terminal of the linear polymer segments not connected to the branched polymer segments.

Claim 36

A process for the preparation of a capped connected branch copolymer, the process comprising: procuring an uncapped connected branch copolymer comprising (A) a core segment having a valence of v, wherein v is an integer, and having correspondingly v terminal bonds connected to: (B) v polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about two, one of said terminal bonds being connected to said core segment, and each of said branched polymer segments being connected via its remaining (t-1) terminal bonds to: (C) a set of linear polymer segments, with an average of t-1 linear polymer segments per set, to provide a group of about v (t-1) linear polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within said group, the connected branch copolymer having a group of terminal linear polymer segments bearing groups capable of effecting hydrogen bonding; and reacting the uncapped connected branch copolymer with an alkylene oxide containing at least about 4 carbon atoms, the amount of the alkylene oxide reacted with the uncapped connected branch copolymer being at least about 0.5 molecule for each terminal of the terminal linear polymer segments of the connected branch copolymer which is not connected to the branched polymer segments, thereby causing the alkylene oxide to react with the terminal linear polymer segments of the uncapped connected branch copolymer to produce a set of cap segments connected to terminals of the terminal linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 4 carbon atoms, there being on average at least about 0.5 of said alkylene oxide residues for each terminal of the terminal linear polymer segments not connected to the branched polymer segments.

Claim 37

A process for the preparation of a capped connected branch copolymer, the process comprising: procuring an uncapped connected branch copolymer comprising (A) a core segment having a valence of v, wherein v is an integer, and having correspondingly v terminal bonds connected to: (B) v polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about two, one of said terminal bonds being connected to said core segment, and each of said branched polymer segments being connected via its remaining (t-1) terminal bonds to: (C) a set of linear polymer segments, with an average of t-1 linear polymer segments per set, to provide a group of about v (t-1) linear polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within said group, the connected branch copolymer having a group of terminal linear polymer segments bearing groups capable of effecting hydrogen bonding; and reacting the uncapped connected branch copolymer with an alkylene oxide containing at least about 4 carbon atoms, the amount of the alkylene oxide reacted with the uncapped connected branch copolymer being at least about 0.5 molecule for each terminal of the terminal linear polymer segments of the connected branch copolymer which is not connected to the branched polymer segments, thereby causing the alkylene oxide to react with the terminal linear polymer segments of the uncapped connected branch copolymer to produce a set of cap segments connected to terminals of the terminal linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 4 carbon atoms, there being on average at least about 0.5 of said alkylene oxide residues for each terminal of the terminal linear polymer segments not connected to the branched polymer segments.

Claim 38

A process according to claim 34 wherein the alkylene oxide reacts with the terminal groups capable of effecting hydrogen bonding so that, in the capped connected branch copolymer, the cap segments are connected to the terminal linear polymer segments via residues of said terminal groups.

Claim 39

A process according to claim 34 wherein the capped connected branch copolymer produced comprises only the elements carbon, hydrogen, oxygen, nitrogen, phosphorus and silicon.

Claim 40

A process according to claim 36 wherein the capped connected branch copolymer produced comprises only the elements carbon, hydrogen, oxygen and nitrogen.

Claim 41

A process according to claim 34 wherein, in the uncapped connected branch copolymer, the groups capable of effecting hydrogen bonding comprise carboxylic acid groups, esters, salts or amides of carboxylic acid groups, amino groups, phosphate groups, esters, salts or amides of phosphate groups, or hydroxyl groups.

Claim 42

A process according to claim 38 wherein, in the uncapped connected branch copolymer, the terminal linear polymer segments comprise hydroxyl-terminated polyoxyalkylene linear polymer segments.

Claim 43

A process according to claim 34 wherein the amount of the alkylene oxide reacted with the connected branch copolymer is from about 0.75 to about 3 molecules of the alkylene oxide for each terminal linear polymer segment of the uncapped connected branch copolymer.

Claim 44

A process according to claim 40 wherein the amount of the alkylene oxide reacted with the connected branch copolymer is from about 1 to about 2 molecules of the alkylene oxide for each terminal linear polymer segment of the uncapped connected branch copolymer.

Claim 45

A process according to claim 34 wherein the alkylene oxide is an epoxyalkane containing from about 8 to about 16 carbon atoms.

Claim 46

A process according to claim 42 wherein the alkylene oxide is a 1,2-epoxy straight-chain alkane containing from about 8 to about 16 carbon atoms.

Claim 47

A process according to claim 34 wherein the uncapped connected branch copolymer reacted with the alkylene oxide comprises: (A) a core segment comprising a linear polyether connected to: (B) two polyvalent, non-crosslinked branched polymer segments each having an average of t terminals bonds, wherein t is greater than about 2, one of the branched polymer segments being connected, via one of its t terminal bonds, to each end of the linear core segment, and each of the branched polymer segments being connected to: (C) a set of linear polyether polymer segments, with an average of (t-1) linear polymer segments per set, to provide a group of about 2(t-1) linear polyether polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition within the group, the linear polyether polymer segments comprising residues of alkylene oxide monomers containing not more than about five carbon atoms.

