A polyurethane or polyurethane urea aqueous dispersion and its preparation method and application

Abstract

The present invention provides a polyurethane or polyurethane urea aqueous dispersion and a preparation method and application thereof. The dispersion comprises the following components: a polyol, a polyisocyanate, a hydrophilic compound component, a phosphorus-containing alkylamine, a neutralizer, and a small molecule amine compound. The polyurethane or polyurethane urea aqueous dispersion of the present invention has simple raw materials and processes for preparation. When preparing water-based leisure leather, it can be achieved under high filler conditions without adding a foaming stabilizer, and has good foaming and foam stability. The obtained water-based leisure leather has a smooth surface, high peeling, and excellent low-temperature bending performance. Under high temperature and high humidity conditions, the peeling strength and bending retention rate are above 80%, the thickness does not become thin, and the surface does not become shiny and sticky.

Description

Technical Field

[0001] The invention belongs to the technical field of waterborne polyurethane, and in particular relates to a polyurethane or polyurethane urea aqueous dispersion and a preparation method and application thereof. Background Art

[0002] At present, synthetic leather has good comprehensive performance and is widely used in the shoemaking, clothing, luggage and other industries. The raw materials of traditional synthetic leather technology are all oily polyurethane. During the production process, DMF solvent evaporates, and some toxic chemical components may remain, which causes great harm to the physical and mental health of producers and users. Waterborne polyurethane uses natural pollution-free water as a solvent. There is no toxic gas release during the production and use process, and it is harmless to the human body. Casual shoe leather is an application with relatively large demand at present, which requires high peeling, tortuosity, and tolerance, and at the same time has high cost requirements.

[0003] Synthetic leather is composed of a base layer, a laminating layer, and a surface layer. The base layer of synthetic leather is designed by imitating the structure of dermis tissue. The conventional method is to use physical or chemical foaming technology to produce a micro-foam structure. In order to ensure that the obtained base has excellent performance and a stable pore structure, it is usually necessary to add foaming and foam stabilizing agents. The addition of foaming agents and foam stabilizers increases the cost and the complexity of the batching process. At the same time, the conventionally added foaming agents and foam stabilizers are generally anionic non-ionic emulsifiers, which have migration problems after addition. After migrating to the surface of the base, the water resistance and solvent resistance of the base will decrease, and the feel will be affected.

[0004] Patent CN111732708A discloses a soft high-resilience water-based polyurethane resin and a preparation method and application thereof. In the application, when preparing a soft high-resilience water-based polyurethane coating for synthetic leather, a foaming agent and a foam stabilizer need to be added to provide good foaming and foam stabilization performance. The addition of the foaming and foam stabilizer increases the cost and there is a certain migration risk.

[0005] Patent CN109535377B discloses a waterborne polyurethane having a self-stabilizing foam function and a preparation method and application thereof. Nonionic polyethylene glycol monobutyl ether is added during the preparation process to make the resin have a self-stabilizing foam property. However, a small amount of foaming aid still needs to be added when preparing the foaming slurry. At the same time, the addition of a large amount of monofunctional polyethylene glycol monobutyl ether has a capping effect, which makes the molecular weight smaller and reduces the comprehensive performance of the prepared synthetic leather.

[0006] Therefore, in order to obtain better water-based leisure leather, it is necessary to prepare a kind of self-foaming and stable foam, excellent comprehensive performance, and at the same time, the preparation of raw materials, the process is simple, the preparation steps during application are simple, and the comprehensive cost is low. Summary of the invention

[0007] In view of the problems existing in the existing preparation of casual shoe leather base, an object of the present invention is to provide an aqueous dispersion of polyurethane or polyurethane urea, the resin of which has good powder encapsulation and self-foaming and foam stabilization properties, and no additional foaming stabilizer needs to be added when preparing the foaming slurry.

[0008] In order to achieve the above object, the technical solution of the present invention is as follows:

[0009] A polyurethane or polyurethane urea aqueous dispersion, characterized in that the dispersion comprises a reaction product obtained from the following components:

[0010] a) at least one polyol,

[0011] b) at least one polyisocyanate,

[0012] c) at least one hydrophilic compound component,

[0013] d) at least one phosphorus-containing alkylamine,

[0014] e) at least one neutralizing agent,

[0015] f) at least one small amine compound;

[0016] Wherein, the component a) is polypropylene oxide glycol and / or polyethylene oxide glycol having a number average molecular weight of 2000-8000, selected from a composition of polypropylene oxide glycol having a molecular weight of 3000 and polyethylene oxide glycol having a molecular weight of 8000 and a mass ratio of 95%:5% to 85%:15%;

[0017] Wherein, the component c) contains 2 to 3 NCO reactive functional groups, and its hydrophilic group comprises one or more of ionic groups and potential ionic groups. Preferably, the NCO reactive groups are hydroxyl groups and / or amino groups, and the ionic groups are carboxylate groups -COO - and / or sulfonate -SO 3 - The potential ion groups are carboxyl -COOH and / or sulfonic acid -SO 3 H.

