ALLOPHANATE MODIFIED DIPHENYLMETHANE DIISOCYANATES, PREPOLYMERS THEREOF, AND THEIR USE IN THE PREPARATION OF POLYUREAS AND POLYURETHANES

1 . An allophanate-modified diphenylmethane diisocyanate having an NCO group content of 0.25 to 30%, and comprising the reaction product of:

(a) diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1000 up to about 10,000;

in the presence of:

(c) a suitable catalyst.

2 . The allophanate-modified diphenylmethane diisocyanate of claim 1 having an NCO group content of from 1 to 26%, wherein

(a) said diphenylmethane diisocyanate comprises from 1 to 81% by weight of the 2,4′-isomer, from 19 to 99% by weight of the 4,4′-isomer and from 0 to 6% by weight of the 2,2′-isomer, with the sum of the %'s by weight of the isomers totaling 100% by weight of said diphenyli - nethane diisocyanate;

(b) said polyether monol has an equivalent weight of greater than 1000 to 10,000.

3 . A process for the preparation of the allophanate-modified diphenylmethane diisocyanate of claim 1 , comprising reacting

(a) diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1000 up to about 10,000;

in the presence of:

(c) a suitable catalyst.

4 . A prepolymer of an allophanate-modified diisocyanate having an NCO group content of 0.25 to 26% and comprising the reaction product of:

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 0.25 to 30% and which comprises the reaction product of:

(a) diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1000 up to about 10,000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 6 and a molecular weight of from 500 to 10,000.

5 . The prepolymer of claim 4 having an NCO group content of 0.5 to 23%, wherein

(1) said allophanate-modified diphenylmethane diisocyanate has an NCO group content of 1 to 26%, and comprises the reaction product of:

(a) diphenylmethane diisocyanate comprising from 1 to 81% by weight of the 2,4′-isomer, from 19 to 99% by weight of 4,4′-isomer and from 0 to 6% by weight of the 2,2′-isomer, with the sum of the %'s by weight of the isomers totaling 100% by weight of said diphenylmethane diisocyanate;

and

(b) a polyether monol having an equivalent weight of from 1000 to 10,000;

in the presence of

(c) a suitable catalyst;

and

(2) said polyether polyol has a functionality of from 1.5 to 6 and a molecular weight of from 500 to 10,000.

6 . A process for the preparation of the prepolymer of the allophanate-modified diphenylmethane diisocyanate having an NCO group content of 0.25 to 26% of claim 4 , comprising reacting

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 0.25 to 30% and which comprises the reaction product of:

(a) diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1000 up to about 10,000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 6 and a molecular weight of from 500 to 10,000.

7 . A two-component polyurea comprising the reaction product of:

(A) the prepolymer of claim 4 ; and

(B) an isocyanate-reactive component comprising at least one compound selected from the group consisting of:

(1) one or more amine group containing compound having a functionality of at least 1.8 and a molecular weight of greater than 750 to about 7000;

and

(2) at least one diamine or polyamine having a functionality of at least 1.8 and a molecular weight of less than or equal to 750.

8 . The two-component polyurea of claim 7 , wherein

(A) said prepolymer of the allophanate-modified diphenylmethane diisocyanate has an NCO group content of 0.25 to 26% by weight and comprises the reaction product of:

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 1 to 26% by weight and which comprises the reaction product of:

(a) diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1100 up to about 7000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 4 and a molecular weight of from 1000 to 7000.

9 . A two-component polyurea comprising the reaction product of:

(A) a prepolymer of an allophanate-modified diphenylmethane diisocyanate which has an NCO group content of 5 to 26% by weight and comprises the reaction product of:

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 10 to 30% by weight and which comprises the reaction product of:

(a) diphenylmethane diisocyanate which comprises from 1 to 81% by weight of the 2,4′-isomer, from 19 to 99% by weight of the 4,4′-isomer and from 0 to 6% by weight of the 2,2′-isomer, with the sum of the %'s by weight of the isomers totaling 100% by weight of said diphenylmethane diisocyanate;

with

(b) a polyether monol having an equivalent weight of from 1100 up to 5,000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 6 and a molecular weight of from 500 to 10,000;

and

(B) said isocyanate-reactive component comprising at least one compound selected from the group consisting of:

(1) one or more amine group containing compound having a functionality of at least 1.8 and a molecular weight of greater than 750 up to about 7000;

and

(2) at least one diamine or polyamine having a functionality of at least 1.8 and a molecular weight of less than or equal to 750.

10 . The two-component polyurea of claim 7 , wherein (B) said isocyanate-reactive component additionally comprises (3) one or more hydroxyl group containing compounds

11 . A process for preparing a polyurea, comprising reacting:

(A) the prepolymer of claim 4 ;

with

(B) an isocyanate-reactive component comprising at least one compound selected from the group consisting of:

(1) one or more amine group containing compound having a functionality of at least 1.8 and a molecular weight of greater than 750 to about 5000;

and

(2) at least one diamine or polyamine having a functionality of at least 1.8 and a molecular weight of less than or equal to 750.

12 . A one-component polyureaurethane comprising the reaction product of:

(A) the prepolymer of claim 4 ;

with

(B) water;

optionally, in the presence of

(C) one or more catalysts.

13 . The one-component polyureaurethanes of claim 12 , wherein

(A) said prepolymer of an allophanate-modified diisocyanate has an NCO group content of 0.5 to 23% and comprises the reaction product of:

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 1 to 26% and which comprises the reaction product of:

(a) diphenylmethane diisocyanate comprising (i) from 20 to 73% by weight of the 2,4′-isomer, (ii) from 27 to 80% by weight of the 4,4′-isomer, and (iii) from 0 to 3% by weight of the 2,2′-isomer, with the sum of the %'s by weight of (i), (ii) and (iii) totaling 100% by weight of diphenylmethane diisocyanate,

with

(b) a polyether monol having an equivalent weight of greater than 1100 up to about 7000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 3.5 and a molecular weight of from 1000 to 7000.

14 . A one-component polyureaurethane which comprises

(A) a prepolymer of an allophanate-modified diphenylmethane diisocyanate which has an NCO group content of 0.25 to 23% and comprises the reaction product of:

(1) an allophanate-modified diphenylmethane diisocyanate having an NCO group content of 0.25 to 30% and which comprises the reaction product of:

(a) diphenylmethane diisocyanate which comprises from 1 to 81% by weight of the 2,4′-isomer, from 19 to 99% by weight of the 4,4′-isomer and from 0 to 6% by weight of the 2,2′-isomer, with the sum of the %'s by weight of the isomers totaling 100% by weight of said diphenylmethane diisocyanate;

with

(b) a polyether monol having an equivalent weight of 1000 up to about 10,000;

in the presence of

(c) a suitable catalyst;

and

(2) at least one polyether polyol having a functionality of from 1.5 to 4 and a molecular weight of from 500 to 7000;

and

(B) water;

optionally, in the presence of

(C) one or more catalysts.

15 . A process of preparing a polyureaurethane comprising reacting:

(A) the prepolymer of claim 4 ;

and

(B) water;

optionally in the presence of

(C) one or more catalysts.

16 . A sealant comprising the two-component polyurea of claim 9 .

17 . A caulking agent comprising the one-component polyureaurethane of claim 14 .