Water-thinnable mixtures of base-neutralized products of reaction of H3 PO4 with polyether epoxides and with other type epoxides

Claim 2

The process for preparing water-thinnable, base-salified reaction products of orthophosphoric acid and polyether epoxides which comprises: (I) reacting orthophosphoric acid with (1) a polyether epoxide resin E 1 consisting essentially of molecules, each of which is of the formula ##STR47## wherein Q, independently, in each occurence, is ##STR48## n is an integer of from 0 to 40, r is zero, 1 or 2 and, independently in each occurrence; R 1 is H, methyl or ethyl, R 2 is --Br, --Cl or a C 1 to C 4 alkyl or alkenyl group, R 3 is a C 1 -C 4 alkylene or alkenylene group, >C(CF 3 ) 2 , --CO, --SO 2 --, --S--, --O-- or a valence bond, and R 4 is --Br, --Cl or a C 1 to C 4 alkyl or alkenyl group, R 20 is H or alkyl of 1 to 12 carbons; and (2) E 2 , a vicinal epoxide, other than one of formula (a) or (q), which has an EEW (epoxide equivalent weight) within the range of from about 90 to about 2000 and is convertible to a water-dispersible material by reaction with orthophosphoric acid and neutralization with a base, said reaction being carried out by contacting E 1 and E 2 with an orthophosphoric acid source material and from 0 to 25 molecular proportions of water per molecular proportion of H 3 PO 4 provided by said source material until the fraction of the oxirane groups in E 1 and E 2 converted is at least sufficient to render the resulting mixed product water-thinnable when contacted with a base, the amount of orthophosphoric acid included as such in said source material, or obtainable therefrom by hydrolysis, being such as to provide at least 0.3 P--OH groups per oxirane group, and the mole ratio of E 1 to E 2 epoxides being within the range of from about 0.1 to about 100, and (II) contacting the resulting mixed reaction product with at least enough of a base to render it water-thinnable.

