Terminally unsaturated macromolecular monomers of polyformals and copolymers thereof

Claim 2

A process for the manufacture of a polyformal macromer having an ethylenically unsaturated functional group neat one end and a hydroxyl group at the other, comprising, polymerizing (A) a cationically ring-openable cyclic formal having a structure selected from: ##STR30## wherein, x is an integer in the range from 2 to 6; x' is in the range from 1 to 3; and, no more than two ring c atoms, other than the 2-carbon atom, may have a single substituent selected from halogen, and lower alkyl, haloalkyl, and alkoxy each C 1 -C 5 ; said cyclic formal alone, or with a comonomer selected from the group consisting of (i) formaldehyde (ii) 1,3,5-trioxane and (iii) a cationically ring-openable ether; and, (B) a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group said alcohol having the structure ##STR31## wherein, R 1 is H or C 1 -C 20 alkyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxylene, haloalkoxylene, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxylene, and haloaralkoxylene, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a numeral average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond connecting R 2 to OH; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR32## wherein R 2 and G, if either is present, is in an ortho-, meta, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 2 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the aliphatic structure ##STR33## wherein only G is optionally present; or, by the alicyclic structure ##STR34## wherein, the olefin bond is part of the ring which is a single or fused ring structure having from 5 to 10 ring carbon atoms, both R 2 and G are optionally present; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralykyl; in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions; so as to produce a polyformal macromer represented by the structure R--(M).sub.m --OH (FM) wherein, R represents the residue of said alcohol (B), having a vinyl group, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal, the chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened, and, m represent an integer in the range from 2 to about 500.

Claim 3

The process of claim 1 wherein said macromer is a random copolymer derived from a first cyclic formal monomer (M1) in combination with a second cyclic formal monomer (M2), so as to have the structure R--[(M1).sub.m' --r--(M2).sub.m" ]--OH (7a) wherein, m' and m' are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 4

The process of claim 1 wherein said macromer is a random copolymer derived from a first cyclic formal monomer (M1) in combination with a ring-openable cyclic ether monomer (Et), so as to have the structure R--[(M1).sub.m' --r--(Et).sub.m" ]--OH (7b) wherein, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 5

The process of claim 3 wherein said ring openable ether is selected from the group consisting of (i) an epoxide having the structure ##STR35## wherein, y is an integer in the range from 0 to 4, excluding 3, and, R 8 , R 9 and R 10 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl (Ar) and aralkyl, and at least one of R 8 , R 9 and R 10 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR36## wherein R 11 represents a member selected from the group consisting of a alkyl, haloalkyl, alkoxyalkyl, each C 1 -C 20 , Ar, or substituted aryl (Ar--Q), where Q represents alkyl or haloalkyl each C 1 -C 10 .

Claim 6

The process of claim 1 wherein said macromer is a random copolymer derived from a first cyclic formal monomer (M1) in combination with trioxane (TOX) so as to have the structure R--[(M1).sub.m' --r--(TOX).sub.m" ]--OH (7c) wherein, TOX represents a ring-opened repeating unit of trioxane, and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 7

The process of claim 1 wherein said macromer is a formal-formal block copolymer derived from a first cyclic formal monomer (M1) in combination with a second cyclic formal monomer (M2), sequentially, so as to have the structure R--(M1).sub.m' --b--(M2).sub.m" --OH (7) wherein, M1 and M2 each represents a formal repeating unit derived from said ring-openable cyclic formal; and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 8

The process of claim 1 wherein said macromer is a formal-ether block copolymer derived from a first cyclic formal monomer (M1) in combination with a cyclic ether (Et), sequentially, so as to have the structure R--(M1).sub.m' --b--(Et).sub.m" --OH (7) wherein, M1 and Et represent a formal and ether repeating unit derived from said ring-openable cyclic formal and ether, respectively; and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 9

The process of claim 1 wherein G is present as (PolyEt) and represents a chain of ring-opened cyclic ether repeating units in said macromer, forming a block copolymer of ether-formal represented by the formula R'--(polyEt)--b--(M).sub.m' --OH comprising first forming a macromer of polyether R'--(PolyEt)--OH from a cyclic ether (Et), then, polymerizing said macromer of polyether with said formal monomer (M), to form said block copolymer of etherformal, wherein, M represents a formal repeating unit derived from said ring-openable cyclic formal; R'=R-G, and represents the head of a chain derived from an unsaturated alcohol having unsaturation selected from allyl, styryl, or acryloyl; and, m is an integer in the range from 2 to about 300; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 10

The process of claim 8 wherein said ring openable ether is selected from the group consisting of (i) an epoxides having the structure ##STR37## wherein, y is an integer in the range from 0 to 4, excluding 3, and, R 8 , R 9 and R 10 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl (Ar) and aralkyl, and at least one of R 8 , R 9 and R 10 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR38## wherein R 11 represents a member selected from the group consisting of a alkyl, haloalkyl, alkoxyalkyl, each C 1 -C 20 , Ar, or substituted aryl (Ar--Q), where Q represents alkyl or haloalkyl each C 1 -C 10 .