[0018] The invention adopts a large molecular weight polyether as a soft segment and adds materials in a two-step method, so that the hard segment content in the molecular weight chain is concentrated, good phase separation can be formed, the hydrogen bond force of the hard segment microregion is strong, and a physical cross-linking effect can be played. At the same time, a small amount of phosphorus-containing alkylamine is added to improve the adhesion to the substrate. The combination of the two conditions makes the finally prepared casual shoe leather have high peeling properties and excellent bending properties at room temperature and low temperature. Under high temperature and high humidity conditions, the peeling strength and bending retention rate are above 80%, the thickness does not become thin, and the surface does not become shiny and sticky. By adding high molecular weight polyethylene oxide polyether and a small amount of alkylamine, after preparing the foaming slurry, high-speed shearing is performed, at which time the added polyethylene oxide chain segments will extend in the water phase, and the terminal alkyl groups on the main chain of the molecule will bridge to the emulsion in the aqueous system to form a hydrophobic association effect, forming a spatial three-dimensional network structure on solid particles and micelles, thereby achieving thickening of the aqueous system, and achieving self-thickening of the emulsion without increasing the viscosity too much and solidifying. Under the condition of high-speed stirring, the bubbles formed by shearing into the emulsion are not easy to break, thereby achieving better foaming and foam stability, and thus there is no need to add a foaming agent or a foam stabilizer, thereby ensuring the performance of the resulting product.

[0019] In the present invention, based on the total weight of each component being 100%, the weight percentage of each component is as follows:

[0020] The amount of component a) is 69-75%, preferably 70-74%,

[0021] The amount of component b) is 16-22%, preferably 17-20%,

[0022] The amount of component c) is 1.9-2.9%, preferably 2.0%-2.7%,

[0023] The amount of component d) is 1.0-2.1%, preferably 1.1-1.9%,

[0024] The amount of component e) is 1.4-2.1%, preferably 1.5-2.0%,

[0025] The amount of component f) is 1.5-6.0%, preferably 1.6-5.8%,

[0026] In the present invention, the component b) is one or more of aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, preferably diisocyanates, more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.

[0027] In the present invention, the component c) is one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-3-aminopropanesulfonic acid and N-(2-aminoethyl)-3-aminopropanesulfonic acid.

[0028] In the present invention, the component d) is a phosphine-containing monoamine with a molecular weight of 100 to 300, preferably one or more of 3-aminopropyl (hexyl) hypophosphorous acid, 2-(diethylphosphino)ethylamine, 2-(diisopropylphosphino)ethylamine, and more preferably 2-(diisopropylphosphino)ethylamine.

[0029] In the present invention, the component e) is one or more of a primary amine, a secondary amine, a tertiary amine, an alkali metal compound and an alkaline earth metal compound, preferably one or more of ammonia, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.

[0030] In the present invention, the component f) is a polyamine having a molecular weight of 60 to 500, preferably one or more of ethylenediamine, hydroxyethylethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,6-hexamethylenediamine, hexamethylenediamine and isophoronediamine, more preferably one or more of isophoronediamine, hydroxyethylethylenediamine and 1,6-hexamethylenediamine.

[0031] In the present invention, the solid content of the dispersion is 40-55wt%, preferably 45-50wt%.

[0032] In the present invention, the pH value of the dispersion is 7.5-9, preferably 8-8.5.

[0033] In the present invention, the average particle size of the dispersion is 160 to 750 nm, preferably 200 to 450 nm.

[0034] Another object of the present invention is to provide a method for preparing a polyurethane or polyurethane urea aqueous dispersion. The method is simple to operate, and the prepared casual shoe bass has a stiff feel, good resilience, high peel strength, and does not become thinner after a jungle test at high temperature and humidity, and the surface does not become shiny and sticky.

[0035] A method for preparing the above-mentioned polyurethane or polyurethane urea aqueous dispersion, the method comprising the following steps:

[0036] S1: Component a), component b, catalyst and solvent A are mixed and reacted to obtain a prepolymer I having an isocyanate terminal;

[0037] S2: cooling the prepolymer I of S1, adding component c) and solvent B, and performing a chain extension reaction to obtain an isocyanate-terminated prepolymer II;

[0038] S3: Add solvent C to the prepolymer II system of S2 to dilute, cool, add component e) to neutralize, add component d) to react, add water to disperse after the reaction, add component f) after dispersion for further reaction to obtain a water dispersion containing solvent;

[0039] Optionally, S4: removing the solvent to obtain the aqueous dispersion of the polyurethane or polyurethane urea.

[0040] In the present invention, the S1 is reacted at 60-90°C.

[0041] In the present invention, the reaction of S1 reaches or is slightly lower than the theoretical isocyanate content to obtain prepolymer I.

[0042] In the present invention, the solvent A of S2 is an organic solvent having a boiling point lower than 100° C., preferably acetone.

[0043] In the present invention, the S2 is reacted at 60-80°C.

[0044] In the present invention, the reaction of S2 reaches or is slightly lower than the theoretical isocyanate content to obtain prepolymer II.

[0045] In the present invention, the solvent B in S2 is an organic solvent having a boiling point lower than 100° C., preferably acetone.

