Waterborne polyurethane-polyurea dispersion and preparation method thereof, single-sided sizing waterborne polyurethane adhesive and application thereof

Abstract

The present invention belongs to the technical field of waterborne polyurethane adhesive preparation, and particularly relates to a waterborne polyurethane-polyurea dispersion and a preparation method thereof, a single-sided sizing waterborne polyurethane adhesive and its application, wherein the waterborne polyurethane-polyurea dispersion contained in the waterborne polyurethane adhesive is a product obtained by reacting raw materials containing the following components: S1, polyisocyanate; S2, macromolecular polyol; S3, small molecule alcohol chain extender containing steric structure; S4, alcohol front end capping agent; S5, polyamine small molecule chain extender containing active hydrogen; S6, hydrophilic compound; S7, small molecule amine rear end capping agent. The waterborne polyurethane adhesive of the present invention has the characteristics of wide crystal range and narrow molecular weight distribution, and can have good wettability in the single-sided sizing process, thereby improving viscosity and peel strength.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of waterborne polyurethane adhesives, and in particular relates to a waterborne polyurethane-polyurea dispersion and a preparation method thereof, and a single-sided glued waterborne polyurethane adhesive and applications thereof. Background Art

[0002] The use of waterborne polyurethane-urea dispersion as an adhesive not only brings performance comparable to that of an oil-based system, but also does not pollute the environment during use. It is in line with current international development trends and national policy orientations, and is attracting more and more attention from the manufacturing industry.

[0003] In the traditional shoemaking industry, adhesive is usually applied to both sides of the sole, upper, or midsole-outsole, which is the so-called double-sided gluing process. However, this process is costly and complicated, which has become a key link affecting production efficiency. In sharp contrast, the single-sided gluing process, on the one hand, reduces the amount of glue and the steps of gluing, saving costs; on the other hand, it saves labor and greatly improves production efficiency; therefore, it has been widely favored. However, the difficulty of the single-sided gluing process is that, under the same substrate treatment conditions, it requires the adhesive to have better wettability, adhesion maintenance and open period, and better stability.

[0004] Patent document CN111746074A discloses a method for preparing adhesive products by gluing on one side. The patent document uses a substrate cleaning agent containing a polar organic solvent and polyisocyanate to improve the adhesion of the single-sided adhesive to the other side of the substrate. At the same time, the cleaning agent containing polyisocyanate also acts as a curing agent, which can improve the later resistance of the product. However, the cleaning agent used on the non-gluing substrate surface in this method will cause the exposure of organic solvents and polyisocyanates.

[0005] Patent document CN107802056A discloses a method for making shoes by single-sided gluing using powder glue. The method attempts to make improvements from the resin aspect by using powder glue containing polyurethane resin and polyamide resin. However, compared with the performance of the shoe material made by double-sided gluing, the mechanical properties of the shoe material made by single-sided gluing are much worse.

[0006] In view of this, it is particularly important to improve the wettability and viscosity of single-sided water-based polyurethane adhesives and enhance their overall performance. Summary of the invention

[0007] The purpose of the present invention is to provide an aqueous polyurethane-polyurea dispersion and a preparation method thereof, and an aqueous polyurethane adhesive for single-sided gluing and an application thereof, aiming at the problems existing in improving wettability, adhesion and the like of adhesives for single-sided gluing. The aqueous polyurethane adhesive has the characteristics of wide crystal range and narrow molecular weight distribution, which can make it have good wettability in the process of single-sided gluing, thereby improving the viscosity and peel strength of the adhesive, and at the same time also having good later endurance.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] In one aspect, an aqueous polyurethane-polyurea dispersion is provided, wherein the aqueous polyurethane-polyurea dispersion is a product obtained by reacting raw materials comprising the following components:

[0010] S1, polyisocyanate;

[0011] S2, macromolecular polyol, having an average molecular weight of 500 to 5000 g / mol (e.g., 800 g / mol, 1200 g / mol, 1500 g / mol, 2000 g / mol, 4000 g / mol), preferably 1000 to 3000 g / mol;

[0012] S3, a sterically hindered small molecule alcohol chain extender, which contains at least two groups that can react with isocyanate (for example, contains at least two hydroxyl groups), and has an average molecular weight of 60 to 499 g / mol (for example, 80 g / mol, 120 g / mol, 150 g / mol, 200 g / mol, 400 g / mol);

[0013] S4, an alcohol pre-capping agent, which contains at least one group capable of reacting with isocyanate, and has an average molecular weight of 200 to 8000 g / mol (e.g., 600 g / mol, 1200 g / mol, 2000 g / mol, 3500 g / mol, 5000 g / mol), preferably 500-3000 g / mol;