Claim 11

The process of claim 9 wherein (PolyEt) is derived from a cationically ring-openable monomer selected from the group consisting of (i) an epoxide selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxydodecane, 1,2-epoxyoctadecane; (ii) oxetane; (iii) 1-chloro-2,3-epoxypropane (ECH), 1-bromo-2,3-epoxypropane; (iv) tetrahydrofuran (THF); (v) oxepane (OXP); (vi) an aliphatic or aromatic glycidyl ether selected from methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether; and, (vii) an aliphatic or aromatic glycidyl ester selected from glycidyl acetate, glycidyl chloroacetate, glycidyl butyrate, and glycidyl stearate.

Claim 12

The process of claim 1 wherein said cyclic formal (M) has a structure selected from (a) a ring containing two O atoms, including a ring wherein x is an integer in the range from 2 to 4; and, (b) a ring containing plural O atoms, the additional O atoms being part of an ethylene oxide (--CH 2 --CH 2 --O--) repeating unit, said plural O atoms ranging from three to six.

Claim 13

The process of claim 11 wherein said cyclic formal (M) is selected from the group consisting of 1,3-dioxolane (DOL), 1,3-dioxane (DOX), 1,3-dioxepane (DOP), 1,3,6,9-tetraoxacycloundecane or triethyleneglycolformal (TGF), 1,3,6,11-tetraoxacyclotridecane (DDF), 1,3,6,9,12-pentaoxacyclotetradecane (POC), 1,3,5-trioxetane, 1,3,6-trioxocane and, 1,3,6,9,12,15-hexaoxacycloheptadecane (HOC).

Claim 14

The process of claim 12 wherein said G represents a polyether chain derived from a monomer selected from the group consisting of (i) an epoxide selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxydodecane, 1,2-epoxyoctadecane; (ii) oxetane; (iii) 1-chloro-2,3-epoxypropane (ECH), 1-bromo-2,3-epoxypropane; (iv) tetrahydrofuran (THF); (v) oxepane (OXP); (vi) an aliphatic or aromatic glycidyl ether selected from methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether; and, (vii) an aliphatic or aromatir: glycidyl ester selected from glycidyl acetate, glycidyl chloroacetate, glycidyl butyrate, and glycidyl stearate.

Claim 15

The process of claim 13 wherein G is derived from an essentially linear polyether having Mn in the range from 100 to about 1000.

Claim 16

The process of claim 12 wherein said acryloyl alcohol is selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, hydroxymethyl acrylate, hydroxymethyl methacrylate, and, 12-hydroxydecyl acrylate.

Claim 17

The process of claim 12 wherein said styrylically unsaturated alcohols is an ortho-, meta- or para-derivative, or mixtures of derivatives selected from the group consisting of hydroxyl styrene, vinyl benzyl alcohol, 2-hydroxyethyl styrene and hydroxypropyl styrene.

Claim 18

The process of claim 12 wherein said allylically unsaturated alcohol is selected from the group consisting of (a) relatively short chain alcohols having from 3 to about 6 carbon atoms selected from the group consisting of allyl alcohol, 2-methyl-2-propene-1-ol, 2-buten-1-ol, and 1-buten-3-ol; (b) relatively long chain alcohols having from 7 to about 20 carbon atoms selected from the group consisting of 10-undecen-1-ol and oleyl alcohol; (c) arylalcohols selected from the group consisting of cinnamyl alcohol, and allyl phenol; (d) monoadducts of a single 1,2-epoxide unit to said allylically unsaturated primary of secondary alcohol, selected the group consisting of 2-hydroxyethyl allyl ether, 2-hydroxy-1-methylethyl allyl ether, and 2-hydroxy-2-methyl ether; and, (e) alcohols in which the olefinic bond is in a sin or fused ring structure having from 5 to 10 carbon at selected from the group consisting of 2-cyclopenten-1-ol, 2-cyclohexen-1-ol, and 5-norbornene-2-methanol.

Claim 19

The of claim 12 wherein said cationic initiator from the group consisting of trialkloxonium salts of tetrafluoroborate, hexaf hexafluoroantimonate, and hexachloroantimonate; and, SbF 5 , SbCl 5 , AsF 3 , AsF 5 , PF 5 , SnCl 4 , and , BF 3 etherate.

