Polyether polymer or copolymer, monomer therefor, and process for production thereof

Abstract

A polyether polymer or copolymer with a pendant group of the formula ##STR1## in its molecule, said polymer or copolymer consisting essentially of (1) 1 to 100 mole % of recurring units represented by the following formula (I) ##STR2## and (2) 0 to 99 mole % of at least one type of recurring units represented by the following formula (II) ##STR3## and having a reduced vicsocisty η red , determined at 45° C. in its 0.1% benzene solution or at 80° C. in its 0.1% monochlorobenzene solution, of at least 0.01; a process for producing thereof and novel epoxyether compound therefor.

What is claimed is: 
     
       1. A polyether polymer or copolymer with a pendant group of the formula ##STR27## in its molecule, said polymer or copolymer consisting essentially of (1) .[.1.]. .Iadd.5 .Iaddend.to 100 mole % of recurring units represented by the following formula (I) ##STR28## and (2) .[.0 to 99.]. .Iadd.0 to 95 .Iaddend.mole % of at least one type of recurring units represented by the following formula (II) ##STR29## wherein R represents a member selected from the class consisting of a hydrogen atom, substituted or unsubstituted C 1  -C 18  alkyl groups, substituted or unsubstituted C 2  -C 18  alkenyl groups, substituted or unsubstituted C 3  -C 8  cycloalkyl groups and substituted or unsubstituted C 6  -C 14  aryl groups, and having a reduced viscosity η red , determined at 45° C. in its 0.1% benzene solution or at 80° C. in its 0.1% monochlorobenzene solution, of at least .Badd.0.01. 
     
     
       2. The polyether polymer or copolymer of claim 1 wherein in the definition of R in formula (II), the substituent on the alkyl groups is selected from the class consisting of halogen, C 1  -C 10  alkoxy, C 2  -C 10  alkoxy-carbonyl, C 2  -C 10  acyl, C 1  -C 10  alkylthio, and optionally substituted C 6  -C 14  aryl; the substituent on the alkenyl groups is selected from the class consisting of halogen, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio; the substituent on the cycloalkyl groups is selected from the class consisting of halogen, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio; and the substituent on the aryl groups is selected from the class consisting of halogen, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio. 
     
     
       3. The polyether polymer or copolymer .Iadd.of claim 1 .Iaddend.having a reduced viscosity η red  of 0.01 to 5. 
     
     
       4. A process for producing the polyether polymer or copolymer of claim 1, which comprises polymerizing 2,3-epoxypropyl-2',3'-epoxy-2'-methylpropyl ether of the following formula (I-a) ##STR30## or copolymerizing it with a compound .Iadd.of .Iaddend.the following formula (III) ##STR31## wherein R represents a member selected from the class consisting of a hydrogen atom, substituted or unsubstituted C 1  -C 18  alkyl groups, substituted or unsubstituted C 2  -C 18  alkenyl groups, substituted or unsubstituted C 3  -C 8  cycloalkyl groups and substituted or unsubstituted C 6  -C 14  aryl groups, in the present of, as a catalyst, a heat-reaction product of (A) an organotin compound and .[.(b).]. .Iadd.(B) .Iaddend.a complete or partial ester compound of the formula (HO) 3  PO, said organotin compound (A) being selected from the group consisting of compounds of the following formulae (i) to (iv)   R.sub.a.sup.1 SnX.sub.4-a                                  (i)     wherein R 1  represents a C 1  -C 12  alkyl group unsubstituted or substituted by a substituent selected from halogen, hydroxy, C 1  -C 10  alkoxy and C 1  -C 10  alkylthio, a C 2  -C 8  alkenyl group unsubstituted or substituted by a substituent selected from halogen, hydroxy, C 1  -C 10  alkoxy, C 1  -C 10  alkylthio, and optionally substituted C 6  -C 14  aryl, a C 3  -C 8  cycloalkyl group unsubstituted or substituted by a substituent selected from halogen, hydroxy, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 1  -C 10  alkylthio and optionally substituted C 6  -C 14  aryl, a C 6  -C 14  aryl group unsubstituted or substituted by a substituent selected from .[.halogn.]. .Iadd.halogen.Iaddend., hydroxy, C 1  -C 12  alkyl, C 1  -C 10   alkoxy, C 1  -C 10  alkylthio and optionally substituted C 6  -C 14  aryl, or a C 7  -C 18  aralkyl group unsubstituted or substituted by a substituent selected from halogen, hydroxy, C 1  -C 12  alkyl, C 1  -C 10  alkoxy and C 1  -C 10  alkylthio; .[.x.]. .Iadd.X .Iaddend.represents an atom or group selected from halogen atoms, C 1  -C 12  alkoxy groups, aryloxy groups having .[.C 6  -C 14  .]. .Iadd.C 6  -C 18  aryl .Iadd.substituents.]..Iaddend., .[.acyloxy.]. groups having C 2  -C 12  acyl .Iadd.substituents .Iaddend.and residues of partial esters of phosphoric acid; and an is an integer of 1 to 4, provided that when a is an integer of 2 to 4, R 1  groups may be identical or different, and when a is 1 or 2, the X's may be identical or different;     R.sub.b.sup.1 SnO.sub.c                                    (ii)     wherein R 1  is as defined with regard to formula (i), b is 1 or 2, and when b is 1, c is 3/2 or when b is 2, c is 1, the compound of formula (ii) may form a complex with the compound of formula (i);     R.sup.2 --R.sub.2.sup.1 SnOSnR.sub.2.sup.1 --R.sup.2       (iii)     wherein R 1  is as defined with regard to formula (i), R 2  is as defined with regard to R 1  and X, and the two R 2  groups may be identical and different; and     (R.sub.3.sup.2 Sn).sub.d X'                                (iv)     wherein R 2  is the same as defined with regard to formula (iii) provided that at least one of the three R 2  groups is a group selected from the groups defined for R 1  in formula (i); X' is a member selected from the group consisting of a carbonate group, a phosphorus or oxyacid group, a polybasic carboxylic acid group and a residual moiety of a polyhydric alcohol; and d is a number greater than 1 and corresponds to the basicity of the member X'.   
     