[0014] Optionally, S5, a polyamine small molecule chain extender containing active hydrogen, having an average molecular weight of 60 to 499 g / mol (e.g., 80 g / mol, 120 g / mol, 150 g / mol, 200 g / mol, 400 g / mol);

[0015] S6, a hydrophilic compound containing an ionic group or a potentially ionic group, which contains at least one group capable of reacting with an isocyanate;

[0016] S7, a small molecule amine post-capping agent, which contains a group capable of reacting with isocyanate and has an average molecular weight of 60 to 499 g / mol (e.g., 80 g / mol, 120 g / mol, 150 g / mol, 200 g / mol, 400 g / mol);

[0017] Optionally, also include:

[0018] S8, water;

[0019] S9, a catalyst (which can catalyze the reaction of isocyanate groups with hydroxyl groups); and

[0020] S10. Organic solvent (which does not contain a group capable of reacting with isocyanate).

[0021] According to the aqueous polyurethane-polyurea dispersion provided by the present invention, in some embodiments, based on the total mass of components S1 to S7 (e.g., 100 wt%), the amount of each component is as follows:

[0022] Component S1 is 5.0 to 18.0 wt% (e.g., 6 wt%, 8 wt%, 12 wt%, 15 wt%, 17 wt%), preferably 10.0 to 16.5 wt%;

[0023] Component S2 is 68.0 to 85.0 wt% (e.g., 70 wt%, 74 wt%, 78 wt%, 80 wt%, 84 wt%), preferably 75.0 to 85.0 wt%;

[0024] Component S3 is 0.1 to 5.0 wt% (e.g., 0.5 wt%, 1.5 wt%, 2.5 wt%, 4 wt%, 4.5 wt%), preferably 1.0 to 3.0 wt%;

[0025] Component S4 is 0.1 to 4.0 wt% (e.g., 0.2 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 3.0 wt%), preferably 0.5 to 1.5 wt%;

[0026] Component S5 is 0.01 to 1.0 wt% (e.g., 0.02 wt%, 0.08 wt%, 0.1 wt%, 0.4 wt%, 0.8 wt%), preferably 0.05 to 0.5 wt%;

[0027] Component S6 is 0.5 to 3.0 wt% (e.g., 0.8 wt%, 1.2 wt%, 1.5 wt%, 2 wt%), preferably 1.0 to 2.5 wt%;

[0028] Component S7 is 0.1 to 1.5 wt% (e.g., 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 1.2 wt%), preferably 0.3 to 1.0 wt%.

[0029] In some embodiments, component S9 is selected from an organic bismuth catalyst or an organic tin catalyst, more preferably selected from Bi@8108 or butyltin laurate from a leading American company, and further preferably selected from Bi@8108 from a leading American company.

[0030] In some embodiments, component S10 is selected from low boiling point organic solvents having a boiling point of 40 to 85° C., more preferably selected from acetone or butanone, and further preferably selected from acetone.

[0031] In some embodiments, based on the total mass of components S1 to S4, the amount of component S9 is 0 to 1000 ppm (e.g., 10 ppm, 100 ppm, 500 ppm); the amount of component S10 is 1.0 to 2.0 times the total mass of components S1 to S4.

[0032] In the present invention, component S1 is an isocyanate containing at least two isocyanate groups, which may be an aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate. In some embodiments, the polyisocyanate described in component S1 is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, preferably one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

[0033] In some embodiments, the macromolecular polyol described in component S2 is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, poly1,4-butylene adipate diol, polyneopentyl adipate diol, poly1,6-hexanediol adipate diol and polyneopentyl adipate 1,6-hexanediol adipate diol, preferably selected from poly1,4-butylene adipate diol and / or polyneopentyl adipate 1,6-hexanediol adipate diol.

[0034] In some embodiments, the sterically hindered small molecule alcohol chain extender described in component S3 is selected from one or more of neopentyl glycol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol, preferably selected from one or more of neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol.

[0035] In some embodiments, the alcohol pre-capping agent described in component S4 is selected from one or more of 1-octadecanol, Ymer120 and polyoxyethylene ether containing one hydroxyl group, preferably selected from one or more of monofunctional polyoxyethylene ethers with a number average molecular weight of 200 to 8000 and 4 to 200 ethylene oxides, and more preferably selected from one or more of polyethylene glycol monomethyl ethers with a number average molecular weight of 500 to 3000 and 12 to 75 ethylene oxides. For example, MPEG1200 or MPEG520.

[0036] In some embodiments, the polyamine small molecule chain extender containing active hydrogen described in component S5 is selected from one or more of ethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine and 4,4-diphenylmethanediamine, preferably ethylenediamine and / or isophoronediamine.

