Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof

Abstract

A self-crosslinkable polyurethane or polyurethane-urea aqueous dispersion, a preparation method therefor, and a use thereof. Side chains of the polyurethane or polyurethane-urea contain non-sterically-hindered siloxy groups. During the drying and activation of the aqueous dispersion, the siloxys in the side chains are hydrolyzed and crosslinked with each other to increase the cross-linking density, significantly improving the heat resistance, the humidity resistance, and other properties of an adhesive obtained therefrom. The aqueous dispersion itself has a good stability. In addition, an application system based thereon has an excellent stability and a long storage time. The aqueous dispersion is suitable for the preparation of high quality paints and sealants, especially adhesives.

Claims

1. A polyurethane or polyurethane-urea aqueous dispersion, wherein the polyurethane or polyurethane-urea aqueous dispersion is a reaction product obtained by reacting a composition comprising the following components: a) at least one silane component having a general formula of ##STR00002## wherein group R contains at least two NCO-reactive groups, wherein at least two of groups R.sub.1, R.sub.2 and R.sub.3 are methoxyls and/or ethoxyls, and the remaining groups R.sub.1, R.sub.2 and/or R.sub.3 is an alkyl; b) at least one polyol component having a functionality of 2-4, wherein the component b) comprises a mixture of a crystalline polyol having a number average molecular weight of 400-15,000 and at least one non-crystalline polyol having a number average molecular weight of 400-15,000; c) at least one polyisocyanate component; d) at least one hydrophilic compound component, the hydrophilic group of the hydrophilic compound comprises one or two of an ionic group and a potentially ionic group, the hydrophilic compound contains 2-3 NCO-reactive groups; e) at least one NCO-reactive, monofunctional nonionic hydrophilic compound component; and f) optionally, a compound containing 1-3 aminos and/or hydroxys in the molecule; and g) optionally, other isocyanate-reactive compounds.

2. The aqueous dispersion according to claim 1, wherein based on the total weight of the composition, the component a) is used in an amount of 0.02-5 wt %; the component b) is used in an amount of 30-94 wt %; the component c) is used in an amount of 5-40 wt %; the component d) is used in an amount of 0.2-10 wt %; the component e) is used in an amount of 0.01-10 wt %; the component f) is used in an amount of 0-10 wt %; the component g) is used in an amount of 0-15 wt %.

3. The aqueous dispersion according to claim 1, wherein the NCO-reactive functional group of component a), the silane component is selected from the group consisting of hydroxy, primary aminos, secondary aminos and combinations thereof.

4. The aqueous dispersion according to claim 1, wherein component b) has a number average molecular weight of 20-15,000.

5. The aqueous dispersion according to claim 1, wherein component b) comprises a mixture of a crystalline diol having a number average molecular weight of 1,000-4,000 and a non-crystalline diol having a number average molecular weight of 1,000-4,000.

6. The aqueous dispersion according to claim 5, wherein the weight ratio of the crystalline diol to the non-crystalline diol is 1-25:1.

7. The aqueous dispersion according to claim 1, wherein the hydrophilic compound containing an ionic group or a potentially ionic group in the component d) comprises a component selected from the group consisting of dimethylolpropionic acid, dimethylolbutanoic acid, dimethylol acetic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-3-aminopropanesulfonic acid, N-(2-aminoethyl)-3-aminopropanesulfonic acid and alkali metal salts, alkaline earth metal salts and ammonium salts thereof and combinations thereof.

8. The aqueous dispersion according to claim 1, wherein component e) has an ethylene oxide number of 4-200.

9. The aqueous dispersion according to claim 1, wherein the component f) is a compound containing 2-3 NCO-reactive functional groups, wherein at least one of the NCO-reactive functional groups is a primary amino or a secondary amino.

10. A method for preparing the aqueous dispersion as defined in claim 1, comprising the following steps: components b), c), d), e) and optionally g) react through a one-step or multi-step reaction to form a prepolymer with a terminal isocyanate, then the prepolymer reacts with component a) and optional f) through a one- or two-stage reaction, followed by water dispersion or dissolution, wherein a solvent which can be partially or completely removed by distillation during or after the dispersion is optionally used.

11. The aqueous dispersion according to claim 1, wherein the polyisocyanate component c) is a mixture of hexamethylene diisocyanate and isophorone diisocyanate with a weight ratio of 1-50:1 or a mixture of hexamethylene diisocyanate and 4,4′-dicyclohexylmethane diisocyanate with a weight ratio of 1-50:1, and the ionic group is carboxylate and/or sulfonate; the potentially ionic group is carboxyl and/or sulfonic group; and the NCO-reactive group is hydroxy and/or amino.