Claim 20

The process of claim 1 wherein said macromer is a formal-formal block copolymer derived from a formal homopolyformal macromer R--(M) m --OH used as a propagator, so that upon addition of a formal monomer (M2) said block copolymer is formed having the structure R--(M).sub.m --b--(PolyForm)--OH wherein, M represents a formal repeating unit derived from said ring-openable cyclic formal; (PolyForm) represents a chain of from 2 to about 300 formal repeating units; and, m is an integer in the range from 2 to about 300; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 21

The process of claim 1 wherein said macromer is a formal-ether block copolymer derived from a formal homopolyformal macromer R--(M) m --OH used as a propagator, so that upon addition of a cyclic ether monomer (Et) said block copolymer is formed, having the structure R--(M).sub.m --b--(PolyEt)--OH (10) wherein, M represents a formal repeating unit derived from said ring-openable cyclic formal; (PolyEt) is a polyether chain having a mol wt of from about 500 to about 5000; and, m is an integer in the range from 2 to about 300; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 22

A process for the manufacture of a copolymer of a polyformal macromer and, an olefinically unsaturated monomer, comprising, polymerizing (A) said polyformal macromer having the structures R--(M) m --OH for non-end-capped and, R--(M) m --OZ for end-capped polyformals, respectively, wherein, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal the chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened; Z is the residue of an end-capping unit selected from the group consisting of --R 5 , ##STR39## --SiR 3 5 , --CH 2 CH 2 CN, --SO 3 Na, --SO 3 K, and, --SO 3 NH 4 , but R 5 cannot be H; and, R represents the residue of a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR40## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl, and most preferably methyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxyl, haloalkoxyl, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxyl, and haloaralkoxyl, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR41## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 6 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; most preferably, both are H, or, if one is H, the other is CH 3 ; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the structure ##STR42## wherein only G is optionally present; and, (ii) ##STR43## wherein, both R 2 and G are optionally present; that is, when both are absent, they are replaced with a bond directly connecting the OH group to the ring; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; with, (B) at least one olefinically unsaturated monomer, in the presence of an effective amount of (C) a free radical generating catalyst, wherein a free radical polymerization is initiated by heat, peroxide, or hydroperoxide decomposition, redox catalysts, or radiation, so as to yield a comb-shaped graft copolymer of formal macromer presented by the structure [R--(M).sub.m --OH].sub.n' [M.sub.o ].sub.n" ( 27) [R--(M).sub.m --OZ].sub.n' [M.sub.o ].sub.n" ( 27') wherein, M o represents the olefinically unsaturated monomer; n' represents an integer in the range from 1 to about 10 4 , and refers to the number of pendant polyformal chains; n" represents an integer in the range from 1 to about 10 6 , and, m represents an integer in the range from 2 to about 500.

Claim 23

A process for the manufacture of a copolymer of a polyformal macromer and, an olefinically unsaturated monomer, comprising, polymerizing (A) said polyformal macromer having the structures R--(M) m --OH for non-end-capped and, R--(M) m --OZ for end-capped polyformals, respectively, wherein, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal the chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened; Z is the residue of an end-capping unit selected from the group consisting of --R 5 , ##STR39## --SiR 3 5 , --CH 2 CH 2 CN, --SO 3 Na, --SO 3 K, and, --SO 3 NH 4 , but R 5 cannot be H; and, R represents the residue of a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR40## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl, and most preferably methyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxyl, haloalkoxyl, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxyl, and haloaralkoxyl, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR41## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 6 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; most preferably, both are H, or, if one is H, the other is CH 3 ; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the structure ##STR42## wherein only G is optionally present; and, (ii) ##STR43## wherein, both R 2 and G are optionally present; that is, when both are absent, they are replaced with a bond directly connecting the OH group to the ring; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; with, (B) at least one olefinically unsaturated monomer, in the presence of an effective amount of (C) a free radical generating catalyst, wherein a free radical polymerization is initiated by heat, peroxide, or hydroperoxide decomposition, redox catalysts, or radiation, so as to yield a comb-shaped graft copolymer of formal macromer presented by the structure [R--(M).sub.m --OH].sub.n' [M.sub.o ].sub.n" ( 27) [R--(M).sub.m --OZ].sub.n' [M.sub.o ].sub.n" ( 27') wherein, M o represents the olefinically unsaturated monomer; n' represents an integer in the range from 1 to about 10 4 , and refers to the number of pendant polyformal chains; n" represents an integer in the range from 1 to about 10 6 , and, m represents an integer in the range from 2 to about 500.

Claim 24

The process of claim 21 wherein said olefinically unsaturated monomer is selected from the group consisting of (i) C 2 -C 12 vinyl monomers selected from the group consisting of vinyl chloride, vinyl acetate, acrylonitrile, ethylene, propylene, 4-vinyl pyridine, vinyl pyrrolidone, vinyl benzoic acid, ethyl vinyl ether, salts of vinyl sulfonate, vinylidene chloride, and N-vinyl carbazole: (ii) C 8 -C 16 styryl monomers selected from the group consisting of styrene, 4-chlorostyrene, vinyl toluene, and alpha-methyl styrene; (iii) alpha,beta-ethylenically unsaturated carboxylic acids, acrylic acid and methacrylic acid, and those having from 3 to 8 carbon atoms, and derivatives thereof selected from the group consisting of esters of C 1 -C 20 alcohols said esters selected from the group consisting of ethyl acrylate, ethyl methacrylate, glycidyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; acrylamide and amides of C 1 -C 20 amines such as N,N-dimethylacrylamide; and, metal salts such as sodium acrylate; and, the corresponding analogs of methacrylates and methacrylamide; (iv) C 4 -C 8 diene monomers selected from the group consisting of butadiene and isoprene; (v) C 5 -C 10 allylically unsaturated monomers selected from the group consisting of allyl acetate, and diallylphthalate; and, (vi) C 5 -C 14 cyclic olefins selected from the group consisting of norbornene, dicyclopentadiene, cyclopentene, 1,5-cyclooctadiene and norbornadiene.