[0037] In the present invention, component S6 may be a compound containing 2 to 3 NCO reactive groups and at least one ionic group or potential ionic group. The potential ionic group refers to a functional group having a covalent bond, which is easily converted into a corresponding salt by adding a neutralizing agent as the pH of the solution changes. The potential ionic group may be an acid group; the acid group is selected from a carboxyl group (-COOH) and / or a sulfonic acid group (-SO3H). The ionic group includes a carboxylate group (-COO - ) and / or sulfonate (-SO3 - In some embodiments, the hydrophilic compound containing an ionic group or a potential ionic group described in component S6 is selected from one or more of sulfonic acid-type hydrophilic compounds, preferably selected from one or more of sodium 2-(2-aminoethyl)aminoethanesulfonate, sodium 2-(2-aminoethyl)aminopropanesulfonate, sodium 1,4-butanediol-2-sulfonate and sodium 1,2-dihydroxy-3-propanesulfonate, more preferably sodium 2-(2-aminoethyl)aminoethanesulfonate.

[0038] In some embodiments, the small molecule amine post-capping agent described in component S7 is selected from one or more of aliphatic primary or secondary monoamines, alicyclic primary or secondary monoamines, and amino alcohols containing both amino groups and hydroxyl groups, preferably selected from one or more of ethylamine, diethylamine, isopropylamine, butylamine, cyclohexylamine, ethanolamine, diethanolamine, N-methylethanolamine, diisopropanolamine and diethylenetriamine, more preferably diethanolamine.

[0039] In some embodiments, the solid content of the aqueous polyurethane-polyurea dispersion is 40-55 wt% (e.g., 43 wt%, 48 wt%, 52 wt%), preferably 45-50 wt%; the average particle size of the solids contained therein is 130-300 nm (e.g., 160 nm, 200 nm, 250 nm), preferably 150-230 nm.

[0040] In another aspect, a method for preparing the aqueous polyurethane-polyurea dispersion as described above is provided, comprising the following steps:

[0041] (1-1) Component S1, component S2, component S4 and an optional portion of component S10 are uniformly mixed and reacted at 75 to 85° C. (e.g., 78° C., 80° C., 82° C.), and component S3 is added to the reaction system after 60 min to 80 min (e.g., 65 min, 70 min), and the reaction is continued at 75 to 85° C. until the NCO% of the system reaches a theoretical value, thereby obtaining an isocyanate-terminated prepolymer;

[0042] (1-2) The system containing the isocyanate-terminated prepolymer obtained in step (1-1) is cooled to 50-60° C. (e.g., 55° C., 58° C.), and then the remaining component S10 is added to dissolve and dilute, and then components S5 and S6 are added, and the reaction is carried out at 30-45° C. (e.g., 35° C., 40° C.) for 5-10 min, and then component S7 is added, and the reaction is continued at 30-45° C. for 5-10 min; component S8 is then added for shear dispersion to obtain an emulsion; and the solvent is optionally removed (e.g., the solvent is partially or completely removed by reduced pressure distillation) to obtain an aqueous polyurethane-polyurea dispersion.

[0043] In some embodiments, after the reaction system is subjected to solvent removal, some emulsifiers, for example, emulsifier Tween 20, may be optionally added.

[0044] According to the preparation method provided by the present invention, in some embodiments, in step (1-2), component S5 and component S6 are added to the system in the form of an aqueous solution, and the amount of water used is 3 to 5 times the sum of the mass of component S5 and component S6. The amount of water involved here, for example, can be included in the total amount of component S8, that is, the water contained in the aqueous solution involved here and the mass of component S8 added in step (1-2) are added as the amount of component S8 in the raw material.

[0045] In some embodiments, in step (1-2), component S7 is added to the system in the form of an aqueous solution, and the amount of water used is 2 to 5 times the sum of the mass of component S3 and component S4. The amount of water involved here can be included in the total amount of component S8, that is, the water contained in the aqueous solution involved here and the mass of component S8 added in step (1-2) are added as the amount of component S8 in the raw material.

[0046] The total amount of component S10 added is the sum of the mass added in step (1-2) and step (1-1). In some embodiments, the mass ratio of component S10 added in step (1-2) to step (1-1) is 5 to 12:1; for example, the mass ratio of component S10 added in step (1-2) to component S10 added in step (1-1) is 6:1, 8:1 or 10:1.

[0047] In some embodiments, in step (1-2), the pH value of the obtained dispersion emulsion is greater than 7.

[0048] The single-sided glued water-based polyurethane adhesive of the present invention may be a two-component formula adhesive. In another aspect, a single-sided glued water-based polyurethane adhesive is provided, which comprises the water-based polyurethane-polyurea dispersion as described above or the water-based polyurethane-polyurea dispersion prepared by the preparation method as described above, and an auxiliary agent. The auxiliary agent may be an additive commonly used in the art for preparing adhesives, which will not be described in detail here.

[0049] The preparation method of the single-sided glue-applied water-based polyurethane adhesive of the present invention can also be achieved by conventional methods in the art, which will not be described in detail here.