12. The aqueous dispersion according to claim 2, wherein based on the total weight of the composition, the component a) is used in an amount of 0.2-2.5 wt %; the component b) is used in an amount of 70-90 wt %; the component c) is used in an amount of 8-20 wt %; the component d) is used in an amount of 1-5 wt %; the component e) is used in an amount of 0.5-3 wt %; the component f) is used in an amount of 0.5-3 wt %; the component g) is used in an amount of 1-8 wt %.

13. The aqueous dispersion according to claim 3, wherein component a) is a silane having at least two primary aminos and/or secondary aminos.

14. The aqueous dispersion according to claim 3, wherein component a) is selected from the group consisting of N-β-(aminoethyl)-γ-aminopropyltrimethoxy silane, N-β-(aminoethyl)-γ-aminopropyltriethoxy silane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxy silane and combinations thereof.

15. The aqueous dispersion according to claim 4, wherein component b) comprises a component selected from the group consisting of a polyester polyol, a polycarbonate polyol, a polylactone polyol having a number average molecular weight of 500-5,000 and a functionality of 2-3, a small molecular alcohol having a number average molecular weight of 80-400 and a functionality of 2-4 and combination thereof.

16. The aqueous dispersion according to claim 5, wherein the non-crystalline diol is a polycarbonate diol prepared by the reaction of a component with dimethyl carbonate and/or diethyl carbonate, wherein the component is selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol and combinations thereof; the crystalline diol is a polyester glycol prepared by the reaction of a component and adipic acid, wherein the component is selected from the group consisting of 1,4-butanediol, 1,6-hexanediol and combinations thereof.

17. The aqueous dispersion according to claim 6, wherein the weight ratio of the crystalline diol to the non-crystalline diol is 5-10:1.

18. The aqueous dispersion according to claim 8, wherein component e) is a monofunctional polyethoxy ether having a number average molecular weight of 200-8,000 and an ethylene oxide number of 4-200.

19. The aqueous dispersion according to claim 8, wherein component e) is a methoxy polyethylene glycol having a number average molecular weight of 500-3,000 and an ethylene oxide number of 12-75.

20. The aqueous dispersion according to claim 9, wherein the component f) is a mixture of isophoronediamine and N-(2-hydroxyethyl)ethylenediamine with a molar ratio of 0.5-10:1.

Description

EMBODIMENTS

(1) The method provided by the present invention is further described in detail below, but the present invention is not limited thereby.

(2) The chemical reagents used in the following examples are analytical reagents;

(3) Materials used:

(4) Polyester I: a polyester diol prepared from adipic acid and 1,4-butanediol, OH value=56 mg KOH/g

(5) Polyester II: a polyester diol prepared from 1,6-hexanediol, neopentyl glycol and adipic acid, OH value=74 mg KOH/g

(6) Polyester III: a polyester diol prepared from adipic acid and 1,4-butanediol, OH value=112 mg KOH/g

(7) Polyester IV: a polyester diol prepared from phthalic acid and 1,6-hexanediol, OH value=56 mg KOH/g

(8) Polyester V: polycarbonate diol (PCDL T5652, Asahi Kasei Corporation), OH value=56 mg KOH/g

(9) Isocyanate I: hexamethylene diisocyanate (Wannate® HDI, Wanhua Chemical)

(10) Isocyanate II: isophorone diisocyanate (Wannate® IPDI, Wanhua Chemical)

(11) Polyether I: a monofunctional polyethoxy ether with an average molecular weight of 1200 g/mol (MPEG 1200, LG Chemical)

(12) Polyether II: a monofunctional polyethoxy ether with an average molecular weight of 520 g/mol (MPEG520, LG Chemical)

EXAMPLE 1

(13) 210 g of dehydrated polyester I, 28.35 g of isocyanate I, 2 g of dehydrated polyether I, 23 g of acetone, and 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.00%. The prepolymer was dissolved in 400 g of acetone and cooled to 50° C. 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.26 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 180 nm as determined by laser-related measurements (laser particle size analyzer) in the dispersed phase, and a pH of 7.5.