Claim 25

A process for preparing a non-hydrolyzable formal-siloxane block copolymer of an end-capped formal macromer possessing an allyl head group comprising, reacting said end-capped formal macromer with an organohydrosiloxane having from 1 to about 30 Si--H bonds and an average mol wt Mn in the range from 300 to 5000 having the formula R".sub.3 SiO(R".sub.2 SiO).sub.k (R"SiHO).sub.k' SiR".sub.3 ( 19) wherein R" is an unsubstituted or halogen-substituted monovalent C 1 -C 5 hydrocarbon group, k is an integer in the range from 0 to about 300, and k' is an integer in the range from 1 to about 30, under addition reaction conditions, at a temperature in the range from about 50°-100° C. in the presence of a solvent unreactive with the reactants, and a Pt-containing hydrosilylation catalyst, so as to produce a formal-silaxane block copolymer of macromer formed with a polyhydrosiloxane, said block copolymer being represented by the formula A'A".sub.k' wherein, A' represents the residue of a polysiloxane block, and, A" represents the residue of a polyformal block of end-capped macromer.

Claim 26

A process for preparing a non-hydrolyzable formal-siloxane block copolymer of an end-capped formal macromer possessing an allyl head group comprising, reacting said end-capped formal macromer with an organohydrosiloxane having from 1 to about 30 Si--H bonds and an average mol wt Mn in the range from 300 to 5000 having the formula R".sub.3 SiO(R".sub.2 SiO).sub.k (R"SiHO).sub.k' SiR".sub.3 ( 19) wherein R" is an unsubstituted or halogen-substituted monovalent C 1 -C 5 hydrocarbon group, k is an integer in the range from 0 to about 300, and k' is an integer in the range from 1 to about 30, under addition reaction conditions, at a temperature in the range from about 50°-100° C. in the presence of a solvent unreactive with the reactants, and a Pt-containing hydrosilylation catalyst, so as to produce a formal-silaxane block copolymer of macromer formed with a polyhydrosiloxane, said block copolymer being represented by the formula A'A".sub.k' wherein, A' represents the residue of a polysiloxane block, and, A" represents the residue of a polyformal block of end-capped macromer.

Claim 27

A polyformal macromer having an ethylenically unsaturated functional group near one end and a hydroxyl group at the other, produced by polymerizing (A) a cationically ring-openable cyclic formal having a structure selected from: ##STR44## wherein, x is an integer in the range from 2 to 6; x' is in the range from 1 to 3; and, no more than two ring C atoms, other than the 2-carbon atom, may have a single substituent selected from halogen, and lower alkyl, haloalkyl, and alkoxy each C 1 -C 5 ; said cyclic formal alone, or with a comonomer selected from the group consisting of (i) formaldehyde (ii) 1,3,5-trioxane and (iii) a cationically ring-openable ether; and, (B) a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR45## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxylene, haloalkoxylene, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxylene, and haloaralkoxylene, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond connecting R 2 to OH; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR46## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 2 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the aliphatic structure ##STR47## wherein only G is optionally present; and, by the alicyclic structure ##STR48## wherein, the olefin bond is part of the ring which is a single or fused ring structure having from 5 to 10 ring carbon atoms, both R 2 and G are optionally present; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel-Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions; so as to produce a polyformal macromer represented by the structure R--(M).sub.m --OH (FM) wherein, R represents the residue of said alcohol (B), having a vinyl group, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal, the Z chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened, and, m represents an integer in the range from 2 to about 500.

Claim 28

A polyformal macromer having an ethylenically unsaturated functional group near one end and a hydroxyl group at the other, produced by polymerizing (A) a cationically ring-openable cyclic formal having a structure selected from: ##STR44## wherein, x is an integer in the range from 2 to 6; x' is in the range from 1 to 3; and, no more than two ring C atoms, other than the 2-carbon atom, may have a single substituent selected from halogen, and lower alkyl, haloalkyl, and alkoxy each C 1 -C 5 ; said cyclic formal alone, or with a comonomer selected from the group consisting of (i) formaldehyde (ii) 1,3,5-trioxane and (iii) a cationically ring-openable ether; and, (B) a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR45## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxylene, haloalkoxylene, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxylene, and haloaralkoxylene, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond connecting R 2 to OH; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR46## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 2 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the aliphatic structure ##STR47## wherein only G is optionally present; and, by the alicyclic structure ##STR48## wherein, the olefin bond is part of the ring which is a single or fused ring structure having from 5 to 10 ring carbon atoms, both R 2 and G are optionally present; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; in the presence of an effective amount of (C) a cationic initiator selected from the group consisting of Friedel-Crafts acids, relatively strong protic organic and inorganic acids, oxonium salts and stable carbenium ions; so as to produce a polyformal macromer represented by the structure R--(M).sub.m --OH (FM) wherein, R represents the residue of said alcohol (B), having a vinyl group, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal, the Z chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened, and, m represents an integer in the range from 2 to about 500.