[0050] In another aspect, there is provided an application of the above-mentioned single-sided glued water-based polyurethane adhesive in the fields of shoe glue, automobile interior glue, and electronic glue.

[0051] The waterborne polyurethane adhesive prepared by the present invention has the characteristics of wide crystal range and narrow molecular weight distribution, and can have good wettability and viscosity in the single-sided gluing process, and can be well applied in the fields of shoe glue, automobile interior glue, and electronic glue. In addition, the waterborne polyurethane-polyurea dispersion is used as a main agent and a curing agent and other components are prepared through a two-component formula, and the obtained adhesive can also obtain excellent later performance, and can be applied to the fields of shoe glue, automobile interior glue, electronic glue, etc., simplifying the process and improving efficiency.

[0052] According to the application provided by the present invention, in one embodiment, the single-sided glued water-based polyurethane adhesive is used as a shoe glue, that is, a water-based shoe glue, which includes the water-based polyurethane-polyurea dispersion of the present invention, and the content of the water-based polyurethane-polyurea dispersion is 70-95wt% based on the total weight of the water-based shoe glue as 100wt%. Further, the water-based shoe glue also contains other additives, such as a curing agent, a wetting agent, a defoaming agent, a thickener, water, etc.

[0053] The waterborne polyurethane-polyurea dispersion of the present invention adopts the formulation process of front end-capping and rear end-capping during the synthesis process, so that the polymer can have a relatively narrower molecular weight distribution under the same chain extension time. Therefore, in the state of water dispersion, the polymer mostly exists in a low molecular weight straight chain structure, so that the viscosity of the water dispersion is low, which meets the current downstream use conditions of adhesives while maintaining high rheological and high wetting properties, and can also enable the prepared adhesive to better infiltrate the substrate and enhance viscosity. At the same time, because a hard segment component (i.e., component S3) containing a steric hindrance structure is introduced into the polymer and matched with a soft segment component (i.e., component S2) containing a steric hindrance structure, the steric effect plays a synergistic role. On the one hand, it plays a delaying role in the microphase separation of the soft and hard segments to construct the microcrystalline region, so that it has the characteristics of a wide crystal range, which can improve the adhesive open period, and it is also easier to form better infiltration with the other side of the un-glued substrate before crystallization after glue activation, so as to achieve good adhesion; on the other hand, the polarity of the polymer is tuned, which can better adapt to the polarity of the substrate, overcome the problem of poor wetting and adhesion of the adhesive to the substrate during single-sided gluing, and make contributions to the most challenging aspect of the single-sided gluing process, which is the substrate wetting and adhesion.

[0054] Compared with the prior art, the beneficial effects of the technical solution of the present invention are:

[0055] In the present invention, the open period of the single-sided glued water-based polyurethane adhesive is improved, and it is easier to form better wetting between the other side of the un-glued substrate before crystallization after glue activation, thereby improving the adhesion of the adhesive; in addition, the polarity of the polymer in the single-sided glued water-based polyurethane adhesive is tuned, and it can better adapt to the polarity of the substrate, thereby overcoming the problem of poor wetting and adhesion of the adhesive to the substrate during single-sided glue application, thereby improving the viscosity of the adhesive. At the same time, the single-sided glued adhesive can also have good late-stage resistance. In addition, when the single-sided glued water-based polyurethane adhesive of the present invention is used in a single-sided glue process, the production process is simple, easy to operate, safe and non-toxic. DETAILED DESCRIPTION

[0056] In order to understand the technical features and contents of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described here.

[0057] <Main raw material sources>

[0058] Component S1:

[0059] Hexamethylene diisocyanate (HDI): industrial grade, Wanhua Chemical Group Co., Ltd.

[0060] Isophorone diisocyanate (IPDI): industrial grade, Wanhua Chemical Group Co., Ltd.

[0061] Component S2:

[0062] Polyester polyol I (PBA2000): poly(1,4-butylene adipate diol), Mn=2000 g / mol, ( WHP-204, Wanhua Chemical);

[0063] Polyester polyol II (CMA654): poly(neopentyl adipate 1,6-hexanediol adipate diol), Mn=1500 g / mol, ( WHP-1556, Wanhua Chemical);

[0064] Component S3:

[0065] Neopentyl glycol (NPG): industrial grade, Wanhua Chemical Group Co., Ltd.;

[0066] 2-Methyl-1,3-propanediol: analytical grade, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0067] 2-Ethyl-1,3-propanediol: industrial grade, Zhengzhou Huiju Chemical Co., Ltd.;

[0068] 2,2-Diethyl-1,3-propanediol: analytical grade, Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0069] 1,4-Butanediol (BDO): analytical grade, Sinopharm Chemical Reagent Co., Ltd.;

[0070] Component S4:

[0071] MPEG1200: Polyethylene glycol monomethyl ether, Mn = 1200 g / mol (Lotte, South Korea)

[0072] MPEG520: Polyethylene glycol monomethyl ether, Mn = 520 g / mol (Lotte, South Korea)

[0073] Component S5:

[0074] Ethylenediamine: analytical grade, Sinopharm Chemical Reagent Co., Ltd.;

[0075] Isophorone diamine (IPDA): industrial grade, Wanhua Chemical Group Co., Ltd.