Claim 3

The process of claim 1 in which Q, in all occurrences, is ##STR49##

Claim 4

The process of claim 1 in which E 2 consists essentially of molecules, each of which, independently, is of a kind represented by one of formulas (b) through (p) following: (b) a methylol- or alkoxymethyl-substituted phenylglydicyl ether of the following formula ##STR50## wherein Y is H or a C 1 to C 4 alkyl or alkenyl group, each YO--CH 2 --group is either ortho or para to a glycidyloxy group, x is 1, 2 or 3, p is 0 or 1 and a is 1 or 2, R 1 , independently in each occurrence, is H, methyl or ethyl, R 5 is a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl, phenoxy, --Br, --Cl group or a ##STR51## wherein y is 0, 1 or 2 Y and R 1 are as above defined, T is a C 1 -C 4 alkylene or alkenylene group, >C(CF 3 ) 2 , --SO 2 --, --S--, --O-- or a valence bond, R 6 is --Br, --Cl or a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl or phenoxy group, and t is 0 or 1; with the proviso that (x+a) cannot exceed 4 and (x+y) is from 2 to 4; (c) a methylol- or alkoxymethyl-substituted, (2,3-epoxy) propylbenzene of the formula ##STR52## wherein: b is 1 to 3, d is 0 or 1, R 7 is C 1 -C 12 alkyl or ##STR53## Y' is H or a C 1 to C 4 alkyl or alkenyl group, R 1 is H, methyl or ethyl, with the proviso that (b+d) cannot exceed 3; (d) di- and trioxides of acyclic or cyclic, C 4 to C 28 hydrocarbons or esters containing two or three non-aromatic, carbon-to-carbon double bonds and, optionally, a --Br, --Cl or --F or hydroxy substituent; (e) epoxy ethers of the formula R 8 --O--R 9 , wherein each of R 8 and R 9 is the same or a different monovalent radical deriveable by abstraction of hydrogen from a C 3 -C 12 aliphatic-, alicyclic- or phenalkylene-oxide; (f) 2,3-epoxypropyl halides, alcohols or esters of the formula ##STR54## wherein A is --Cl, --Br, --OH or ##STR55## R 1 is --H, --CH 3 or --C 2 H 5 and R 21 is a C 1 -C 15 hydrocarbyl group; (g) glycol monoethers of the formula ##STR56## and glycol diethers of the formula ##STR57## wherein, R 1 is --H, --CH 3 or --C 2 H 5 , R 10 is --H or --CH 3 , X is --H, --CH 3 or --C 2 H 5 , g is 1, 2 or 3 and h is an integer of from 2 to about 10; (h) diglycidyl ether or esters of the formula ##STR58## wherein R 11 is a divalent hydrocarbon radical of from 2 to 20 carbons, R 1 is --H, --CH 3 or --C 2 H 5 and i and j independently are 0 or 1; (i) mono or diglycidyl ethers of ##STR59## (j) mono-, di- or triglycidyl ethers of glycerine; (k) trifunctional aromatic epoxides ##STR60## wherein Z is ##STR61## R 12 is C 1 -C 2 alkoxy, C 1 -C 6 alkyl or C 2 -C 6 alkenyl R 13 is H, C 1 -C 12 alkyl or C 2 -C 12 alkenyl, R 14 is a C 1 -C 8 alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl group, ortho or para to those Z--CH 2 -- moieties on the benzene ring to which said group is attached, R 1 is as previously defined and R 15 is a C 1 -C 4 alkylene or alkenylene group or --SO 2 --; (l) tetraglycidyl ethers of the formula ##STR62## wherein R 16 is a C 1 to C 6 , divalent aliphatic hydrocarbon radical, ##STR63## >C(CF 3 ) 2 , --SO 2 --, --S--, --O-- or a valence bond and Z is ##STR64## (m) tri- to pentafunctional epoxy novolaks of the formula ##STR65## wherein p is 1 to 3, R 17 is H or --CH 3 , independently in each occurrence, R 18 is an alkylene group of 1 to 4 carbons and Z is ##STR66## (n) methylol substituted, oligomeric monoepoxides of the formula ##STR67## wherein u is 0, 1, 2 or 3, R 1 , independently in each occurrence, is H, methyl or ethyl and R 19 , independently in each occurrence, is a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl group; (o) epoxidized triglycerides of unsaturated fatty acids of up to 18 carbons each; and (p) one to one adducts of substituted phenols with diglycidyl ethers of substituted bis-phenols, of the formula ##STR68## wherein R 1 , R 2 , R 3 and r are as defined in preceding formula (a), Y, R 5 and p are as above defined in formula (b), v is 1, 2 or 3 and w, independently in each occurrence, is 0, 1 or 2.

Claim 5

The process of claim 2 in which E 1 consists essentially of molecules of formula (a).

Claim 6

The process of claim 3 in which E 2 consists essentially of molecules, each of which, independently, is of a kind represented by one of formulas (b), (c), (n) and (p).

Claim 7

The process of claim 2 in which Q, in essentially all occurrences is either ##STR69##

Claim 8

The process of claim 3 in which E 2 consists essentially of molecules, each of which, independently, is of a kind represented by one of formulas (d), (g), (m) or (o).

Claim 9

The process of claim 5 in which E 2 consists essentially of molecules of formula (b).

Claim 10

The process of claim 5 in which E 2 consists essentially of molecules of formula (n).

Claim 11

The process of claim 7 in which E 2 consists essentially of molecules of formula (d).

Claim 12

The process of claim 7 in which E 2 consists essentially of molecules of formula (m).

Claim 13

The process of claim 1 in which the amount of said acid source material employed is sufficient to convert essentially all of the oxirane groups in E 1 and E 2 and E 1 is reacted with the acid source material before E 2 is introduced to the reaction mixture.

Claim 14

The process of claim 12 in which E 1 is a mixture of two epoxides of formula (a), one of which has an average n value of from about 10 to about 13 and the other has an average n value of from 0 to about 1; and E 2 is an epoxide of formula (b) or (n).

