Allyl terminated macromolecular monomers of polyethers

Claim 2

A process for the manufacture of a polyether macromer having an allylic group at one end and a hydroxyl group at the other, comprising, polymerizing (A) a cationically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure ##STR14## wherein, x is an integer in the range from 0 to about 4, except that when x>1, a second alkylene oxide having x=1 or 0 must be present, and, R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) and haloalkyl, and, C 6 -C 20 aryl and aralkyl, and, at least one of R 1 , R 2 , and R 3 is hydrogen; and (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR15## wherein R 1 has the same connotation as hereinabove; and, R 4 represents a member selected from the group consisting of, C 1 -C 20 alkyl or substituted alkyl, haloalkyl, alkoxyalkyl, aryl (Ar), substituted aryl (Ar-Q), wherein Q represents C 1 -C 10 alkyl, haloalkyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of ##STR16## wherein, G, if present, is a spacer selected from the group consisting of branched or linear alkyl, aralkyl, haloalkyl, haloaralkyl, alkoxyl and aralkoxy, each having from 1 to about 20 carbon atoms (C 1 -C 20 ); and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) 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 macromer having the structure R--(M).sub.m --OH (V) wherein R represents the residue of said monoolefinically unsaturated alcohol, M represents the residue of at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500 with Mn=200-10,000.

Claim 3

The process of claim 1 wherein said ring-opened cyclic ether macromer is selected from the group consisting of a homomacromer of said alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, haloalkyl-1,2-epoxide, aliphatic glycidyl ether, aromatic glycidyl ether, and oxetane; a macromer copolyether copolymer of tetrahydrofuran or oxepane with a comonomer selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide, oxetane, an aliphatic glycidyl ether, and an aromatic glycidyl ether; and, a macromer block copolyether of an alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide, oxetane, an aliphatic glycidyl ether, and an aromatic glycidyl ether.

Claim 4

The process of claim 1 wherein said ring-opened cyclic ether macromer is selected from the group consisting of a homomacromer of said alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, haloalkyl-1,2-epoxide, aliphatic glycidyl ether, aromatic glycidyl ether, and oxetane; a macromer copolyether copolymer of tetrahydrofuran or oxepane with a comonomer selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide, oxetane, an aliphatic glycidyl ether, and an aromatic glycidyl ether; a macromer block copolyether of an alkylene oxide (I) selected from the group consisting of a 1,2-epoxide, a haloalkyl-1,2-epoxide and oxetane, an aliphatic glycidyl ether, and an aromatic glycidyl ether.

Claim 5

The process of claim 3 wherein said monoolefinically unsaturated alcohol is selected from the group consisting of (i) a monoolefinically unsaturated acyclic "allylic" alcohol having the structure (III) selected from the group consisting of (a) a relatively short chain alcohol having from 3 to about 6 carbon atoms including allyl alcohol, 2-methyl-2-propene-1-ol, 2-buten-1-ol, 1-buten-3-ol (1-methallyl alcohol), 3-buten-1-ol, 4-penten-1-ol, 2-pentene-1-ol, 3-penten-2-ol, 4-penten-2-ol, 2-methyl-1-buten-3-ol, 2-methyl-1-buten-4-ol, 3-methyl-2-buten-1-ol, 2-ethyl-1-propen-3-ol, 2-ethyl-1-penten-3-ol, 5-hexen-1-ol, 4-hexen-1-ol, 5-hexene-1-ol, 2-methyl-1-penten-3-ol, 2-methyl-4-penten-3-ol, and 4-methyl-3-penten-1-ol; (b) a relatively long chain alcohol having from 7 to about 20 carbon atoms including 9-decen-1-ol, 10-undecen-1-ol, citronellol and oleyl alcohol; and, (c) arylalcohols in which the OH group is on the side-chain including cinnamyl alcohol, and those in which the OH group is a phenolic OH group including 2-allyl phenol; (ii) allylic cyclic alcohols having the structure (IV) wherein the olefinic bond is in a single or fused ring structure having from 5 to 10 carbon atoms, including penten-1-ol, 2-cyclohexen-1-ol, 3-cyclohexen-1-methanol, 6,6-dimethyl bicyclo[3.3.1]hept-2-ene-2-ethanel[(IS)-(-)-Nopol], 5-norbornene-2-methanol, and bicyclo(2.2.2)oct-5-ene-2-methanol; and, (iii) monoadducts of a single cyclic ether with the foregoing "allylic" alcohols, including a monoadduct with an alcohol selected from the group consisting of 2-hydroxyethyl allyl ether, 2-hydroxy-1-methylethyl allyl ether, 2-hydroxy-2-methylethyl allyl ether, 4-hydroxybutyl allyl ether, diethylene glycol monoallyl ether, 2-hydroxy-2-chloromethyl ethyl allyl ether.