[0076] Component S6:

[0077] A95: aminoalkylsulfonate hydrophilic chain extender, Evonik Chemical Co., Ltd.;

[0078] Component S7:

[0079] Diethanolamine: industrial grade, Wanhua Chemical Group Co., Ltd.;

[0080] Catalyst: Bi@8108, Leading Technologies, Inc.

[0081] Acetone: industrial grade, Wanhua Chemical Group Co., Ltd.;

[0082] Unless otherwise specified, other raw materials were purchased from the market and will not be described here.

[0083] Preparation of waterborne polyurethane-polyurea dispersion

[0084] Example 1

[0085] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% of the system reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0086] (1-2) The system containing the prepolymer was cooled to 50° C., and 440 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 2.32 g of diethanolamine was added, and the mixture was stirred for another 10 min;

[0087] 398 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 162 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.3.

[0088] Example 2

[0089] (1-1) 360 g of PBA2000, 52 g of HDI, 3.5 g of MPEG1200, 93 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% of the system reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0090] (1-2) The system containing the prepolymer was cooled to 50° C., and 540 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and stirred for 10 min; then 7 g of an aqueous solution containing 3.13 g of diethanolamine was added, and stirring was continued for 10 min;

[0091] 495 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 173 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.1.

[0092] Example 3

[0093] (1-1) 295 g of PBA2000, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG520, 77 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 0.93%, thereby obtaining an isocyanate-terminated prepolymer;

[0094] (1-2) The system containing the prepolymer was cooled to 50° C., and 451 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and stirred for 10 min; then 5 g of an aqueous solution containing 2.17 g of diethanolamine was added, and stirring was continued for 10 min;

[0095] 410 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 188 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.0.

[0096] Example 4

[0097] (1-1) 230 g of dehydrated CMA654, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 63 g of acetone, and 0.09 g of Bi@8108 were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% of the system reached 1.05%, thereby obtaining an isocyanate-terminated prepolymer;

[0098] (1-2) The system containing the prepolymer was cooled to 50° C., and 368 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 1.88 g of diethanolamine was added, and the mixture was stirred for another 10 min;

[0099] 330 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 175 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.5.

[0100] Example 5

[0101] (1-1) 260 g of PBA2000, 26 g of CMA654, 45 g of HDI, 3.5 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 1.04%, thereby obtaining an isocyanate-terminated prepolymer;

[0102] (1-2) The system containing the prepolymer was cooled to 50°C, and 437 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35°C, 20 g of an aqueous solution containing 0.3 g of ethylenediamine and 6 g of A95 was added, and stirred for 10 min; then 6 g of an aqueous solution containing 2.28 g of diethanolamine was added, and stirring was continued for 10 min;

[0103] 396 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 160 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.2.

[0104] Example 6

[0105] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added into a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 6 g of 2-methyl-1,3-propanediol was added into the reaction system and the reaction was continued at 75° C. until the NCO% reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0106] (1-2) The system containing the prepolymer was cooled to 50° C., and 440 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 2.32 g of diethanolamine was added, and the mixture was stirred for another 10 min;

[0107] 398 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 162 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.3.

[0108] Example 7

[0109] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of 2-ethyl-1,3-propanediol was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0110] (1-2) The system containing the prepolymer was cooled to 50° C., and 440 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 2.32 g of diethanolamine was added, and the mixture was stirred for another 10 min;

[0111] 398 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 162 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.3.

[0112] Example 8

[0113] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 8.9 g of 2,2-diethyl-1,3-propanediol was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0114] (1-2) The system containing the prepolymer was cooled to 50°C, and 440 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35°C, 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 2.32 g of diethanolamine was added, and stirring was continued for 10 min.

[0115] 398 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 162 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.3.

[0116] Comparative Example 1

[0117] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 1.00%, thereby obtaining an isocyanate-terminated prepolymer;

[0118] (1-2) The system containing the prepolymer was cooled to 50° C., and 440 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 6 g of an aqueous solution containing 2.32 g of diethanolamine was added, and the mixture was stirred for another 10 min;

[0119] 398 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 162 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.3.

[0120] Comparative Example 2

[0121] The preparation steps of the aqueous polyurethane-polyurea dispersion refer to Example 1, except that diethanolamine is not added in step (1-2); an aqueous polyurethane-polyurea dispersion is obtained, which has a solid content of 45wt% and an average particle size of 183nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.1.