Claim 29

The polyformal macromer of claim 24 wherein said macromer is a random copolymer of formal-formal, derived from a first cyclic formal monomer (M1) in combination with a second cyclic formal monomer (M2), so as to have the structure R--[(M1).sub.m' --r--(M2).sub.m"]--OH ( 7a) wherein, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 30

The polyformal macromer of claim 24 wherein said macromer is a random copolymer of formal-ether, derived from a first cyclic formal monomer (M1) in combination with a ring-openable cyclic ether monomer (Et), so as to have the structure R--[(M1).sub.m' --r--(Et).sub.m" ]--OH (7b) wherein, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 31

The polyformal macromer of claim 26 wherein said ring-openable ether is selected from the group consisting of (i) an epoxide having the structure ##STR49## wherein, y is an integer in the range from 0 to 4, excluding 3, and, R 8 , R 9 and R 10 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl (Ar) and aralkyl, and at least one of R 8 , R 9 and R 10 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR50## wherein R 11 represents a member selected from the group consisting of a alkyl, haloalkyl, alkoxyalkyl, each C 1 -C 20 , Ar, or substituted aryl (Ar--Q), where Q represents alkyl or haloalkyl each C 1 -C 10 .

Claim 32

The polyformal macromer of claim 24 wherein said macromer is a random copolymer derived from a first cyclic formal monomer (M1) in combination with trioxane (TOX) so as to have the structure R--[(M1).sub.m' --r--(TOX).sub.m" ]--OH (7c) wherein, TOX represents a ring-opened repeating unit of trioxane, and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 33

The polyformal macromer of claim 24 wherein said macromer is a block copolymer of formal-formal derived from a first cyclic formal monomer (M1) in combination with a second cyclic formal monomer (M2), sequentially, so as to have the structure R--(M1).sub.m' --b--(M2).sub.m" --OH (7) wherein, M1 and M2 each represent a formal repeating unit derived from said ring-openable cyclic formal; and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 34

The polyformal macromer of claim 24 wherein said macromer is a formal-ether block copolymer derived from a first cyclic formal monomer (M1) in combination with a cyclic ether (Et), sequentially, so as to have the structure R--(M1).sub.m' --b--(Et).sub.m" --OH (7) wherein, M1 and Et represent a formal and ether repeating unit derived from said ring-openable cyclic formal and ether, respectively; and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 35

The polyformal macromer of claim 24 wherein G is present as (PolyEt) and represents a chain of ring-opened cyclic ether repeating units in said macromer, forming a block copolymer of ether-formal represented by the formula R'--(PolyEt)--b--(M).sub.m' --OH comprising first forming a macromer of polyether R'--(PolyEt)--OH from a cyclic ether (Et), then, polymerizing said macromer of polyether with said formal monomer (M), to form said block copolymer of etherformal, wherein, M represents a formal repeating unit derived from said ring-openable cyclic formal; R'=R-G, and represents the head of a chain derived from an unsaturated alcohol having unsaturation selected from allyl, styryl, or acryloyl; and, m is an integer in the range from 2 to about 300; said block copolymer having substantially uniform molecular weight distribution such that its ratio of Mw/Mn is not above about 5.0.

Claim 36

The polyformal macromer of claim 31 wherein said ring openable ether is selected from the group consisting of (i) an epoxide having the structure ##STR51## wherein, y is an integer in the range from 0 to 4, excluding 3, and, R 8 , R 9 and R 10 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl (Ar) and aralkyl, and at least one of R 8 , R 9 and R 10 is hydrogen; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR52## wherein R 11 represents a member selected from the group consisting of a alkyl, haloalkyl, alkoxyalkyl, each C 1 -C 20 , Ar, or substituted aryl (Ar--Q), where Q represents alkyl or haloalkyl each C 1 -C 10 .

Claim 37

The process of claim 32 wherein said G represents a polyether chain derived from a monomer selected from the group consisting of (i) an epoxide selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxydodecane, 1,2-epoxyoctadecane; (ii) oxetane; (iii) 1-chloro-2,3-epoxypropane (ECH), 1-bromo-2,3-epoxypropane; (iv) tetrahydrofuran (THF); (v) oxepane (OXP); (vi) an aliphatic or aromatic glycidyl ether selected from methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether; and, (vii) an aliphatic or aromatic glycidyl ester selected from glycidyl acetate, glycidyl chloroacetate, glycidyl butyrate, and glycidyl stearate.