[0046] In the present invention, the S3 is reacted at 40°C.

[0047] In the present invention, the water in S3 is added in an amount of 45 to 50 wt % of the added solids.

[0048] In the present invention, the solvent C in S3 is an organic solvent having a boiling point lower than 100° C., preferably acetone.

[0049] In the present invention, the solvent is partially or completely removed from S4 by distillation under reduced pressure.

[0050] Another object of the present invention is to provide a water-based bass.

[0051] A water-based base, using the above-mentioned polyurethane or polyurethane urea aqueous dispersion, or the polyurethane or polyurethane urea aqueous dispersion prepared by the above-mentioned preparation method, the base comprises a base fabric and a foaming slurry; wherein the foaming slurry is prepared by the following components:

[0052]

[0053] Another object of the present invention is to provide a method for preparing water-based bass.

[0054] A method for preparing the above-mentioned water-based bass, the method for preparing the bass comprising the following steps:

[0055] SS1: Soak the non-woven fabric with acid solution impregnation liquid, squeeze out the excess impregnation liquid, and dry the non-woven fabric;

[0056] SS2: Under high-speed shearing, the aqueous dispersion of polyurethane or polyurethane urea is mixed with filler powder, color paste, and pH adjuster, and then foamed to obtain a foaming slurry;

[0057] SS3: The foaming slurry of SS2 is coated on the base fabric of SS1, and then dried to obtain the water-based bass.

[0058] In the present invention, the impregnation solution of SS1 is one of the aqueous solutions of oxalic acid, tartaric acid and hydrochloric acid, preferably an aqueous solution of oxalic acid, with a mass concentration of 0.8% to 1%.

[0059] In the present invention, the foaming of SS2 is foaming to 1.1-1.3 times of the original volume.

[0060] In the present invention, the SS2 high-speed shearing speed is greater than or equal to 2000 rpm.

[0061] In the present invention, the coating thickness of SS3 is 0.8 to 1 mm.

[0062] The present invention further provides a use of water-based bass.

[0063] A use of a water-based bass, wherein the water-based bass is the above-mentioned water-based bass, or the water-based bass prepared by the above-mentioned preparation method, and the water-based bass is used as water-based casual shoe leather bass.

[0064] Compared with the prior art, the beneficial effects of the technical solution of the present invention are:

[0065] (1) Good foaming and stabilization can be achieved without adding foam stabilizers, without the migration problem of foam stabilizers, with reduced costs and simple operation

[0066] (2) The prepared base has high peeling performance and excellent bending performance at room temperature and low temperature. In the jungle test, the peeling strength and bending retention rate under high temperature and high humidity conditions are above 80%, the thickness does not become thinner, and the surface does not become shiny and sticky. DETAILED DESCRIPTION

[0067] Materials used:

[0068] C2030 (polypropylene oxide glycol, molecular weight 3000, Wanhua Chemical Group Co., Ltd., industrial grade)

[0069] C2020 (polypropylene oxide glycol, molecular weight 2000, Wanhua Chemical Group Co., Ltd., industrial grade)

[0070] PEG8000 (polyethylene oxide glycol, molecular weight 8000, Wanhua Chemical Group Co., Ltd., industrial grade)

[0071] IPDI (isophorone diisocyanate, Wanhua Chemical Group Co., Ltd., industrial grade)

[0072] HMDI (dicyclohexylmethane diisocyanate, Wanhua Chemical Group Co., Ltd., industrial grade)

[0073] DMPA (2,2-dihydroxymethylpropionic acid, Bailingwei Technology Co., Ltd., industrial grade)

[0074] DMBA (2,2-dihydroxymethylbutyric acid, J&K Technology Co., Ltd., industrial grade)

[0075] NPG (neopentyl glycol, Bailingwei Technology Co., Ltd., industrial grade)

[0076] 2-(Diisopropylphosphino)ethylamine (B&K Technology Co., Ltd., analytical grade)

[0077] 3-Aminopropyl(hexyl) hypophosphorous acid (CHEMICAL LAND21, analytical grade)

[0078] TEA (Triethylamine, Shanghai Aladdin Biochemical Technology Co., Ltd., analytical grade)

[0079] IPDA (isophorone diamine, Wanhua Chemical Group Co., Ltd., industrial grade)

[0080] EDA (ethylenediamine, Bailingwei Technology Co., Ltd., industrial grade)

[0081] Bismuth neodecanoate (American leading chemical company, analytical grade)

[0082] Kaolin (Shouchang Kaolin Factory, Qingshuihe County, Inner Mongolia, industrial grade)

[0083] AN-130 (Solvay, industrial grade)

[0084] Non-woven fabric (Huachang Group, industrial grade)

[0085] Room temperature bending tester (Dongguan Hengyu Instrument Co., Ltd., HY-761)

[0086] Low temperature bend tester (High Speed ​​Rail Testing Instrument Co., Ltd., GT-7006-V30)

[0087] Peel tester (GT-TCS-2000-D, High Speed ​​Rail Testing Instrument Co., Ltd.)