[0122] Comparative Example 3

[0123] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 15 g of MPEG1200, 76 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% of the system reached 0.97%, thereby obtaining an isocyanate-terminated prepolymer;

[0124] (1-2) The system containing the prepolymer was cooled to 50°C, and 443 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35°C, 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and the mixture was stirred for 10 min; then 8 g of an aqueous solution containing 5.52 g of diethanolamine was added, and stirring was continued for 10 min.

[0125] 402 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 151 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.0.

[0126] Comparative Example 4

[0127] (1-1) 295 g of PBA2000, 36.4 g of HDI, 10.92 g of IPDI, 3.5 g of MPEG1200, 77 g of acetone, and 0.11 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 6 g of BDO was added to the reaction system and the reaction was continued at 75° C. until the NCO% reached 0.98%, thereby obtaining an isocyanate-terminated prepolymer;

[0128] (1-2) The system containing the prepolymer was cooled to 50° C., and 450 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and stirred for 10 min; then 5 g of an aqueous solution containing 2.36 g of diethanolamine was added, and stirring was continued for 10 min;

[0129] 408 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 166 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.2.

[0130] Comparative Example 5

[0131] (1-1) 260 g of PBA2000, 26 g of CMA654, 36.4 g of HDI, 10.92 g of IPDI, 0.3 g of MPEG1200, 75 g of acetone, and 0.1 g of Bi@8108 that had been dehydrated were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 75° C. After 60 min, 7 g of NPG was added to the reaction system and the reaction was continued at 75° C. until the NCO% of the system reached 1.02%, thereby obtaining an isocyanate-terminated prepolymer;

[0132] (1-2) The system containing the prepolymer was cooled to 50° C., and 437 g of acetone was added to dissolve and dilute; then the temperature was lowered to 35° C., 20 g of an aqueous solution containing 0.4 g of IPDA and 6 g of A95 was added, and stirred for 10 min; then 2 g of an aqueous solution containing 0.21 g of diethanolamine was added, and stirring was continued for 10 min;

[0133] 395 g of water was then added for shear dispersion to obtain an emulsion; after acetone was separated by reduced pressure distillation, 4 g of emulsifier Tween 20 was added, and water was added to adjust the solid content; a solvent-free aqueous polyurethane-polyurea dispersion was obtained, which had a solid content of 45 wt % and an average particle size of 193 nm in the dispersed phase measured by a laser particle size analyzer, and pH = 7.0.

[0134] Preparation of single-sided adhesive water-based polyurethane adhesive

[0135] Take 100g of each of the aqueous polyurethane-polyurea dispersion emulsions prepared in the above embodiments and comparative examples, and put them in steel cups respectively, mark and number them, and add the following additives to each steel cup (the amount of each additive is based on 100g of the dispersion emulsion): 0.2wt% wetting agent, 0.05wt% defoaming agent, 0.3wt% thickener, 5wt% isocyanate curing agent, stir evenly, and prepare each adhesive for standby use.

[0136] Preparation of test samples

[0137] The test substrate is a rubber strip of 2 cm × 100 cm.

[0138] Apply each adhesive on the substrate with a single-sided adhesive: 100g / m 2 After applying the glue, dry it in an oven at 65°C for 3 minutes, press it at 0.1MPa for 10 seconds to obtain the sample to be tested, and set it aside.

[0139] <Performance Test>

[0140] Adhesion: After the test sample is prepared, bend and fix the rubber strip on one side of the test sample into a semicircle at 25°C, and then measure the bounce length of the rubber strip on the other side within 15 seconds.

[0141] 15min strength: After the test sample is prepared, the peel strength of the test sample is tested within 15min at 25℃, 180°, and a tensile rate of 200mm / min.

[0142] Later heat resistance: After the test sample is prepared, it is cured at 25°C for 24 hours, and then tested at 180°, 80°C×500g×1h, and the debonding length within 1 hour is measured.

[0143] Later moisture and heat resistance: After the test sample is prepared, it is cured at 25°C for 24 hours, and then tested at 180°, 80°C×40% humidity×200g×1h, and the debonding length within 1 hour is measured.

[0144] The performance test results of each test sample are shown in Table 1.