Claim 48

A process according to claim 34 wherein the uncapped connected branch copolymer reacted with the alkylene oxide has been produced by a process comprising: (1) reacting a core reactant having at least one reactive terminal group with non-crosslinking, branching polymerization monomers by polymerizing these monomers to completion under polymerization conditions sufficient to produce a branched, core compound having a mono-, di- or polyvalent core segment terminated with non-crosslinked, branching polymer segments each having at least two branch sites remote from the core segment; followed by (2) polymerizing at least one linear polymerization monomer onto the branch sites of the branched, core compound under polymerization conditions sufficient to provide a linearly extended, branched, core compound as a connected branch copolymer having linear polymer segments with substantially similar chain lengths and compositions extending from the branch sites.

Claim 49

A process according to claim 44 wherein the core reactant is a linear or star compound.

Claim 50

A process according to claim 46 wherein the core reactant is a divalent linear compound.

Claim 51

A process according to claim 47 wherein the core reactant comprises an alkylene oxide, or a random or block copolymer of alkylene oxides.

Claim 52

A process according to claim 48 wherein the core reactant comprises an ethylene oxide/propylene oxide random copolymer or an ethylene oxide homopolymer.

Claim 53

A process according to claim 34 wherein the branching polymerization monomer is glycidol.

Claim 54

A process according to claim 45 wherein the linear polymerization monomer comprises a co-monomer mixture of alkylene oxides.

Claim 55

A process according to claim 51 wherein the co-monomers are added sequentially to form linear, block copolymer segments.

Claim 56

A process according to claim 45 wherein the linear polymerization monomers are ethylene oxide, propylene oxide or mixtures thereof.

Claim 57

A composition for use in the preparation of carbonless copying sheets, the composition comprising a capped connected branch copolymer comprising: (A) a core segment having a valence of v, wherein v is an integer, and having correspondingly v terminal bonds connected to: (B) v polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about two, one of said terminal bonds being connected to said core segment, and each of said branched polymer segments being connected via its remaining (t-1) terminal bonds to: (C) a set of linear polymer segments, with an average of t-1 linear polymer segments per set, to provide a group of about v (t-1) linear polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition with said group, the capped connected branch copolymer having a group of terminal linear polymer segments bearing groups capable of effecting hydrogen bonding; and (D) a set of cap segments connected to terminals of the terminal linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 4 carbon atoms, there being on average at least about 0.5 of said alkylene oxide residues for each terminal of the terminal linear polymer segments not connected to the branched polymer segments; and a plurality of microcapsules dispersed in the capped connected branch copolymer, these microcapsules comprising a color precursor.

Claim 58

A composition for use in the preparation of carbonless copying sheets, the composition comprising a capped connected branch copolymer comprising: (A) a core segment having a valence of v, wherein v is an integer, and having correspondingly v terminal bonds connected to: (B) v polyvalent, non-crosslinked branched polymer segments each having an average of t terminal bonds, wherein t is greater than about two, one of said terminal bonds being connected to said core segment, and each of said branched polymer segments being connected via its remaining (t-1) terminal bonds to: (C) a set of linear polymer segments, with an average of t-1 linear polymer segments per set, to provide a group of about v (t-1) linear polymer segments wherein the linear polymer segments have substantially similar chain lengths and composition with said group, the capped connected branch copolymer having a group of terminal linear polymer segments bearing groups capable of effecting hydrogen bonding; and (D) a set of cap segments connected to terminals of the terminal linear polymer segments which are not connected to the branched polymer segments, each of the cap segments comprising at least one residue of an alkylene oxide containing at least about 4 carbon atoms, there being on average at least about 0.5 of said alkylene oxide residues for each terminal of the terminal linear polymer segments not connected to the branched polymer segments; and a plurality of microcapsules dispersed in the capped connected branch copolymer, these microcapsules comprising a color precursor.

Claim 59

A composition according to claim 54 wherein, in the capped connected branch copolymer, the terminal groups capable of effecting hydrogen bonding comprise carboxylic acid groups, esters, salts or amides of carboxylic acid groups, amino groups, phosphate groups, esters, salts or amides of phosphate groups, hydroxyl groups, or residues of any of such groups remaining after attachment of the cap segments to the terminal linear polymer segments via the terminal groups.

Claim 60

A composition according to claim 55 wherein, in the capped connected branch copolymer, the terminal group capable of effecting hydrogen bonding comprise ether linkages remaining after attachment of the cap segments to the terminal linear polymer segments via terminal hydroxyl groups on the terminal linear polymer segments.

Claim 61

A composition according to claim 56 wherein, in the capped connected branch copolymer, the terminal linear polymer segments comprise polyoxyalkylene linear polymer segments.

Claim 62

A composition according to claim 54 wherein the core segment of the capped connected branch copolymer comprises a linear polyether comprising alkylene oxide residues.

Claim 63

A composition according to claim 54 wherein, in the capped connected branch copolymer, at least one branched polymer segment comprises a glycidyl polyether.

Claim 64

A composition according to claim 54 wherein, in the cap segments of the capped connected branch copolymer, the alkylene oxide residues comprise residues of an epoxyalkane containing from about 8 to about 16 carbon atoms.

Claim 65

A composition according to claim 60 wherein, in the capped connected branch copolymer, the alkylene oxide residues forming the cap segments comprise residues of a 1,2-epoxy straight-chain alkane containing from about 8 to about 16 carbon atoms.

Claim 66

A composition according to claim 54 wherein the capped connected branch copolymer has a transition temperature not in excess of about 70° C.