[0088] Electric constant temperature blast oven (Shanghai Jinghong Experimental Equipment Co., Ltd., DUG-9632A)

[0089] Rotary evaporator (Shanghai Yarong Biochemical Instrument Factory, RE-52AA)

[0090] 25 kg standard weight (Shanghai Shirun Industrial Co., Ltd., industrial grade)

[0091] <Test Method>

[0092] The test method for the foaming and foam stability of the resin is as follows: first, add 80 parts of filler to 100 parts of polyurethane resin, disperse it in a disperser at 2000r / min for 15 minutes, observe whether it can self-foam, and test the foaming ratio of the resin; secondly, continue to stir the slurry at a speed of 1000r / min for 10 minutes after the foaming is completed, and observe whether the foaming ratio decreases.

[0093] The peel strength of the water-based casual shoe leather base sample is tested according to the national standard QB / T2711-2005 and is required to be greater than 1.0N / mm

[0094] Room temperature bending of water-based casual shoe leather base samples, tested according to national standard QB / T2714-2005

[0095] Low temperature bending of water-based casual shoe leather base samples, tested at -15℃ according to national standard QB / T2714-2005

[0096] Jungle test: temperature 70℃, humidity 95%, time 4 weeks, thickness does not become thinner, surface does not become shiny and sticky, no other obvious changes

[0097] Example 1

[0098] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0099] 1) Under the protection of inert gas, 266 g of C2030, 14 g of PEG8000, 80 g of IPDI, 0.12 g of catalyst bismuth neodecanoate and 22.7 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 5.9%, which was slightly lower than the theoretical isocyanate content of 5.92%, to obtain an isocyanate-terminated prepolymer I;

[0100] 2) cooling the system containing the prepolymer I to 40° C., adding 11 g DMPA and 20.37 g acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.8%, which is slightly lower than the theoretical isocyanate content of 3.81%, to obtain an isocyanate-terminated prepolymer II;

[0101] 3) 296.8 g of acetone solvent was added to the system containing the prepolymer II for dilution and the temperature was lowered to 40° C., and 8.29 g of TEA was added for neutralization reaction for 5 min; 5 g of 2-(diisopropylphosphine)ethylamine was added for reaction for 15 min, and after the reaction was completed, 441.71 g of water was slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 23.44 g of IPDA was diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 48 wt%, a pH value of 7.9, and an average particle size of 255 nm.

[0102] Preparation of water-based casual shoe leather base:

[0103] SS1: Prepare an oxalic acid aqueous solution with a mass concentration of 1% to make an impregnation solution, then soak the non-woven fabric with the impregnation solution, stack it up and place it on a table, press it with a 25 kg standard weight for 5 minutes to squeeze out excess impregnation solution, and place the non-woven fabric in a 100°C oven for drying;

[0104] SS2: Under high-speed shearing at 2000 rpm, 100 g of the aqueous dispersion of the polyurethane or polyurethane urea is mixed with 80 g of filler powder, 1 g of color paste, and 1 g of pH adjuster AN-130, and then foamed to 1.3 times of its original volume to obtain the foamed slurry;

[0105] SS3: Iron the surface of the non-woven fabric treated with SS1 to make it smooth, then coat the foaming slurry obtained by SS2 on the non-woven fabric, preferably with a coating thickness of 0.8 mm; then place the non-woven fabric coated with the foaming slurry in an oven at 100°C for drying to obtain the water-based casual shoe leather base.

[0106] Example 2

[0107] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0108] 1) Under the protection of inert gas, 213 g of C2030, 37.5 g of PEG8000, 62 g of IPDI, 0.12 g of catalyst bismuth neodecanoate and 20.16 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 5.14%, which reached the theoretical isocyanate content of 5.14%, to obtain an isocyanate-terminated prepolymer I;

[0109] 2) cooling the system containing the prepolymer I to 40° C., adding 8 g of DMPA and 18.1 g of acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.32%, which is slightly lower than the theoretical isocyanate content of 3.36%, to obtain an isocyanate-terminated prepolymer II;

[0110] 3) 256.4 g of acetone solvent was added to the system containing the prepolymer II for dilution and the temperature was lowered to 40° C., and 6.03 g of TEA was added for neutralization reaction for 5 min; 7.5 g of 2-(diisopropylphosphine)ethylamine was added for reaction for 15 min, and after the reaction was completed, 393.79 g of water was slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 15.18 g of IPDA was diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, the polyurethane or polyurethane urea aqueous dispersion having a solid content of 47 wt%, a pH value of 8.3, and an average particle size of 294 nm.

[0111] Preparation of water-based casual shoe leather base:

[0112] SS1: Prepare an oxalic acid aqueous solution with a mass concentration of 0.8% to make an impregnation solution, then soak the non-woven fabric with the impregnation solution, stack it up and place it on a table, press it with a 25 kg standard weight for 5 minutes to squeeze out excess impregnation solution, and place the non-woven fabric in a 100°C oven for drying;

[0113] SS2: Under high-speed shearing at 2300 rpm, 100 g of the aqueous dispersion of the polyurethane or polyurethane urea is mixed with 100 g of filler powder, 2 g of color paste, and 2 g of pH adjuster AN-130, and then foamed to 1.2 times of its original volume to obtain the foamed slurry;

[0114] SS3: Iron the surface of the non-woven fabric treated with SS1 to make it smooth, then coat the foaming slurry obtained by SS2 on the non-woven fabric, preferably with a coating thickness of 1 mm; then place the non-woven fabric coated with the foaming slurry in an oven at 100°C for drying to obtain the water-based casual shoe leather base.

