Polyfluoropolyethers having pendant perfluoroalkoxy groups

Claim 2

Perfluoropolyether compositions comprising (1) normally liquid peroxidic poly(perfluorooxyalkylene) compositions comprising a mixture of peroxidic poly(perfluorooxyalkylene) compounds, each compound comprising a backbone of randomly distributed, perfluorooxyalkylene units represented by the formulas --CF 2 O--, ##STR157## and --O--, which, when bonded to an --O-- of any of the perfluorooxyalkylene units, forms a peroxy group, --O--O--, which imparts the peroxidic characteristics to the composition, and backbone-pendant perfluoroalkoxy groups, the terminal ether oxygen atoms of which are bonded to carbon atoms of the ##STR158## backbone units; (2) derivatives of the poly(perfluorooxyalkylene) compositions comprising a mixtures of non-peroxidic polyfluoropolyether compounds; and (3) derivatives of the non-peroxidic polyfluoropolyether compounds comprising functional and non-functional polyfluoropolyether compounds.

Claim 3

Compositions according to claim 1 wherein said backbone is represented by the formula ##STR159## where each R 1 is independently a fluorine or a perfluoroalkyl group selected from linear, branched, and cyclic groups; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a perfluoroalkyl group or a perfluoroalkyl group substituted with one or more further ether oxygen atoms; w is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 or greater; x is a number representing the average number of ##STR160## units randomly distributed within the chain and has a value of 1 or greater; y and y' are each a number representing the average number of ##STR161## units; respectively, randomly distributed within the chain, the sum of y and y' having a value of 1 or greater, and the ratio y/y' being 0 to 5; z is a number representing the average number of oxygen atoms, --O--, randomly distributed within the chain which when bonded to an --O-- of the --CF 2 O--, ##STR162## forms a peroxy group, --O--O--, and has a value of 0 or greater; the ratio w/x is 5 or less; the ratio (y+y')/(w+x) is 0.01 to 1.5; and the ratio z/(w+x+y+y') is 0 to 1.

Claim 4

Poly(perfluorooxyalkylene) compositions according to claim 2 wherein R 2 is independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 --, and ##STR163## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6.

Claim 5

Poly(perfluorooxyalkylene) compositions according to claim 2 wherein w is 1 to about 10,000; x is 1 to about 10,000, and the sum of y and y' is 1 to about 800; and z is 0 to about 5000.

Claim 6

Poly(perfluorooxyalkylene) compositions according to claim 2 wherein said ratio (y+y')/(w+x) is 0.05 to 1.5.

Claim 7

Poly(perfluorooxyalkylene) compositions according to claim 2 wherein said compounds have a number average molecular weight of about 650 to 1,000,000.

Claim 8

Polyfluoropolyether compositions according to claim 1 comprising polyfluoropolyethers represented by the formula ##STR164## where each R 1 is independently a fluorine or a perfluoroalkyl group selected from linear, branched, and cyclic groups; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms, independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR165## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6; w is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 or greater; x is a number representing the average number of ##STR166## units randomly distributed within the chain and has a value of 1 or greater; y and y' are each a number representing the average number of ##STR167## units, respectively, randomly distributed withn the chain, the sum of y and y' having a value of 1 or greater, and the ratio y/y' being 0 to 5; z is a number representing the average number of oxygen atoms, --O--, randomly distributed within the chain which when bonded to an --O-- of the --CF 2 O--, ##STR168## forms a peroxy group, and has a value of 0 or greater; the ratio w/x is 5 or less; the ratio (y+y')/(w+x) is 0.01 to 1.5; the ratio z/(w+x+y+y') is 0 or 1; when z is zero, G and J are independently selected from --C j F 2j X in which X is hydrogen or halogen and when X is hydrogen, then j is 1 or 2, and when X is halogen, then j is a integer of 1 to 5, or G and J are terminal functional groups which can enter into an addition or condensation reaction to form a homopolymer or copolymer, and when z is 1 or greater, and when z is zero, G is selected from --COF, --CF 2 COF, ##STR169## --CF 2 COCF 3 , --CF 2 C(OH) 2 CF 3 , ##STR170## and --CF 2 COOH and J is selected from --COF, --CF 2 COF, ##STR171## --CF 2 COCF 3 , --CF 2 C(OH) 2 CF 3 , ##STR172## --CF 2 COOH, --C a F 2a+1 and --C a F 2a Cl where a is an integer of 1 to 5; and the number average molecular weight of the polyfluoropolyether is from about 650 to 1,000,000.

Claim 9

Peroxidic poly(perfluorooxyalkylene) compositions according to claim 1 comprising peroxidic poly(perfluorooxyalkylenes) represented by the formula ##STR173## wherein Q is selected from --COF, --CF 2 COF, and --CF 2 COOH; W is a terminal group selected from Q and --C a F 2a+1 and --C a F 2a Cl where a is an integer up to 5; each R 1 is independently a fluorine or a perfluoroalkyl group selected from linear, branched, and cyclic groups; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms independently selected from units having the structure (R 3 O) f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR174## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6; and b is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 or greater; c is a number representing the average number of ##STR175## units randomly distributed within the chain and has a value of 1 or greater; d and d' are each a number representing the average number of ##STR176## units, respectively, randomly distributed within the chain, the sum of d and d' has a value of 1 or greater and the ratio d/d' is 0 to 5; e is a number representing the average number of --O-- units randomly distributed within the chain and has a value of 1 or greater; the ratio b/c is less than 5; the ratio (d+d')/(b+c) is 0.01 to 1.5; the ratio e/(b+c+d+d') is 0.0001 to 1; and the number average molecular weight of the poly(perfluorooxyalkylene) is from about 650 to 1,000,000.