Claim 38

The polyformal macromer of claim 24 wherein said cyclic formal (M) has a structure selected from (a) a ring containing two O atoms, including a ring wherein x is an integer in the range from 2 to 4; and, (b) a ring containing plural O atoms, the additional O atoms being part of an ethylene oxide (--CH 2 --CH 2 --O--) repeating unit, said plural O atoms ranging from three to six.

Claim 39

The process of claim 34 wherein said cyclic formal (M) is selected from the group consisting of 1,3-dioxolane (DOL), 1,3-dioxane (DOX), 1,3-dioxepane (DOP), 1,3,6,9-tetraoxacycloundecane or triethyleneglycolformal (TGF), 1,3,6,11-tetraoxacyclotridecane (DDF), 1,3,6,9,12-pentaoxacyclotetradecane (POC), 1,3,5-trioxetane, 1,3,6-trioxocane and, 1,3,6,9,12,15-hexaoxacycloheptadecane (HOC).

Claim 40

The polyformal macromer of claim 35 wherein said G represents a polyether chain derived from a monomer selected from the group consisting of (i) an epoxide selected from ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, cis- and trans-, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxydodecane, 1,2-epoxyoctadecane; (ii) oxetane; (iii) 1-chloro-2,3-epoxypropane (ECH), 1-bromo-2,3-epoxypropane; (iv) tetrahydrofuran (THF); (v) oxepane (OXP); (vi) an aliphatic or aromatic glycidyl ether selected from methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether; and, (vii) an aliphatic or aromatic glycidyl ester selected from glycidyl acetate, glycidyl chloroacetate, glycidyl butyrate, and glycidyl stearate.

Claim 41

The polyformal macromer of claim 36 wherein G is derived from an essentially linear polyether having Mn in the range from 100 to about 1000.

Claim 42

The polyformal macromer of claim 35 wherein said acryloyl alcohol is selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, hydroxymethyl acrylate, hydroxymethyl methacrylate, and, 12-hydroxydecyl acrylate.

Claim 43

The polyformal macromer of claim 38 wherein (M) is 1,3-dioxolane (DOL), said macromer having an acryloylethyl group at the head of each chain, and the structure ##STR53## where m=about 6 to 250.

Claim 44

The polyformal macromer of claim 35 wherein said styrylically unsaturated alcohols is an ortho-, meta- or para- derivative, or mixtures of derivatives selected from the group consisting of hydroxyl styrene, vinyl benzyl alcohol, 2-hydroxyethyl styrene and hydroxypropyl styrene.

Claim 45

The polyformal macromer of claim 40 wherein (M) is 1,3-dioxolane (DOL), said macromer having a styryl group at the head of -each chain, and the structure: ##STR54## where m=about 6 to 50.

Claim 46

The polyformal macromer of claim 35 wherein said allylically unsaturated alcohol is selected from the group consisting of (a) relatively short chain alcohols having from 3 to about 6 carbon atoms selected from the group consisting of allyl alcohol, 2-methyl-2-propene-1-ol, 2-buten-1-ol, and 1-buten-3-ol; (b) relatively long chain alcohols having from 7 to about 20 carbon atoms selected from the group consisting of 10-undecen-1-ol and oleyl alcohol; (c) arylalcohols selected from the group consisting of cinnamyl alcohol, and allyl phenol; (d) monoadducts of a single 1,2-epoxide unit to said allylically unsaturated primary of secondary alcohol, selected from the group consisting of 2-hydroxyethyl allyl ether, 2-hydroxy-1-methylethyl allyl ether, and 2-hydroxy-2-methylethyl allyl ether; and, (e) cyclic olefinic alcohols in which the olefinic bond is in a single or fused ring structure having from 5 to 10 carbon atoms, selected from the group consisting of 2-cyclopenten-1-ol, 2-cyclohexen-1-ol, and 5-norbornene-2-methanol.

Claim 47

The polyformal macromer of claim 42 wherein (M) is 1,3-dioxolane (DOL), said macromer having an olefinic bond in a cyclic group at the head of each chain, and the structure: ##STR55## where m=about 6 to 250.

Claim 48

The polyformal macromer of claim 42 wherein (M) is 1,3-dioxolane (DOL), said macromer having an allyl group at the head of each chain, in the structure: CH.sub.2 ═CHCH.sub.2 --(OCH.sub.2 OCH.sub.2 CH.sub.2).sub.m --OH where m=about 6 to 250.

Claim 49

The polyformal macromer of random copolymer of claim 26 of 1,3-dioxolane (DOL) and propylene oxide (PO), said macromer having an acryloyl head group, in which macromer (Ml) is a (DOL) repeating unit, and (Et) is a PO repeating unit, and said macromer has the structure: ##STR56## where m=5 to about 50 and m'=3 to about 50.