[0145] Table 1

[0146] Dispersion No. viscosity 15min strength (N / mm) Heat resistance in later stage Later stage resistance to humidity and heat Example 1 1mm 2.7 2mm 6mm Example 2 12mm 3.2 5mm 15mm Example 3 14mm 3.3 6mm 17mm Example 4 5mm 1.7 8mm 23mm Example 5 5mm 3.0 3mm 6mm Example 6 6mm 2.5 4mm 8mm Example 7 5mm 2.3 3mm 7mm Example 8 4mm 1.7 6mm 10mm Comparative Example 1 8mm 3.5 4mm 8mm Comparative Example 2 9mm 3.2 12mm 28mm Comparative Example 3 16mm 0.6 47mm Completely debonded Comparative Example 4 11mm 3.8 4mm 8mm Comparative Example 5 25mm 1.8 25mm 33mm

[0147] One of the foundations for the good performance of adhesive viscosity and bonding strength is excellent wetting of the substrate. Appropriate polymer molecular weight and crosslinking degree play an important role in improving the late-stage resistance of the adhesive. When the prepared waterborne polyurethane dispersion is used as an adhesive formulation component, it can be matched with the curing agent in the two-component to obtain a suitable crosslinking degree, further improving the late-stage resistance.

[0148] The introduction of the front and rear end-capping agents in the dispersion formula of Example 1 is beneficial to improving the spreading and wetting of the adhesive on the substrate, obtaining good substrate adhesion and enhancing viscosity. Compared with Example 1, the adhesive obtained from the dispersion of Comparative Example 1 has poor viscosity; the adhesive obtained from the dispersion of Comparative Example 2 shows obvious lack of late resistance, which further illustrates the necessity of the front and rear end-capping processes used in the present invention and the rationality of the selection of the rear end-capping agent.

[0149] Compared with Example 1, the viscosity, bonding strength and late-stage resistance of the adhesives prepared from the dispersions of Comparative Examples 3 and 5 all deteriorated, indicating that the appropriate front and rear end-capping ratio is also an important condition for giving the adhesive excellent viscosity, bonding strength and late-stage resistance. Too high an end-capping ratio will lead to too much low molecular weight polymer, which is difficult to contribute sufficient cohesion; too low an end-capping ratio will not provide qualified wettability and viscosity.

[0150] By comparing Example 1 with Comparative Example 4, it can be seen that the combination of hard segment and soft segment structures containing steric hindrance can exert a steric synergistic effect, so that the adhesive has better viscosity, thereby improving the mechanical properties and later durability.

[0151] In the single-sided gluing working scenario used in the present invention, the adhesive prepared by the technical solution of the present invention has excellent wettability, which is a necessary property for achieving rapid spreading and bonding on the substrate.

[0152] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. An aqueous polyurethane-polyurea dispersion, characterized in that: It is a product obtained by reacting the following raw materials: S1, polyisocyanate; S2, macromolecular polyol, the average molecular weight of which is 500 to 5000 g / mol; S3, a sterically hindered small molecule alcohol chain extender, which contains at least two groups that can react with isocyanate and has an average molecular weight of 60 to 499 g / mol; it is selected from one or more of neopentyl glycol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol; S4, an alcohol pre-capping agent, selected from one or more of 1-octadecanol, Ymer120 and a polyoxyethylene ether containing one hydroxyl group, and having an average molecular weight of 200 to 8000 g / mol; S5, a polyamine small molecule chain extender containing active hydrogen, with an average molecular weight of 60 to 499 g / mol; S6, a hydrophilic compound containing an ionic group or a potentially ionic group, which contains at least one group capable of reacting with an isocyanate; S7, a small molecule amine post-capping agent, which contains a group that can react with isocyanate and has an average molecular weight of 60 to 499 g / mol; Optionally, also include: S8, water; S9, catalyst; and S10, organic solvent; Based on the total mass of components S1 to S7, the amount of each component used is as follows: Component S1 is 5.0 to 18.0 wt%; Component S2 is 68.0-85.0wt%; Component S3 is 0.1 to 5.0 wt%; Component S4 is 0.1 to 4.0 wt%; Component S5 is 0.01 to 1.0 wt%; Component S6 is 0.5 to 3.0 wt%; Component S7 is 0.1 to 1.5 wt%.

2. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that Based on the total mass of components S1 to S7, the amount of each component used is as follows: Component S1 is 10.0 to 16.5 wt%; Component S2 is 75.0-85.0 wt%; Component S3 is 1.0 to 3.0 wt%; Component S4 is 0.5 to 1.5 wt%; Component S5 is 0.05-0.5wt%; Component S6 is 1.0 to 2.5 wt%; Component S7 is 0.3-1.0 wt%.

3. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that Component S9 is selected from an organobismuth catalyst or an organotin catalyst; and / or Component S10 is selected from low boiling point organic solvents having a boiling point of 40 to 85°C.

4. The aqueous polyurethane-polyurea dispersion according to claim 3, characterized in that Component S9 is selected from Bi@8108 or butyltin laurate from a leading American company; and / or Component S10 is selected from acetone or butanone.

5. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that Based on the total mass of components S1 to S4, the amount of component S9 used is 0 to 1000 ppm; the amount of component S10 used is 1.0 to 2.0 times the total mass of components S1 to S4.

6. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that The polyisocyanate described in component S1 is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and / or The macromolecular polyol described in component S2 is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polyhexanediol adipate diol and polyneopentyl adipate 1,6-hexanediol diol; and / or The sterically hindered small molecule alcohol chain extender described in component S3 is selected from one or more of neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol; and / or The alcohol pre-capping agent described in component S4 is selected from one or more monofunctional polyethoxy ethers having a number average molecular weight of 200 to 8000 and a number of ethylene oxides of 4 to 200; and / or The polyamine small molecule chain extender containing active hydrogen described in component S5 is selected from one or more of ethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine and 4,4-diphenylmethanediamine; and / or The hydrophilic compound containing an ionic group or a potential ionic group described in component S6 is selected from one or more of sulfonic acid type hydrophilic compounds, selected from one or more of sodium 2-(2-aminoethyl)aminoethanesulfonate, sodium 2-(2-aminoethyl)aminopropanesulfonate, sodium 1,4-butanediol-2-sulfonate and sodium 1,2-dihydroxy-3-propanesulfonate; and / or The small molecule amine post-capping agent described in component S7 is selected from one or more of aliphatic primary or secondary monoamines, alicyclic primary or secondary monoamines, and amino alcohols containing both amino groups and hydroxyl groups.

7. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The polyisocyanate described in component S1 is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

8. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The macromolecular polyol described in component S2 is selected from poly(1,4-butylene adipate) diol and / or poly(1,6-hexanediol adipate) neopentyl glycol diol.

9. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that The average molecular weight of the macromolecular polyol described in component S2 is 1000 to 3000 g / mol.

10. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The alcohol pre-capping agent described in component S4 is selected from one or more polyethylene glycol monomethyl ethers having a number average molecular weight of 500 to 3000 and a number of ethylene oxides of 12 to 75.

11. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The polyamine small molecule chain extender containing active hydrogen described in component S5 is ethylenediamine and / or isophoronediamine.

12. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The hydrophilic compound containing ionic groups or potential ionic groups described in component S6 is sodium 2-(2-aminoethyl)aminoethanesulfonate.

13. The aqueous polyurethane-polyurea dispersion according to claim 6, characterized in that The small molecule amine post-capping agent described in component S7 is selected from one or more of ethylamine, diethylamine, isopropylamine, butylamine, cyclohexylamine, ethanolamine, diethanolamine, N-methylethanolamine, diisopropanolamine and diethylenetriamine.

14. The aqueous polyurethane-polyurea dispersion according to claim 13, characterized in that The small molecule amine post-capping agent described in component S7 is diethanolamine.

15. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 14, characterized in that The solid content of the aqueous polyurethane-polyurea dispersion is 40-55 wt %; the average particle size of the solid content is 130-300 nm.

16. The aqueous polyurethane-polyurea dispersion according to claim 15, characterized in that The solid content of the aqueous polyurethane-polyurea dispersion is 45-50 wt %; the average particle size of the solid content is 150-230 nm.

17. The method for preparing an aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 16, characterized in that: The following steps are involved: (1-1) Component S1, component S2, component S4 and an optional part of component S10 are mixed uniformly and reacted at 75-85° C. After 60-80 minutes, component S3 is added to the reaction system and the reaction is continued at 75-85° C. until the NCO% of the system reaches the theoretical value, thereby obtaining an isocyanate-terminated prepolymer; (1-2) The system containing the isocyanate-terminated prepolymer obtained in step (1-1) is cooled to 50-60° C., and then the remaining component S10 is added to dissolve and dilute, and then components S5 and S6 are added, and the reaction is carried out at 30-45° C. for 5-10 minutes, and then component S7 is added, and the reaction is continued at 30-45° C. for 5-10 minutes; component S8 is then added for shear dispersion to obtain an emulsion; and after the solvent is optionally removed, an aqueous polyurethane-polyurea dispersion is obtained.

18. The preparation method according to claim 17, characterized in that: In step (1-2), component S5 and component S6 are added to the system in the form of an aqueous solution, and the amount of water used is 3 to 5 times the sum of the mass of component S5 and component S6; and / or In step (1-2), component S7 is added to the system in the form of an aqueous solution, and the amount of water used is 2 to 5 times the sum of the masses of component S3 and component S4.

19. The preparation method according to claim 17, characterized in that: The mass ratio of component S10 added in step (1-2) to step (1-1) is 5 to 12:1; and / or In step (1-2), the pH value of the obtained dispersion emulsion is greater than 7.

20. A single-sided adhesive water-based polyurethane adhesive, characterized in that: The invention comprises an aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 16 or an aqueous polyurethane-polyurea dispersion prepared by the preparation method according to any one of claims 17 to 19, and an auxiliary agent.

21. Application of the single-sided glued water-based polyurethane adhesive as claimed in claim 20 in the fields of shoe glue, automobile interior glue and electronic glue.