Claim 6

The process of claim 3 wherein said cationic initiator is selected from the group consisting of boron trifluoride (BF 3 ), boron trifluoride etherate complexes, tin tetrachloride (SnCl 4 ), a fluorinated metallic acid catalyst having the formula HMF 6 wherein M is selected from P, As or Sb; an oxonium salt of said acid and oxonium salts of tetrafluoroboron.

Claim 7

The process of claim 4 wherein said monoolefinically unsaturated alcohol is at least partially soluble in the reaction mass subjected to polymerization.

Claim 8

The process of claim 5 wherein polymerization is effected in the range from about 0° C. to about 150° C. and ambient pressure.

Claim 9

The process of claim 6 wherein said cationic initiator is present in an amount in the range from 0.001 part to about 1 part by wt per 100 parts by wt of said cyclic ether.

Claim 10

The process of claim 7 wherein said allylically ended macromer is a macromer block copolyether having the structure R--(M').sub.m' --(M").sub.m" --OH (VI) wherein M' and M" represent two ring-opened cyclic ethers, and, m' and m" are integers each in the range from 1 to about 300 such that m'+m"=m.

Claim 11

A polyether macromer having an allylic group at one end and a hydroxyl group at the other, formed by polymerizing (A) a cationically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure ##STR17## wherein, x is an integer in the range from 0 to about 4, except that when x>1, a second alkylene oxide having x=1 or 0 must be present, and, R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) and haloalkyl, and, C 6 -C 20 aryl and aralkyl, and, at least one of R 1 , R 2 , and R 3 is hydrogn; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR18## wherein R 1 has the same connotation as hereinabove; and, R 4 represents a member selected from the group consisting of, C 1 -C 20 alkyl or substituted alkyl, haloalkyl, alkenyl, substituted alkenyl, haloalkenyl, alkoxyalkyl, aryl (Ar), substituted aryl (Ar-Q), wherein Q is selected from the group consisting of C 1 -C 10 alkyl, haloalkyl, C 2 -C 10 alkenyl or haloalkenyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of ##STR19## wherein, G, if present, is a spacer selected from the group consisting of branched or linear alkyl, aralkyl, haloalkyl, haloaralkyl, alkoxyl and aralkoxyl, each having from 1 to about 20 carbon atoms (C 1 -C 20 ); and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) 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 macromer having the structure R--(M).sub.m --OH (V) wherein R represents the residue of said monoolefinically unsaturated alcohol, M represents the residue of at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500 with Mn=200-10,000; whereby said macromer is produced in conjunction with at least a trace quantity of cyclic oligomer of said cyclic ether.

Claim 12

A polyether macromer having an allylic group at one end and a hydroxyl group at the other, formed by polymerizing (A) a cationically ring-openable cyclic ether selected from the group consisting of (i) at least one alkylene oxide having the structure ##STR17## wherein, x is an integer in the range from 0 to about 4, except that when x>1, a second alkylene oxide having x=1 or 0 must be present, and, R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) and haloalkyl, and, C 6 -C 20 aryl and aralkyl, and, at least one of R 1 , R 2 , and R 3 is hydrogn; and, (ii) an aliphatic or aromatic glycidyl ether having the structure ##STR18## wherein R 1 has the same connotation as hereinabove; and, R 4 represents a member selected from the group consisting of, C 1 -C 20 alkyl or substituted alkyl, haloalkyl, alkenyl, substituted alkenyl, haloalkenyl, alkoxyalkyl, aryl (Ar), substituted aryl (Ar-Q), wherein Q is selected from the group consisting of C 1 -C 10 alkyl, haloalkyl, C 2 -C 10 alkenyl or haloalkenyl; and, (B) a monoolefinically unsaturated primary or secondary alcohol represented by a structure selected from the group consisting of ##STR19## wherein, G, if present, is a spacer selected from the group consisting of branched or linear alkyl, aralkyl, haloalkyl, haloaralkyl, alkoxyl and aralkoxyl, each having from 1 to about 20 carbon atoms (C 1 -C 20 ); and, R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl (having from 1 to about 20 carbon atoms) 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 macromer having the structure R--(M).sub.m --OH (V) wherein R represents the residue of said monoolefinically unsaturated alcohol, M represents the residue of at least one said cyclic ether which is ring-opened, and, m represents an integer in the range from 2 to about 500 with Mn=200-10,000; whereby said macromer is produced in conjunction with at least a trace quantity of cyclic oligomer of said cyclic ether.

Claim 13

The polyether macromer of claim 10 which is a homomacromer having the structure ##STR20## wherein n is in the range from 2 to about 100.

Claim 14

The polyether macromer of claim 10 after it has been aminated so that it has the structure ##STR21## wherein X' represents a halogen, n is an integer in the range from 2 to 100, and R 8 represents the residue of an amine used to aminate the macromer.