Claim 50

The polyformal macromer of random copolymer of claim 26 in which macromer (M1) is a 1,3-dioxolane (DOL) repeating unit, and (ECH) is a epichlorohydrin repeating unit, and said macromer is selected from the group consisting of: (i) a DOL/ECH macromer having an acryloyl head group, and the structure: ##STR57## and, (ii) a DOL/ECH, said macromer having an allyl head group, and the structure: ##STR58## wherein m=3 to about 100 and m'=3 to about 50.

Claim 51

The polyformal macromer of block copolymer of claim 31 of ECH/DOL, said macromer having an acryloyl head group, in which macromer (ECH) is an epichlorohydrin repeating unit and (DOL) is a 1,3-dioxolane repeating unit, and said macromer has the structure: ##STR59## wherein i=2 to about 50, and m=5 to about 100.

Claim 52

The polyformal macromer of block copolymer of claim 30 wherein said macromer has an acryloyl head and is a block copolymer derived from 1,3-dioxolane (DOL) in combination with a cyclic ether (Et) repeating unit, sequentially, so as to have the structure ##STR60## where m=5 to about 50 and m'=3 to about 50.

Claim 53

A copolymer of a polyformal macromer, and, an olefinically unsaturated monomer, produced by polymerizing (A) said polyformal having a structure selected from R--(M) m --OH for non-end-capped and, R--(M) m --OZ for end-capped polyformals, respectively, wherein, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal, the chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened; Z is the residue of an end-capping unit selected from the group consisting of --R 5 , ##STR61## --SiR 3 5 , --CH 2 CH 2 CN, --SO 3 Na, --SO 3 K, and, --SO 3 NH 4 , except that R 5 cannot be H; and, R represents the residue of a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR62## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl, and most preferably methyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxyl, haloalkoxyl, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxyl, and haloaralkoxyl, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR63## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 6 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; most preferably, both are H, or, if one is H, the other is CH 3 ; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the structure ##STR64## wherein only G is optionally present; and, (ii) ##STR65## wherein, both R 2 and G are optionally present; that is, when both are absent, they are replaced with a bond directly connecting the OH group to the ring; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; with, (B) at least one olefinically unsaturated monomer, in the presence of an effective amount of (C) a free radical generating catalyst, wherein a free radical polymerization is initiated by heat, peroxide, or hydroperoxide decomposition, redox catalysts, or radiation, so as to yield a comb-shaped graft copolymer of formal macromer represented by the structure [R--(M).sub.m --OH].sub.n' [M.sub.o ].sub.n" ( 27) or, [R--(M).sub.m --OZ].sub.n' [M.sub.o ].sub.n" ( 27') wherein, M o represents the olefinically unsaturated monomer; n' represents an integer in the range from 1 to about 10 4 , and refers to the number of pendant polyformal chains; n" represents an integer in the range from 1 to about 10 6 ; and, m represents an integer in the range from 2 to about 500.

Claim 54

A copolymer of a polyformal macromer, and, an olefinically unsaturated monomer, produced by polymerizing (A) said polyformal having a structure selected from R--(M) m --OH for non-end-capped and, R--(M) m --OZ for end-capped polyformals, respectively, wherein, M represents a repeating unit of a polymeric chain in a homo-, block, or random copolymer of cyclic formal, the chain containing at least 25% by wt of the repeating unit of at least one said cyclic formal which is ring-opened; Z is the residue of an end-capping unit selected from the group consisting of --R 5 , ##STR61## --SiR 3 5 , --CH 2 CH 2 CN, --SO 3 Na, --SO 3 K, and, --SO 3 NH 4 , except that R 5 cannot be H; and, R represents the residue of a primary or secondary alcohol R--OH having a terminal vinyl group, said alcohol being selected from the group consisting of (a) an acryloyl alcohol wherein the vinyl unsaturation is adjacent a carbonyl group as in the structure ##STR62## wherein, R 1 is H or C 1 -C 20 alkyl, preferably lower C 1 -C 5 alkyl, and most preferably methyl; R 2 is selected from a saturated group consisting of branched or linear alkylene, haloalkylene, alkoxyl, haloalkoxyl, each C 1 -C 20 , aralkylene, haloaralkylene, aralkoxyl, and haloaralkoxyl, each C 7 -C 20 ; and, G, when present, is a polyether spacer having a number average molecular weight Mn from about 100 to about 10,000, and when absent, is replaced with a bond; (b) a styrylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to an aromatic ring, represented by the structure ##STR63## wherein, R 2 and G, if either is present, is in an ortho-, meta-, or para-position of the phenyl ring which may be substituted, said position being relative to that of the olefinically unsaturated group; when both R 6 and G are absent, they are replaced with a bond connecting the OH group to the ring; and, R 3 and R 4 are selected from the group consisting of hydrogen, C 1 -C 10 alkyl and haloalkyl, and, at least one of R 3 and R 4 is always H; most preferably, both are H, or, if one is H, the other is CH 3 ; (c) an allylically unsaturated primary or secondary alcohol wherein the ethylenic unsaturation is adjacent to a saturated carbon atom, represented by the structure ##STR64## wherein only G is optionally present; and, (ii) ##STR65## wherein, both R 2 and G are optionally present; that is, when both are absent, they are replaced with a bond directly connecting the OH group to the ring; and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl and haloalkyl, and, C 6 -C 20 aryl and aralkyl; with, (B) at least one olefinically unsaturated monomer, in the presence of an effective amount of (C) a free radical generating catalyst, wherein a free radical polymerization is initiated by heat, peroxide, or hydroperoxide decomposition, redox catalysts, or radiation, so as to yield a comb-shaped graft copolymer of formal macromer represented by the structure [R--(M).sub.m --OH].sub.n' [M.sub.o ].sub.n" ( 27) or, [R--(M).sub.m --OZ].sub.n' [M.sub.o ].sub.n" ( 27') wherein, M o represents the olefinically unsaturated monomer; n' represents an integer in the range from 1 to about 10 4 , and refers to the number of pendant polyformal chains; n" represents an integer in the range from 1 to about 10 6 ; and, m represents an integer in the range from 2 to about 500.