[0115] Example 3

[0116] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0117] 1) Under the protection of inert gas, 250 g C2030, 30 g PEG8000, 68 g IPDI, 0.13 g catalyst bismuth neodecanoate and 22.45 g acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 4.96%, which was slightly lower than the theoretical isocyanate content of 4.97%, to obtain an isocyanate-terminated prepolymer I;

[0118] 2) cooling the system containing the prepolymer I to 40° C., adding 7.8 g of DMPA and 20.15 g of acetone, and performing a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.36%, which is slightly lower than the theoretical isocyanate content of 3.39%, to obtain an isocyanate-terminated prepolymer II;

[0119] 3) 256.4 g of acetone solvent was added to the system containing the prepolymer II for dilution and the temperature was lowered to 40° C., and 6.03 g of TEA was added for neutralization reaction for 5 min; 7.5 g of 2-(diisopropylphosphine)ethylamine was added for reaction for 15 min, and after the reaction was completed, 385.9 g of water was slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 15.18 g of IPDA was diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, the polyurethane or polyurethane urea aqueous dispersion having a solid content of 50 wt%, a pH value of 8.6, and an average particle size of 310 nm.

[0120] Preparation of water-based casual shoe leather base:

[0121] SS1: Prepare an oxalic acid aqueous solution with a mass concentration of 0.9% to make an impregnation solution, then soak the non-woven fabric with the impregnation solution, stack it up and place it on a table, press it with a 25 kg standard weight for 5 minutes to squeeze out excess impregnation solution, and place the non-woven fabric in a 100°C oven for drying;

[0122] SS2: Under high-speed shearing at 2500 rpm, 100 g of the aqueous dispersion of the polyurethane or polyurethane urea is mixed with 90 g of filler powder, 1 g of color paste, and 1 g of pH adjuster AN-130, and then foamed to 1.3 times of its original volume to obtain the foamed slurry;

[0123] SS3: Iron the surface of the non-woven fabric treated with SS1 to make it smooth, then coat the foaming slurry obtained by SS2 on the non-woven fabric, preferably with a coating thickness of 0.8 mm; then place the non-woven fabric coated with the foaming slurry in an oven at 100°C for drying to obtain the water-based casual shoe leather base.

[0124] Example 4

[0125] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0126] 1) Under the protection of inert gas, 266 g of C2030, 14 g of PEG8000, 80 g of IPDI, 0.12 g of catalyst bismuth neodecanoate and 22.7 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 5.89%, which was slightly lower than the theoretical isocyanate content of 5.92%, to obtain an isocyanate-terminated prepolymer I;

[0127] 2) cooling the system containing the prepolymer I to 40° C., adding 11 g DMPA and 20.37 g acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.79%, which is slightly lower than the theoretical isocyanate content of 3.81%, to obtain an isocyanate-terminated prepolymer II;

[0128] 3) 296.8 g of acetone solvent was added to the system containing the prepolymer II for dilution and the temperature was lowered to 40° C., and 8.29 g of TEA was added for neutralization reaction for 5 min; 5.1 g of 3-aminopropyl (hexyl) hypophosphorous acid was added for reaction for 15 min, and after the reaction was completed, 498.98 g of water was slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 23.86 g of IPDA was diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 45 wt%, a pH value of 7.8, and an average particle size of 270 nm.

[0129] Preparation of water-based casual shoe leather base:

[0130] SS1: Prepare an oxalic acid aqueous solution with a mass concentration of 0.8% to make an impregnation solution, then soak the non-woven fabric with the impregnation solution, stack it up and place it on a table, press it with a 25 kg standard weight for 5 minutes to squeeze out excess impregnation solution, and place the non-woven fabric in a 100°C oven for drying;

[0131] SS2: Under high-speed shearing at 3000 rpm, 100 g of the aqueous dispersion of the polyurethane or polyurethane urea is mixed with 90 g of filler powder, 1 g of color paste, and 1 g of pH adjuster AN-130, and then foamed to 1.2 times of its original volume to obtain the foamed slurry;

[0132] SS3: Iron the surface of the non-woven fabric treated with SS1 to make it smooth, then coat the foaming slurry obtained by SS2 on the non-woven fabric, preferably with a coating thickness of 1 mm; then place the non-woven fabric coated with the foaming slurry in an oven at 100°C for drying to obtain the water-based casual shoe leather base.