EXAMPLE 2

(14) 150 g of dehydrated polyester I, 60 g of dehydrated polyester II, 28.5 g of isocyanate I, 24 g of acetone, 0.04 g of bismuth neodecanoate, 3.15 g of polyether II were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 1.95%. The prepolymer was dissolved in 405 g of acetone and cooled to 50° C. 2 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.42 g of isophoronediamine and 0.41 g of hydroxyethylethylenediamine dissolved in 10 g of aqueous solution, and 2.39 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 20 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 197 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 55 wt % and an average particle size of 220 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.2.

EXAMPLE 3

(15) 80 g of dehydrated polyester I, 25 g of dehydrated polyester III, 20 g of dehydrated polyester IV, 12 g of dehydrated polyether I, 22 g of isocyanate I, 18 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.1%. The prepolymer was dissolved in 309 g of acetone and cooled to 50° C. 4.6 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.8 g of isophoronediamine and 1 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 224 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 45 wt % and an average particle size of 150 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.5.

EXAMPLE 4

(16) 80 g of dehydrated polyester I, 110 g of dehydrated polyester II, 35 g of dehydrated polyester III, 28.35 g of isocyanate I, 2 g of dehydrated polyether I, 25 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.00%. The prepolymer was dissolved in 405 g of acetone and cooled to 50° C. 5 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.72 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 180 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.5.

EXAMPLE 5

(17) 150 g of dehydrated polyester I, 120 g of dehydrated polyester II, 28.35 g of isocyanate I, 2 g of dehydrated polyether I were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.19%. The prepolymer was dissolved in 424 g of acetone and cooled to 50° C. 5 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution dissolved, and 0.6 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 558 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 30 wt % and an average particle size of 64 nm as determined by laser-related measurements in the dispersed phase, and a pH of 6.8.

EXAMPLE 6

(18) 210 g of dehydrated polyester I, 43 g of isocyanate I, 2 g of dehydrated polyether I were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 4.98%, then 15.2 g of butanone oxime was added at 50° C. until the NCO was lowered to 2.20%. The prepolymer was dissolved in 450 g of acetone and cooled to 50° C. 5 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.58 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 253 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 180 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.8.

EXAMPLE 7

(19) 210 g of dehydrated polyester I, 20 g of isocyanate I, 11.1 g of isocyanate II, 2 g of dehydrated polyether I, 24 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 1.95%. The prepolymer was dissolved in 405 g of acetone and cooled to 50° C. 4.8 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.26 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine were dissolved in 35 g of aqueous solution, and 0.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred. Stirred for 20 minutes and then dispersed the mixture by adding 241 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 176 nm as determined by laser-related measurements in the dispersed phase, and a pH of 8.

EXAMPLE 8

(20) 210 g of dehydrated polyester I, 35 g of isocyanate I, 5.8 g of dimethylolpropionic acid, 2 g of dehydrated polyether I, 24 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with n nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.09%. The prepolymer was dissolved in 419 g of acetone and cooled to 50° C., and then 4.4 g of triethylamine was added for 5 minutes of neutralization. 2 g of isophoronediamine and 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 6 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 50 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 300 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 40 wt % and an average particle size of 195 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.5.

EXAMPLE 9

(21) 210 g of dehydrated polyester I, 32 g of isocyanate I, 4 g of 1,4-butanediol, 2 g of dehydrated polyether I, 24 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 1.92%. The prepolymer was dissolved in 413 g of acetone and cooled to 50° C. 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 2.4 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 1.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 50 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 300 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 40 wt % and an average particle size of 195 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.5.

EXAMPLE 10

(22) 190 g of dehydrated polyester I, 12 g of dehydrated polyester V, 20 g of isocyanate I, 11 g of isocyanate II, 2 g of dehydrated polyether I, 23 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.15%. The prepolymer was dissolved in 400 g of acetone and cooled to 50° C. 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.26 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 165 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.0.

EXAMPLE 11

(23) 190 g of dehydrated polyester I, 20 g of dehydrated polyester V, 20 g of isocyanate I, 13 g of isocyanate II, 2 g of dehydrated polyether I, 23 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.05%. The prepolymer was dissolved in 400 g of acetone and cooled to 50° C. 4.63 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.26 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.5 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 178 nm as determined by laser-related measurements in the dispersed phase, and a pH of 6.8.

EXAMPLE 12

(24) 80 g of dehydrated polyester I, 120 g of dehydrated polyester II, 30 g of dehydrated polyester III, 28.35 g of isocyanate I, 2 g of dehydrated polyether I, 25 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 1.92%. The prepolymer was dissolved in 395 g of acetone and cooled to 50° C. 5 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.72 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were prepared respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 185 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.2.