     
       5. The process of claim 4 wherein the complete or partial ester compound (B) is a compound of the following formula   (R.sup.3 O).sub.3 P═O     wherein R 3  represents a member selected from the class consisting of a hydrogen atom, C 1  -C 12  alkyl groups C 2  -C 12  alkenyl groups and C 3  -C 8  cycloalkyl groups which may be substituted by halogen, and at least one of the R 3  groups represents groups other than hydrogen atom. .[.6. 2,3-epoxypropyl-2',3'-epoxy-2'-methylpropyl ether of the following formula (I-a).]. ##STR32##   
     
     
         .Iadd.7.  A polyether copolymer with a pendant group of the formula ##STR33## in its molecule, said copolymer comprising (1) from 1 to 99 mole percent of recurring units of formula (I) ##STR34## and (2) from 1 to 99 mole percent of at least one recurring unit derived from a monoepoxy compound selected from the group consisting of glycidyl acetate, glycidyl propionate, glycidyl benzoate, glycidyl cinnamate and glycidyl naphthonate, said copolymer having a reduced viscosity η red , determined at 45° C. in its 0.1% benzene solution or at 80° C. in its 0.1% monochlorobenzene solution, of at least 0.01. 
     
     
        .Iaddend. .Iadd.8.  A polyether copolymer with a pendant group of the formula ##STR35## in its molecule, said copolymer comprising (1) from 1 to 98 mole percent of recurring units of formula (I) ##STR36## (2) 1 to 98 mole percent of at least one type of recurring unit represented by the following formula (II) ##STR37## wherein R represents a member selected from the class consisting of a hydrogen atom, substituted or unsubstituted C 1  -C 18  alkyl groups, substituted or unsubstituted C 2  -C 18  alkenyl groups, substituted or unsubstituted C 3  -C 8  cycloalkyl groups and substituted or unsubstituted C 6  -C 14  aryl groups, wherein in the definition of R in formula (II), the substituent on the alkyl groups is selected from the class consisting of halogen, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl, C 1  -C 10  alkylthio, and optionally substituted C 6  -C 14  aryl; the substituent on the alkenyl groups is selected from the class consisting of halogen, C 1  -C 12  alkenyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio; the substituent on the cycloalkyl groups is selected from the class consisting of halogen, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio; and the substituent on the aryl groups is selected from the class consisting of halogen, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 2  -C 10  alkoxycarbonyl, C 2  -C 10  acyl and C 1  -C 10  alkylthio, and (3) 1 to 98 mole percent of at least one recurring unit derived from a monoepoxy compound selected from the group consisting of glycidyl acetate, glycidyl propionate, glycidyl benzoate, glycidyl cinnamate and glycidyl napthonate, said copolymer having a reduced viscosity η red , determined at 45° C. in its 0.1% benzene solution or at 80° C. in its 0.1% monochlorobenzene solution, of at least 0.01. .Iaddend.