[0133] Example 5

[0134] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0135] 1) Under the protection of inert gas, 260 g of C2030, 16 g of PEG8000, 82 g of HMDI, 0.12 g of catalyst bismuth neodecanoate and 22.31 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 4.9%, which was slightly lower than the theoretical isocyanate content of 4.95%, to obtain an isocyanate-terminated prepolymer I;

[0136] 2) cooling the system containing the prepolymer I to 40° C., adding 10 g of DMBA and 20.02 g of acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.19%, which is slightly lower than the theoretical isocyanate content of 3.20%, to obtain an isocyanate-terminated prepolymer II;

[0137] 3) 294 g of acetone solvent is added to the system containing the prepolymer II for dilution and the temperature is lowered to 40° C., and 6.03 g of TEA is added for neutralization reaction for 5 min; 5 g of 2-(diisopropylphosphine)ethylamine is added for reaction for 15 min, and after the reaction is completed, 452.91 g of water is slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 6.78 g of EDA is diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 46 wt%, a pH value of 7.9, and an average particle size of 260 nm.

[0138] Preparation of water-based casual shoe leather base:

[0139] SS1: Prepare an oxalic acid aqueous solution with a mass concentration of 1% to make an impregnation solution, then soak the non-woven fabric with the impregnation solution, stack it up and place it on a table, press it with a 25 kg standard weight for 5 minutes to squeeze out excess impregnation solution, and place the non-woven fabric in a 100°C oven for drying;

[0140] SS2: Under high-speed shearing at 2600 rpm, 100 g of the aqueous dispersion of the polyurethane or polyurethane urea is mixed with 80 g of filler powder, 1 g of color paste, and 1 g of pH adjuster AN-130, and then foamed to 1.1 times of its original volume to obtain the foamed slurry;

[0141] SS3: Iron the surface of the non-woven fabric treated with SS1 to make it smooth, then coat the foaming slurry obtained by SS2 on the non-woven fabric, preferably with a coating thickness of 0.8 mm; then place the non-woven fabric coated with the foaming slurry in an oven at 100°C for drying to obtain the water-based casual shoe leather base.

[0142] Comparative Example 1

[0143] Compared with Example 1, the component PEG8000 is not included.

[0144] 1) Under the protection of inert gas, 272 g of C2030, 80 g of IPDI, 0.12 g of catalyst bismuth neodecanoate and 22.07 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 6.0%, which was slightly lower than the theoretical isocyanate content of 6.02%, to obtain an isocyanate-terminated prepolymer I;

[0145] 2) cooling the system containing the prepolymer I to 40° C., adding 11 g DMPA and 19.81 g acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.8%, which is slightly lower than the theoretical isocyanate content of 3.89%, to obtain an isocyanate-terminated prepolymer II;

[0146] 3) 296.8 g of acetone solvent was added to the system containing the prepolymer II for dilution and the temperature was lowered to 40° C., and 8.29 g of TEA was added for neutralization reaction for 5 min; 5 g of 2-(diisopropylphosphine)ethylamine was added for reaction for 15 min, and after the reaction was completed, 424 g of water was slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 23.41 g of IPDA was diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 50 wt%, a pH value of 7.7, and an average particle size of 300 nm.

[0147] The preparation of water-based casual shoe leather base is based on Example 1.

[0148] Comparative Example 2

[0149] Compared with Example 1, the PPG3000 component is not included.

[0150] 1) Under the protection of inert gas, 230 g of C2020, 14 g of PEG8000, 80 g of IPDI, and 0.13 g of catalyst bismuth neodecanoate were contacted and mixed with 19.89 g of acetone, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 5.93%, which was slightly lower than the theoretical isocyanate content of 5.95%, to obtain a prepolymer I with a terminal isocyanate;

[0151] 2) cooling the system containing the prepolymer I to 40° C., adding 11 g DMPA and 17.85 g acetone, and performing a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.62%, which is slightly lower than the theoretical isocyanate content of 3.64%, to obtain an isocyanate-terminated prepolymer II;

[0152] 3) 268g of acetone solvent is added to the system containing the prepolymer II for dilution and the temperature is lowered to 40°C, and 8.29g of TEA is added for neutralization reaction for 5min; 5g of 2-(diisopropylphosphine)ethylamine is added for reaction for 15min, and after the reaction is completed, 389g of water is slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 19.86g of IPDA is diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 50wt%, a pH value of 7.7, and an average particle size of 263nm.

[0153] The preparation of water-based casual shoe leather base is based on Example 1.

[0154] Comparative Example 3

[0155] Compared with Example 1, the component 2-(diisopropylphosphino)ethylamine is not contained.

[0156] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0157] 1) Under the protection of inert gas, 266 g of C2030, 14 g of PEG8000, 80 g of IPDI, 0.12 g of catalyst bismuth neodecanoate and 22.7 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 5.9%, which was slightly lower than the theoretical isocyanate content of 5.92%, to obtain an isocyanate-terminated prepolymer I;

[0158] 2) cooling the system containing the prepolymer I to 40° C., adding 11 g DMPA and 20.37 g acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 3.8%, which is slightly lower than the theoretical isocyanate content of 3.81%, to obtain an isocyanate-terminated prepolymer II;

[0159] 3) 296.8 g of acetone solvent is added to the system containing the prepolymer II for dilution and the temperature is lowered to 40° C., and 8.29 g of TEA is added for neutralization reaction for 5 minutes; after the reaction is completed, 432.73 g of water is slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 25.55 g of IPDA is diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for full reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, the polyurethane or polyurethane urea aqueous dispersion having a solid content of 50 wt%, a pH value of 7.9, and an average particle size of 262 nm.