Claim 10

Compositions comprising the mixtures of non-peroxidic polyfluoropolyethers compounds according to claim 1, which compounds are represented by the formula ##STR177## wherein each Z is independently a terminal group which is a functional group Y which is or contains a functional moiety which can enter into an addition or condensation reaction to form a polymer, or Z is a non-functional group --C j F 2j X in which X is hydrogen or halogen and when X is hydrogen, then j is 1 or 2, and when X is halogen, then j is an integer of from 1 to 5; each R 1 is independently a fluorine or a perfluoroalkyl group selected from linear, branched, and cyclic groups; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms, independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR178## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6, and g is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 or greater; h is a number representing the average number of ##STR179## units randomly distributed within the chain and has a value of 1 or greater; i and i' are each a number representing the number of ##STR180## units, respectively, distributed within the chain, the sum of i and i' has a value of 1 or greater and i/i' is 0 to 5; the ratio g/h is less than 5; the ratio (i+i')/(g+h) is 0.01 to 1.5; and the number average molecular weight of the polyfluoropolyether is from about 650 to 20,000.

Claim 11

Non-functional polyfluoropolyether compounds according to claim 1 comprising non-periodic polyfluoropolyethers represented by the formula ##STR181## each X is hydrogen or halogen and when X is hydrogen, then j is 1 or 2, and when X is halogen, then j is an integer of from 1 to 5; each R 1 is independently a fluorine or a perfluoroalkyl group selected from linear, branched, and cyclic groups; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a saturated perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms, independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR182## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6, and g is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 or greater; h is a number representing the average number of ##STR183## units randomly distributed within the chain and has a value of 1 or greater; i and i' are each a number representing the average number of ##STR184## units, respectively, randomly distributed within the chain, the sum of i and i' has a value of 1 or greater and i/i' is 0 to 5; the ratio g/h is less than 5; the ratio (i+i')/(g+h) is 0.01 to 1.5; and the number average molecular weight of the polyfluoropolyether is 650 to 20,000.

Claim 12

Functional polyfluoropolyether compounds according to claim 1 comprising non-peroxidic polyfluoropolyethers represented by the formula ##STR185## where Y is any terminal functional group which is or contains a functional moiety which can enter into an addition or condensation reaction to form a homopolymer or copolymer; R 6 is Y, a perfluoroalkyl group, or a haloperfluoroalkyl group; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms, independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR186## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic groups, and f is zero or a number having a value of 1 to 6; k is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 to 200; l is a number representing the average number of --CF 2 CF 2 O-- units randomly distributed within the chain and has a value of 1 to 200; p and p' are each a number representing the average number of ##STR187## units, respectively, randomly distributed within the chain, the sum of p and p' has a value of 1 to 50, and p/p' is 0 to 5; the ratio k/l is less than 5; the ratio (p+p')/(k+l) is 0.01 to 1.5; and the number average molecular weight of the polyfluoropolyether is from about 650 to 20,000.

Claim 13

The polyfluoropolyethers of claim 11 wherein R 6 is Y.

Claim 14

The polyfluoropolyethers of claim 11 wherein the functional moiety is selected from --OH, --SH, --NHR 9 , --COOR 8 , --SiR 8 .sub.α R 10 3- α, --CN, --NCO, ##STR188## --OSO 2 CF 3 , --OCOCl, --OCN, --N(R 8 )CN, ##STR189## --N═C, --I, --CHO, --CH(OCH 3 ) 2 , --SO 2 Cl, --C(OCH 3 )═NH, and --C(NH 2 )═NH, wherein R 8 is lower alkyl or phenyl, R 9 is hydrogen or R 8 , R 10 is a hydrolyzable group, α is an integer of 1 to 3, R 11 and R 12 are independently hydrogen or lower alkyl of 1 to 4 carbon atoms or R 11 and R 12 together are alkylene and with carbons to which they are attached form a carbocyclic ring of 5 to 6 carbon atoms.

Claim 15

The polyfluoropolyethers of claim 13 wherein said functional moiety is linked to the ##STR190## by the linking group --CF 2 CH 2 --.