Claim 55

The polyformal macromer of claim 49 wherein said olefinically unsaturated monomer is selected from the group consisting of (i) C 2 -C 12 vinyl monomers selected from the group consisting of vinyl chloride, vinyl acetate, acrylonitrile, ethylene, propylene, 4-vinyl pyridine, vinyl pyrrolidone, vinyl benzoic acid, ethyl vinyl ether, salts of vinyl sulfonate, vinylidene chloride, and N-vinyl cabazole; (ii) C 8 -C 16 styryl monomers selected from the group consisting of styrene, 4-chlorostyrene, vinyl toluene, and alpha-methyl styrene; (iii) alpha,beta-ethylenically unsaturated carboxylic acids, acrylic acid and methacrylic acid, and those having from 3 to 8 carbon atoms, and derivatives thereof selected from the group consisting of esters of C 1 -C 20 alcohols said esters selected from the group consisting of ethyl acrylate, ethyl methacrylate, glycidyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; acrylamide and amides of C 1 -C 20 amines such as N,N-dimethylacrylamide; and, metal salts such as sodium acrylate; and, the corresponding analogs of methacrylates and methacrylamide; (iv) C 4 -C 8 diene monomers selected from the group consisting of butadiene and isoprene; (v) C 5 -C 10 allylically unsaturated monomers selected from the group consisting of allyl acetate, and diallylphthalate; and, (vi) C 5 -C 14 cyclic olefins selected from the group consisting of norbornene, dicyclopentadiene, cyclopentene, 1,5-cyclooctadiene and norbornadiene.

Claim 56

A non-hydrolyzable formal-siloxane block copolymer of an end-capped formal macromer possessing an allyl head group, produced by reacting said end-capped formal macromer with an organohydrosiloxane having from 1 to about 30 Si--H bonds and an average mol wt Mn in the range from 300 to 5000 having the formula R".sub.3 SiO(R".sub.2 SiO).sub.k (R"SiHO).sub.k' SiR".sub.3 ( 19) wherein R" is an unsubstituted or halogen-substituted monovalent C 1 -C 5 hydrocarbon group, k is an integer in the range from 0 to about 300, and k' is an integer in the range from 1 to about 30, under addition reaction conditions, at a temperature in the range from about 50°-100° C. in the presence of a solvent unreactive with the reactants, and a neutral Pt-containing hydrosilylation catalyst, so as to produce a formal-siloxane block copolymer of macromer formed with a polyhydrosiloxane, said block copolymer being represented by the formula A'A".sub.k' wherein, A' represents the residue of a polysiloxane block, A" represents the residue of a polyformal block of endcapped macromer.

Claim 57

A non-hydrolyzable formal-siloxane block copolymer of an end-capped formal macromer possessing an allyl head group, produced by reacting said end-capped formal macromer with an organohydrosiloxane having from 1 to about 30 Si--H bonds and an average mol wt Mn in the range from 300 to 5000 having the formula R".sub.3 SiO(R".sub.2 SiO).sub.k (R"SiHO).sub.k' SiR".sub.3 ( 19) wherein R" is an unsubstituted or halogen-substituted monovalent C 1 -C 5 hydrocarbon group, k is an integer in the range from 0 to about 300, and k' is an integer in the range from 1 to about 30, under addition reaction conditions, at a temperature in the range from about 50°-100° C. in the presence of a solvent unreactive with the reactants, and a neutral Pt-containing hydrosilylation catalyst, so as to produce a formal-siloxane block copolymer of macromer formed with a polyhydrosiloxane, said block copolymer being represented by the formula A'A".sub.k' wherein, A' represents the residue of a polysiloxane block, A" represents the residue of a polyformal block of endcapped macromer.