[0160] The preparation of water-based casual shoe leather base is based on Example 1.

[0161] Comparative Example 4

[0162] Does not contain PPG3000, PEG8000, 2-(diisopropylphosphine)ethylamine

[0163] Preparation of aqueous dispersions of polyurethane or polyurethane urea:

[0164] 1) Under the protection of inert gas, 220 g of C2020, 75 g of IPDI, 0.11 g of catalyst bismuth neodecanoate and 17.86 g of acetone were contacted and mixed, and reacted at 80° C. until the isocyanate content of the reaction mixture in the system was 4.15%, which was slightly lower than the theoretical isocyanate content of 4.19%, to obtain an isocyanate-terminated prepolymer I;

[0165] 2) cooling the system containing the prepolymer I to 40° C., adding 9 g DMPA, 6 g NPG and 20.37 g acetone, and carrying out a chain extension reaction at 80° C. until the isocyanate content of the reaction mixture in the system is 2.49%, which is slightly lower than the theoretical isocyanate content of 2.51%, to obtain an isocyanate-terminated prepolymer II;

[0166] 3) 248 g of acetone solvent is added to the system containing the prepolymer II for dilution and the temperature is lowered to 40° C., and 6.78 g of TEA is added for neutralization reaction for 5 minutes; after the reaction is completed, 351 g of water is slowly added to the system under stirring and shearing conditions of 800 rpm for dispersion operation; after dispersion, 14.01 g of IPDA is diluted with 5 times of water and added, and further reacted, and stirred under shearing conditions of 600 rpm for sufficient reaction to obtain a polyurethane or polyurethane urea aqueous dispersion containing solvent; acetone can be partially or completely removed by reduced pressure distillation to obtain a polyurethane or polyurethane urea aqueous dispersion, and the polyurethane or polyurethane urea aqueous dispersion has a solid content of 50 wt%, a pH value of 7.8, and an average particle size of 220 nm.

[0167] The preparation of water-based casual shoe leather base is based on Example 1.

[0168] According to the light industry standard, the performance of the samples of water-based clothing leather prepared in each embodiment and comparative example was tested using the above testing method. The test results are shown in Table 1.

[0169] Table 1 Performance test results of samples

[0170]

[0171]

[0172] It can be seen from the test results of Examples 1 to 5 and the comparative example that when preparing casual shoe leather bases based on the aqueous dispersion of polyurethane or polyurethane urea provided by the present invention, there is no need to add a foaming stabilizer to obtain the casual shoe leather bases, and the surface flatness is good, the peel strength is high, the bending performance at room temperature and low temperature is excellent, the thickness does not become thinner after the jungle test, and the surface does not become shiny and sticky.

[0173] 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 spirit of the present invention.

Claims

1. A polyurethane or polyurethane urea aqueous dispersion, characterized in that: The dispersion comprises the reaction product of: a) at least one polyol, b) at least one polyisocyanate, c) at least one hydrophilic compound component, d) at least one phosphorus-containing alkylamine, e) at least one neutralizing agent, f) at least one small amine compound; Wherein, the component a) is selected from a composition of polypropylene oxide glycol with a molecular weight of 3000 and polyethylene oxide glycol with a molecular weight of 8000 and a mass ratio of 95%:5% to 85%:15%; The component c) contains 2 to 3 NCO reactive functional groups, and its hydrophilic group includes one or more of ionic groups and potential ionic groups.

2. The dispersion according to claim 1, characterized in that In the component c), the NCO reactive group is a hydroxyl group and / or an amino group, and the ionic group is a carboxylate group -COO - and / or sulfonate -SO3 - , the potential ion groups are carboxyl group -COOH and / or sulfonic acid group -SO3H.

3. The dispersion according to claim 1, characterized in that Based on the total weight of each component being 100%, the weight percentage of each component is as follows: The amount of component a) is 69-75%, The amount of component b) is 16-22%, The amount of component c) is 1.9-2.9%, The amount of component d) is 1.0-2.1%, The amount of component e) is 1.4-2.1%, The amount of component f) used is 1.5-6.0%.

4. The dispersion according to claim 3, characterized in that Based on the total weight of each component being 100%, the weight percentage of each component is as follows: The amount of component a) is 70-74%, The amount of component b) is 17-20%, The amount of component c) is 2.0%-2.7%, The amount of component d) is 1.1-1.9%, The amount of component e) is 1.5-2.0%, The amount of component f) used is 1.6-5.8%.

5. The dispersion according to claim 1 or 2, characterized in that The component b) is one or more of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate; and / or, the component c) is one or more of dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-3-aminopropanesulfonic acid and N-(2-aminoethyl)-3-aminopropanesulfonic acid; and / or, the component d) is a phosphine-containing monoamine having a molecular weight of 100 to 300; and / or, the component e) is one or more of a primary amine, a secondary amine, a tertiary amine, an alkali metal compound and an alkaline earth metal compound; And / or, the component f) is a polyamine having a molecular weight of 60-500.

