Ethoxylate isocyanate compound and its use as a emulsifier

Abstract

Provided is a composition comprising one or more compound having the structure of formula II: ##STR00001##
wherein A is a residue of a polyisocyanate, L is a linking group formed by a reaction of an isocyanate group with an isocyanate-reactive group, n is 5 to 25, m is 0 to 100, and Z is methyl or ethyl or propyl, and
wherein the ratio of the sum of the moles of isocyanate groups plus the moles of said L groups to the moles of said Z groups is 2:1 to 30:1. Also provided is an emulsion in which the particles comprise such a composition and further comprise one or more water-insoluble compound that does not have the structure A-NCO.

Claims

1. An emulsion comprising particles suspended in an aqueous medium, wherein said particles comprise (a) one or more compound having structure A-NCO; (b) one or more compound having the structure of formula II: ##STR00013##  wherein A is the same as in compound (a), and (c) one or more water-insoluble compound that is different from compound (b); that does not have the structure A-NCO, wherein A is the same as in formula II; and that is selected from the group consisting of polyepoxy compounds and aromatic polyisocyanates; wherein A is a residue of a polyisocyanate, L is a linking group formed by a reaction of an isocyanate group with an isocyanate-reactive group, n is 5 to 25, m is 0 to 100, and Z is methyl or ethyl or propyl, and wherein the ratio of the sum of the moles of isocyanate groups on said compound (a) plus the moles of isocyanate groups on said compound (b) plus the moles of said L groups to the moles of said Z groups is 5:1 to 30:1.

2. The emulsion of claim 1, wherein m is zero.

3. The emulsion of claim 2, wherein A is the residue of a monomer of a diisocyanate, the residue of a dimer of a diisocyanate, or the residue of a trimer of a diisocyanate.

4. The emulsion of claim 3, wherein A is the residue of a trimer of a diisocyanate.

5. The emulsion of claim 4 wherein A is a residue of a trimer of hexane diisocyanate.

6. The emulsion of claim 4 wherein n is 10 to 14.

7. The emulsion of claim 1 wherein said water-insoluble compound (c) is an aromatic polyisocyanate.

8. The emulsion of claim 2, wherein A is the residue of a monomer of an aliphatic diisocyanate, the residue of a dimer of an aliphatic diisocyanate, or the residue of a trimer of an aliphatic diisocyanate.

9. The emulsion of claim 3, wherein A is the residue of a trimer of an aliphatic diisocyanate.

Description

COMPARATIVE EXAMPLE 1: ETHOXYLATED HDI

(1) HDI was mixed with one of the MPEG polymers as listed below. Each reaction mixture, prior to the reaction taking place, is characterized by the ratio of moles of isocyanate groups to moles of hydroxyl groups. The reaction mixture was held under nitrogen and stirred at 100° C. for five hours. It is contemplated that the following product was formed:

(2) ##STR00009##

(3) After the product was made, a mixture was made of the product and water, with 4 parts by weight product and 96 parts by weight water, and the particle size was measured. The results were as follows:

(4) TABLE-US-00002 Ethoxylated HDI in Water MPEG type NCO:OH mole ratio D50 (nm) 750 2:1 agglomerate 550 2:1 agglomerate 550 6:1 6,414 nm 350 2:1 agglomerate 350 5:1 agglomerate
None of the samples made an acceptable emulsion. It is contemplated that none of the samples would be useful as an emulsifier in a mixture with a compound (c).

COMPARATIVE EXAMPLE 2: ETHOXYLATED HDI DIMER

(5) HDI dimer has the structure

(6) ##STR00010##

(7) HDI dimer was mixed with one of the MPEG polymers as listed below. Each reaction mixture, prior to the reaction taking place, is characterized by the ratio of moles of isocyanate groups to moles of hydroxyl groups. The reaction mixture was held under nitrogen and stirred at 100° C. for five hours. It is contemplated that the following product was formed:

(8) ##STR00011##

(9) After the product was made, two mixtures were made as follows: Mixture 2-1: 4 parts by weight of the product and 96 parts by weight of water, Mixture 2-2: 2 parts by weight of the product; 2 parts by weight of HDI trimer, and 96 parts by weight of water, and

(10) the particle sizes were measured. The results were as follows:

(11) TABLE-US-00003 HDI Trimer plus Ethoxylated HDI Dimer in Water Mixture 2-1 Mixture 2-2 MPEG type NCO:OH mole ratio D50 (nm) D50 (nm) 750 2:1 14 >1,000 550 6:1 163 >1,000 550 5.4:1.sup.  68 >1,000 550 3:1 21 1,074 550 2:1 15 >1,000 350 6:1 114 560 350 3:1 86 8,284 350 2.5:1.sup.  35 >1,000 350 2:1 25 1,105
It is desirable to make emulsion particles with an added crosslinker (in this case, HDI trimer) with D50 of 500 nm or less. None of the samples met this target. None of the samples would be useful as an emulsifier in a mixture with a compound (c).