Claim 15

The process of claim 1 in which said base is an amine of the formula NR 3 , wherein each R is H, methyl or ethyl independently, except that not more than one R is H.

Claim 16

The process of claim 14 in which said base is triethylamine.

Claim 17

The process of claim 1 in which the reaction is carried out in a reaction medium, water and said base are added to the reaction mixture and said medium is removed, thereby forming an aqueous dispersion of the neutralized, mixed reaction products of E 1 and E 2 with said acid source material.

Claim 18

A water-thinnable, resinous phosphate composition comprising: (A) resin molecules, each of which is deriveable by conversion to 1,2-glycol- or to beta-hydroxy phosphomonoester groups of the oxirane groups in an E 1 epoxide represented by one of formulas (a) and (q) in claim 1, (B) other molecules, each of which is deriveable by conversion to 1,2-glycol- or beta-hydroxy phosphomonoester groups of the oxirane groups in E 2 , a vicinal epoxide other than those of formulas (a) and (q), having an EEW within the range of from about 90 to about 2,000, the mole ratio of said E 1 -deriveable molecules to said E 2 -deriveable molecules being within the range of from about 0.1 to about 100, and the number ratio of glycol to monoester groups in each of said types of molecules being within the range of from zero to about 18; (C) from 0 to about 85 parts by weight of ortho phosphoric acid (H 3 PO 4 ) per 100 parts by weight of said E 1 - and E 2 -deriveable molecules, and (D) one or more bases, in such amount that at least enough of the P--OH moieties in said E 1 and E 2 -deriveable molecules are salified thereby to render them dispersible together in water.

Claim 19

The composition of claim 17 wherein said other molecules comprise benzene rings substituted with methylol or loweralkoxymethyl groups.

Claim 20

The composition of claim 17 wherein said base is a fugitive base.

Claim 21

The composition of claim 19 wherein said base is an amine of the formula NR 3 , wherein R is H, methyl or ethyl, independently, except that not more than one R is H.

Claim 22

The composition of claim 20 in which said base is triethylamine.

Claim 23

The composition of claim 17, in an aqueous dispersion.

Claim 24

A dispersion of claim 22, in which said composition is heat-convertible, coated on a substrate.

Claim 25

The coating of claim 23, dehydrated, desalified and cured in place on said substrate, by heating.

Claim 26

The composition of claim 17 wherein Q, in said formulas (a) and (q), is as defined in claim 6.

Claim 27

The composition of claim 17 wherein said resin molecules are deriveable from an E 1 epoxide as defined by formula (a) in claim 1.

Claim 28

The composition of claim 26 wherein Q, in said formula (a), is as defined in claim 6.

Claim 29

The composition of claim 18 in which said other molecules are deriveable from E 2 epoxide molecules, each of which, independently, is of a kind represented by one of formulas (b), (c), (n) and (p) in claim 3.

Claim 30

The composition of claim 28 in which said other molecules are deriveable from an E 2 epoxide of formula (b) or (n) in claim 3.

Claim 31

The composition of claim 29 in which said resin molecules are deriveable from a mixture of two E 1 epoxides of formula (a), Q being as defined in claim 6, the average n value for one of said two epoxides being from about 10 to about 13 and the other having an average n value of from 0 to about 1.

Claim 32

The composition of claim 17 wherein said other molecules are deriveable from E 2 epoxide molecules, each of which, independently, is of a kind represented by one of formulas (d), (g), (m) and (n) in claim 3.

Claim 33

The composition of claim 31 in which said E 2 epoxide molecules are of said formula (d).

Claim 34

The method of preparing the composition of claim 17 which comprises combining: (1) a reaction product of orthophosphoric acid with an E 1 epoxide as defined in claim 1, (2) a reaction product of orthophosphoric acid with an E 2 epoxide as defined in claim 3, and (3) sufficient of a base to render the combination dispersible in water.