EXAMPLE 13

(25) 80 g of dehydrated polyester I, 150 g of dehydrated polyester II, 15 g of dehydrated polyester III, 28.35 g of isocyanate I, 2 g of dehydrated polyether I, 25 g of acetone, 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 2.03%. The prepolymer was dissolved in 415 g of acetone and cooled to 50° C. 5 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution, and 0.72 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane dissolved in 5 g of acetone solution were respectively added to the acetone solution in which the prepolymer was dissolved, and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 238 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 178 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.0.

COMPARATIVE EXAMPLE 14

(26) 210 g of dehydrated polyester I, 28.35 g of isocyanate I, 24 g of acetone, 2 g of dehydrated polyether I, and 0.04 g of bismuth neodecanoate were added to a 1 L four-necked round bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80-90° C. until the NCO reached 1.72%. The prepolymer was dissolved in 405 g of acetone and cooled to 50° C. 5.1 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 3.51 g of isophoronediamine, 0.86 g of hydroxyethylethylenediamine dissolved in 35 g of aqueous solution were added to the acetone solution in which the prepolymer was dissolved and the solution was vigorously stirred at the same time. Stirred for 20 minutes and then dispersed the mixture by adding 300 g of water. 4 g of emulsifier Tween 20 was added after separating the acetone by distillation. A solvent-free polyurethane-polyurea aqueous dispersion was obtained, which has a solid content of 50 wt % and an average particle size of 180 nm as determined by laser-related measurements in the dispersed phase, and a pH of 7.5.

(27) Preparation of Adhesives

(28) 100 g of water dispersion and 0.05 g BYK024 (BYK) were mixed, stirred at 500 rpm for 5 minutes, then 0.2 g of Tego245 (Tego) was added, stirred for another 5 minutes, then 0.15 g of Vesmody U604 (Wanhua Chemical) was added, then stirred at 600 rpm for 10 minutes.

(29) Preparation of Samples

(30) Samples were prepared using the following composite materials:

(31) TABLE-US-00001 Composite materials Substrate 1 Substrate 2 A Rubber Rubber B Canvas Canvas C PVC PVC D Rubber Rubber

(32) (1) First of all, the substrate 1 (rubber) and the substrate 2 (rubber) were treated with a treating agent (acetone solution of trichloroisocyanurate, 2 wt %), and then air-dried for later use. The adhesive was first applied to a substrate strip with a width of 2.5 cm and a length of 15 cm using a brush, dried in an oven at 65° C. for 5 minutes and then taken out and pressed at 30 kg/cm.sup.2 for 10 seconds to prepare composite material A.

(33) (2) Composite material B and composite material C were prepared in the same manner as in step (1).

(34) (3) After the adhesive was placed at 75° C. for 72 hours, the composite material D was prepared in the same manner as in step (1).

(35) Testing the peel strength of the composite materials

(36) The peel strength was measured using a GOTECH tensile machine at a peel rate of 200 mm/minute.

(37) Initial strength: peel strength tested directly on the tensile machine after pressing.

(38) Late strength: the samples were placed at room temperature for 24 hours, then their peel strength were tested.

(39) The test results are shown in Table 1.

(40) TABLE-US-00002 TABLE 1 Peel strengths of the adhesives on different substrates Initial strength N/mm Late strength N/mm Composite materials A B C D A B C D Example 1 5.8 4.0 4.6 5.8 11.9 7.3 8.2 11.5 Example 2 5.3 3.6 4.3 5.3 11.6 7.0 8.0 11.6 Example 3 5.6 3.9 4.8 5.6 11.7 7.6 8.1 11.6 Example 4 5.7 4.1 4.5 5.3 12.0 7.5 8.0 12.5 Example 5 5.2 3.5 4.4 5.0 11.4 7.2 7.9 11.5 Example 6 6.0 4.2 4.5 6.1 12.1 7.5 8.0 12.3 Example 7 5.7 3.9 4.5 5.9 12.1 7.1 8.4 12.5 Example 8 5.1 3.2 4.0 5.0 11.5 7.1 8.0 11.5 Example 9 6.0 4.1 4.3 6.0 12.2 7.0 8.2 12.2 Example 10 6.2 4.3 4.2 6.0 12.6 6.5 7.4 12.5 Example 11 5.6 4.8 4.5 5.3 12.8 7.0 8.0 12.5 Example 12 4.8 4.5 4.0 4.5 10.9 6.2 6.9 10.2 Example 13 5.2 4.9 4.8 5.1 11.5 6.9 8.1 11.2 Comparative 6.0 4.2 4.9 3.5 12.5 7.9 8.3 7.9 example 14.sup.(1) Comparative 6.2 4.4 4.8 3.2 12.5 7.8 8.5 7.8 example 14.sup.(2) Note: .sup.(1)indicates an one-component formulation without adding a curing agent (siloxane component); .sup.(2)indicates that when the adhesive is formulated, Aquolin ® 161 (Yantai Wanhua Chemical, with NCO of 18.5 wt %) corresponding to 5 wt % of the emulsion (the aqueous dispersion prepared in Example 14) was additionally added to prepare a two-component system. In the above table, “example” and “comparative example” mean that the adhesives were prepared by using the aqueous dispersions prepared in the corresponding examples or comparative examples as raw materials.