6. The dispersion according to claim 5, characterized in that The component b) is a diisocyanate; And / or, the component d) is one or more of 3-aminopropyl(hexyl)phosphinophosphine, 2-(diethylphosphino)ethylamine, and 2-(diisopropylphosphino)ethylamine; and / or, the component e) is one or more of ammonia, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide; And / or, the component f) is one or more of ethylenediamine, hydroxyethylethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,6-hexamethylenediamine, hexamethylenediamine and isophoronediamine.

7. The dispersion according to claim 6, characterized in that The component b) is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and / or, the component d) is 2-(diisopropylphosphine)ethylamine; And / or, the component f) is one or more of isophoronediamine, hydroxyethylethylenediamine and 1,6-hexamethylenediamine.

8. The dispersion according to claim 1, characterized in that The solid content of the dispersion is 40-55wt%; and / or, the pH value of the dispersion is 7.5-9; And / or, the average particle size of the dispersion is 160 to 750 nm.

9. The dispersion according to claim 8, characterized in that The solid content of the dispersion is 45-50wt%; and / or, the pH value of the dispersion is 8 to 8.5; And / or, the average particle size of the dispersion is 200 to 450 nm.

10. A method for preparing the polyurethane or polyurethane urea aqueous dispersion according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: S1: Component a), component b), catalyst and solvent A are mixed and reacted to obtain a prepolymer I having an isocyanate terminal; S2: cooling the prepolymer I of S1, adding component c) and solvent B, and performing a chain extension reaction to obtain an isocyanate-terminated prepolymer II; S3: Add solvent C to the prepolymer II system of S2 to dilute, cool, add component e) to neutralize, add component d) to react, add water to disperse after the reaction, add component f) after dispersion for further reaction to obtain a water dispersion containing solvent; Optionally, S4: removing the solvent to obtain an aqueous dispersion of the polyurethane or polyurethane urea.

11. The preparation method according to claim 10, characterized in that: The S1 is reacted at 60-90°C; and / or, the reaction of S1 reaches or is slightly lower than the theoretical isocyanate content to obtain prepolymer I; And / or, the solvent A in S1 is an organic solvent having a boiling point lower than 100°C.

12. The preparation method according to claim 11, characterized in that: The solvent A of S1 is acetone.

13. The preparation method according to claim 10, characterized in that: The S2 is reacted at 60-80°C; and / or, the reaction of S2 reaches or is slightly lower than the theoretical isocyanate content to obtain prepolymer II; And / or, the solvent B in S2 is an organic solvent having a boiling point lower than 100°C.

14. The preparation method according to claim 13, characterized in that: The solvent B of S2 is acetone.

15. The preparation method according to claim 10, characterized in that: The S3 is reacted at 40°C; and / or, the water in S3 is added in an amount of 45-50 wt % of the added solids; And / or, the solvent C in S3 is an organic solvent having a boiling point lower than 100°C.

16. The preparation method according to claim 15, characterized in that: The solvent C of S3 is acetone.

17. The preparation method according to claim 10, characterized in that: The S4 is partially or completely freed of solvent by distillation under reduced pressure.

18. A water-based bass, comprising the polyurethane or polyurethane urea aqueous dispersion according to any one of claims 1 to 9, or the polyurethane or polyurethane urea aqueous dispersion prepared by the preparation method according to any one of claims 10 to 17, characterized in that: The base comprises a base fabric and a foaming slurry; wherein the foaming slurry is prepared by the following components:

19. A method for preparing water-based bass as claimed in claim 18, characterized in that: The preparation method of the bass comprises the following steps: SS1: Soak the non-woven fabric with acid solution impregnation liquid, squeeze out the excess impregnation liquid, and dry the non-woven fabric; SS2: Under high-speed shearing, the aqueous dispersion of polyurethane or polyurethane urea is mixed with filler powder, color paste, and pH adjuster, and then foamed to obtain a foaming slurry; SS3: The foaming slurry of SS2 is coated on the base fabric of SS1, and then dried to obtain the water-based bass.

20. The method for preparing bass according to claim 19, characterized in that: SS1: The impregnation liquid is an aqueous solution of oxalic acid, tartaric acid or hydrochloric acid.

21. The method for preparing bass according to claim 20, characterized in that: The impregnation solution of SS1 is an aqueous solution of oxalic acid with a mass concentration of 0.8% to 1%.

22. The method for preparing bass according to claim 19, characterized in that: The foaming of SS2 is to foam to 1.1-1.3 times of the original volume; And / or, the SS2 high speed shear speed is greater than or equal to 2000 rpm.

23. The method for preparing bass according to claim 19, characterized in that: The coating thickness of SS3 is 0.8 to 1 mm.

24. Use of water-based bass, wherein the water-based bass is the water-based bass according to claim 18, or the water-based bass prepared by the preparation method according to any one of claims 19 to 23, characterized in that: The water-based bass is used as water-based casual shoe leather bass.

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