Claim 16

The polyfluoropolyethers of claim 14 wherein said functional moiety is selected from ##STR191##

Claim 17

The polyfluoropolyethers of claim 11 wherein the functional moiety is selected from --OCH═CH 2 , --NHCH 2 CH 2 OH, --N(CH 2 CH 2 OH) 2 , --OCH 2 CH═CH 2 , --NHCH 2 CH═CH 2 , --N(CH 2 CH═CH 2 ) 2 , ##STR192## --NH(CH 2 ) 3 Si(OCH 3 ) 3 , and --OCH 2 CH(OH)CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 and the functional group is linked to the ##STR193## by linking group ##STR194##

Claim 18

Functional polyfluoropolyether compounds according to claim 1 comprising non-peroxidic polyfluoropolyethers represented by the formula ##STR195## wherein Y is a terminal functional group which is or contains a functional moiety; R 7 is a perfluoroalkyl group, haloperfluoroalkyl, or the terminal functional group Y; each OR 2 is independently a perfluoroalkoxy group wherein R 2 is a saturated perfluoroalkyl group or perfluoroalkyl group substituted with one or more further ether oxygen atoms, independently selected from units having the structure --R 3 O-- f R 4 , in which each R 3 is independently selected from --CF 2 --, --CF 2 CF 2 -- and ##STR196## and R 4 is a perfluoroalkyl group selected from linear, branched, and cyclic grops, and f is zero or a number having a value of 1 to 6; q is a number representing the average number of --CF 2 O-- units randomly distributed within the chain and has a value of 1 up to about 50; r is a number representing the average number of ##STR197## units randomly distributed within the chain and has a value of 5 up to about 50; s and s' are each a number representing the average number of ##STR198## units, respectively, randomly distributed within the chain, the sum of s and s' has a value of 1 up to about 50, and the ratio s/s' is 0 to 5; the ratio q/r is 0.01 to 1.0; the ratio (s+s')/(q+r) is 0.01 to 1.0; and the number average molecular weight of the polyfluoropolyether is from about 650 to 10,000.

Claim 19

The polyfluoropolyethers of claim 17 wherein R 7 is a perfluoroalkyl group.

Claim 20

The polyfluoropolyethers of claim 17 wherein R 7 is selected from --CF 3 , --CF 2 CF 3 , and --CF 2 CF(CF 3 ) 2 .

Claim 21

The polyfluoropolyethers of claim 17 wherein the functional moiety is selected from --OH, --SH, --NHR 9 , --COOR 8 , --SiR 8 .sub.α R 10 3- α, --CN, --NCO, ##STR199## --OSO 2 CF 3 , --OCOCl, --OCN, --N(R 8 )CN, ##STR200## --N═C, --I, --CHO, --CH(OCH 3 ) 2 , --SO 2 Cl, --C(OCH 3 )═NH, --C(NH 2 )═NH, and the like, wherein R 8 is lower alkyl or phenyl, R 9 is hydrogen or R 8 , R 10 is a hydrolyzable group α is an integer of 1 to 3, R 11 and R 12 are independently hydrogen or lower alkyl of 1 to 4 carbon atoms or R 11 and R 12 together are alkylene and with carbons to which they are attached form a carbocyclic ring of 5 to 6 carbon atoms.

Claim 22

The polyfluoropolyethers of claim 17 wherein said functional moiety is linked to the ##STR201## by linking groups selected from --CF 2 CH 2 --, ##STR202##

Claim 23

The polyfluoropolyethers of claim 17 wherein said linking group is --CF 2 CH 2 --, ##STR203## and the terminal functional moiety is selected from ##STR204##

Claim 24

The composition of claim 11 wherein Y is --CF 2 COOCH 3 and R 2 is --CF 3 , --C 2 F 5 , C 3 F 7 , or --C 4 F 9 .

Claim 25

The composition of claim 11 wherein Y is --CF 2 CH 2 OH or 17 wherein Y is --CF 2 CH 2 OH, ##STR205## and R 2 is --CF 3 , --C 2 F 5 , --C 3 F 7 , or C 4 F 9 .

Claim 26

The composition of claim 11 wherein Y is ##STR206## or 17 wherein Y is ##STR207## and R 2 is --CF 3 , --C 2 F 5 , --C 3 F 7 , or --C 4 F 9 .

Claim 27

The composition of claim 11 wherein Y is ##STR208## or 17 wherein Y is ##STR209## and R 2 is --CF 3 , --C 2 F 5 , --C 3 F 7 , or --C 4 F 9 .

Claim 28

The functional polyfluoropolyether compounds according to claim 11 or 17 wherein said functional moiety is hydroxyl, ester, acrylate, methacrylate, or substituted silane.

Claim 29

A polymer having a backbone comprising randomly distributed, perfluorooxyalkylene units represented by the formulas --CF 2 O--, ##STR210## and backbone-pendant perfluoroalkoxy groups, the terminal ether oxygen atoms of which are bonded to carbon atoms of the ##STR211## backbone units.

Claim 30

A polymer having a backbone comprising randomly distributed, perfluorooxyalkylene units represented by the formulas --CF 2 O--, ##STR210## and backbone-pendant perfluoroalkoxy groups, the terminal ether oxygen atoms of which are bonded to carbon atoms of the ##STR211## backbone units.

Claim 31

A release agent comprising a polymerized, functional polyfluoropolyether composition of claim 1.

Claim 32

The release agent of claim 29 wherein said functional polyfluoropolyether composition comprises the polyfluoropolyethers of claim 11 or 17.