(41) As can be seen from Table 1, compared with the one/two-component adhesives based on the dispersions not containing siloxys in the side chains (comparative Examples 14(1), 14(2)), the initial strengths and the late strengths of the one-component adhesives based on the dispersions containing siloxys in the side chains provided by the present invention decreased slightly, with a very small extent of the decrease, which meet the performance requirements, and basically did not affect the normal use.

(42) The bonding strengths of the dispersions containing siloxy segments in the side chains did not change significantly after stored at a high temperature for 3 days. But in the comparative examples, the dispersions without siloxy segments showed a significant decrease in bonding strength. This indicates that the dispersions containing siloxy segments in the side chains have excellent storage stability.

(43) Testing the Heat Resistance of the Composite Materials

(44) Initial heat resistance: a 500 g weight was hung on the prepared sample and the sample was places in an oven of 80° C. to measure the stretch length within 30 minutes.

(45) Late heat resistance: the prepared sample was placed at room temperature for 3 days, then a 1 kg weight was hung on the sample, the sample was placed in an oven of 70° C. to measure the stretch length within 24 hours.

(46) Heat and humidity resistance: the prepared sample was placed at room temperature for 3 days, then a 500 g weight was hung on the sample, the sample was placed in an oven of 70° C./95% humidity to measure the stretch length within 24 hours.

(47) The test results are shown in Table 2.

(48) TABLE-US-00003 TABLE 2 Heat resistances of adhesives on different substrates Initial heat Late heat Heat and humidity resistance/mm resistance/mm resistance/mm Composite materials A B C A B C A B C Example 1 2 2 1 0 0 0 30 60 42 Example 2 4 6 3 1 2 1 56 75 49 Example 3 6 8 5 3 5 4 78 102 62 Example 4 1 2 1 1 0 0 35 52 48 Example 5 5 5 6 2 1 0 62 71 53 Example 6 1 2 2 0 0 0 32 53 41 Example 7 1 1 2 0 1 0 36 56 39 Example 8 5 7 5 2 3 1 62 71 55 Example 9 1 1 1 1 0 1 36 52 51 Example 10 1 2 1 0 1 1 45 71 48 Example 11 1 1 2 1 0 0 49 35 59 Example 12 1 2 7 1 0 0 45 38 42 Example 13 1 4 5 1 0 0 53 42 55 Comparative 50 46 38 61 58 53 150 150 150 example 14.sup.(1) Comparative 20 18 15 0 0 0 20 25 12 example 14.sup.(2) Note: .sup.(1)indicates an one-component formulation without adding a curing agent; .sup.(2)indicates that when the adhesive is formulated, Aquolin ® 161 (Yantai Wanhua Chemical, with NCO of 18.5 wt %) corresponding to 5 wt % of the emulsion was additionally added to prepare a two-component system. In the above table, “example” and “comparative example” mean that the adhesives were prepared by using the aqueous dispersions prepared in the corresponding examples or comparative examples as raw materials.

(49) As can be seen from Table 2, compared with the one-component adhesive based on the dispersion not containing siloxys in the side chains (comparative Examples 14(1)), the initial heat resistance, the late heat resistance and the heat and humidity resistance of the one-component adhesives based on the dispersions containing siloxys in the side chains provided by the present invention increased significantly, the initial heat resistances were obviously superior to the performance of the two-component adhesive (comparative example 14(2)), and the late heat resistances were close to the performance of the two-component adhesive (comparative example 14(2)). This is mainly because the siloxys in the side chains are hydrolyzed and crosslinked with each other to increase a cross-linking density of the coating film, improving the heat resistance and heat and humidity resistance of the coating film remarkably.