EXAMPLE 3: ETHOXYLATED HDI TRIMER WITHOUT COMPOUND (C)

(12) HDI trimer was mixed with one of the MPEG polymers as listed below. Each reaction mixture, prior to the reaction taking place, is characterized by the ratio of moles of isocyanate groups to moles of hydroxyl groups. The reaction mixture was held under nitrogen and stirred at 100° C. for five hours. It is contemplated that the reaction product included a compound having structure III where R is —(CH.sub.2).sub.6—.

(13) After the product was made, a mixture was made of the product and water, with 4 parts by weight product and 96 parts by weight water, and the particle size was measured. The results were as follows:

(14) TABLE-US-00004 Ethoxylated HDI Trimer in Water MPEG type NCO:OH mole ratio D50 (nm) 750 14:1  230 550 14:1  144 350 14:1  450 550 8:1 50 550 6:1 32 550 4:1 dissolved 550 2:1 agglomerated

EXAMPLE 4: ETHOXYLATED HDI TRIMER WITH COMPOUND (C)

(15) Reaction products of HDI trimer and MPEG 550, at NCO:OH mole ratio of 6:1, were made as in Example 3. Mixtures were made with various additional compounds, as follows:

(16) TABLE-US-00005 Abbreviation Compound Supplier Epoxy D.E.R. ™ 331 ™ liquid epoxy resin The Dow Chem- ical Co. MDI-L Isonate ™ 50 OP isocyanate; liquid; The Dow Chem- 50% 4,4′ MDI and 50% 2,4′ MDI ical Co. MDI-S Isonate ™ 125M isocyanate; solid; The Dow Chem- 98% 4,4′ MDI and 2% 2,4′ MDI ical Co.
Each mixture contained 96 parts by weight of water, X parts by weight of reaction product (of the reaction between HDI trimer and MPEG), and Y parts by weight of additional compound, where X+Y equaled 4 parts by weight. The ratio X:Y is shown below. The particle sizes of the mixtures were measured with the results as follows:

(17) TABLE-US-00006 additional compound X:Y D50 (nm) MDI-L 0.5:1 130 MDI-S 0.5:1 162 Epoxy 0.5:1 125 Epoxy 0.75:1  145 Epoxy 1.0:1 266 Epoxy 1.5:1 1,186

(18) The reaction product of HDI trimer with MPEG 550 at NCO:OH mole ratio of 6:1 acts as an useful emulsifier for a variety of additional compounds. Also, it is possible to vary D50 by varying the ratio X:Y.

EXAMPLE 5: ETHOXYLATED ADI TRIMER

(19) ADI trimer was mixed with an MPEG compound and butyl acetate and held with stirring under nitrogen at 100° C. for 4 hours. The amount of butyl acetate was 30% by weight based on the weight of the total mixture. The amount of ADI trimer plus the amount of MPEG compound was 70% by weight based on the weight of the total mixture. It is contemplated that the reaction product included a compound having structure III where R is

(20) ##STR00012##

(21) It is contemplated that a mixture of isomers was present.

(22) Reaction products were mixed with water in the proportion of 4 parts by weight reaction product and 96 parts by weight water. Where an emulsion resulted, the particle size was measured. The results were as follows. “nt” means not tested.

(23) TABLE-US-00007 Emulsion Formation of Ethoxylated ADI Trimer Compounds (Emulsion formation = “yes”, lack of emulsion = “fail”) Mole Ratio NCO:OH MPEG 550 MPEG 750 MPEG 1000 MPEG 2000 10:1 192 112  89 111 12:1 agglomerate nt nt nt 14:1 nt 160 153 nt 15:1 nt nt 156 nt 18:1 nt 227 187 250 20:1 nt agglomerate nt agglomerate 25:1 nt nt 237 fail 30:1 nt nt 272 nt 35:1 nt nt agglomerate nt
All of the reaction products showed some ability to form an emulsion in water. The products made with MPEG 1000 showed the best ability to form an emulsion. It is contemplated that useful reaction products of ADI trimer with MPEG compounds could be made at mole ratio of NCO:OH below 10:1.