A foamed polyurethane or polyurea aqueous dispersion, and a preparation method and application thereof

Abstract

The present invention discloses a self-foaming polyurethane or polyurea water dispersion, which is characterized by being prepared by a reaction comprising the following components: a) at least one polyether polyol, b) at least one polyisocyanate, c) at least one fatty amine polyoxyethylene ether reactive to isocyanate, d) optionally, a small-molecule chain-extending alcohol, e) at least one hydrophilic compound, f) at least one neutralizing agent containing a tertiary amine group, g) optionally, a low-molecular compound containing at least two NCO-reactive amino groups, h) at least one piperidine alcohol containing a tertiary amine group and at least one hydroxyl group. The present invention has the advantages of slow surface skinning speed of the water dispersion, fast drying speed, high foaming property and foam stability of the dispersion itself, and high strength of the resin and flexibility of the foaming layer.

Description

Technical Field

[0001] This invention relates to the field of aqueous dispersions, and more particularly to a foamed polyurethane or polyurea aqueous dispersion, its preparation method, and its application. Background Technology

[0002] The synthetic leather industry typically uses polyurethane or polyurea foaming resins. Traditional solvent-based resins usually generate large amounts of wastewater and waste gas, which is detrimental to human health and does not align with environmentally friendly development principles. In recent years, waterborne polyurethane or polyurea resins have been increasingly used in the synthetic leather field. Waterborne PU leather production processes are divided into dry and wet processes. Wet-process PU leather preparation is cumbersome and requires complex equipment, while dry-process PU leather is simple to operate, highly operable, safe, and environmentally friendly, effectively reducing harmful substance emissions. However, at high speeds, the dry process is prone to surface skinning too quickly while the underlying layer is not completely dried, resulting in a significant decrease in the adhesion between the foam layer and the substrate. PU leather for clothing requires a soft and breathable feel, but during storage and transportation, it often develops irreversible indentations due to prolonged folding. Leather factories typically mitigate these indentations through ironing and other post-treatment methods, but these cannot completely restore the original appearance. Summary of the Invention

[0003] The purpose of this invention is to provide a foamed polyurethane or polyurea aqueous dispersion, its preparation method and application, which is used to prepare synthetic leather and has advantages such as fast drying speed, less susceptibility to indentation, soft hand feel and good air permeability.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A self-foaming polyurethane or polyurea aqueous dispersion is prepared by a reaction comprising the following components:

[0006] a) At least one polyether polyol,

[0007] b) At least one polyisocyanate,

[0008] c) At least one fatty amine polyoxyethylene ether that is reactive to isocyanates.

[0009] d) Optional, small molecule chain-extending alcohols,

[0010] e) at least one hydrophilic compound,

[0011] f) At least one neutralizing agent containing a tertiary amine group.

[0012] g) Optional, a low-molecular-weight compound containing at least two NCO-reactive amino groups.

[0013] h) at least one piperidine alcohol containing a tertiary amine group and at least one hydroxyl group.

[0014] Furthermore, the amounts of each component in the aqueous dispersion are as follows:

[0015] Component a) 50-90 wt%, preferably 60-80 wt%;

[0016] Component b) 8-45 wt%, preferably 15-30 wt%;

[0017] Component c) 0.5-5 wt%, preferably 1-3 wt%;

[0018] Component d) 0-5 wt%, preferably 1-4 wt%;

[0019] Component e) 0.5-3 wt%, preferably 0.5-2 wt%;

[0020] Component f) 0.4-3 wt%, preferably 0.4-1.5 wt%;

[0021] Component (g) 0-3wt%, preferably 1-2.5wt%;

[0022] Component h) 0.5-2wt%, preferably 0.6-1.5wt%;

[0023] The total mass of the above components is taken as 100%.

[0024] The polyols described in this invention include diols, and the polyisocyanates include diisocyanates.

[0025] Further, component a) is a polyether polyol with a number average molecular weight of 1000-15000, preferably a polyether diol and / or triol and / or tetraol with a number average molecular weight of 1000-5000; more preferably one or more of polypropylene oxide ether diol and polytetrahydrofuran ether diol with a number average molecular weight of 1000-5000.

[0026] Further, component b) is an aliphatic, alicyclic, and aromatic polyisocyanate, preferably one or more of aliphatic or alicyclic isocyanates having two isocyanate groups; preferably, diisocyanate Y(NCO)2 is used, wherein Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms, a divalent aromatic hydrocarbon group containing 6-15 carbon atoms, or a divalent aryliphatic hydrocarbon group containing 7-15 carbon atoms. Suitable diisocyanates may be one or more of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, dodecylmethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate, and terephthalic diisocyanate.

[0027] Further, component c) is a fatty amine polyoxyethylene ether containing two terminal hydroxyl groups. Preferably, the molar mass of component c) is 200-800, more preferably 300-500, and the polymer unit is a fatty amine polyoxyethylene ether with ethylene oxide. The number of ethylene oxide molecules in each molecule is 3-20, more preferably 3-9.

[0028] The initiator of the aliphatic amine polyoxyethylene ether is a monohydric aliphatic amine with carbon atoms of C12-C18, including but not limited to saturated monohydric amines, such as n-dodecylamine, 2-dodecylamine, n-tetrideamine, n-tetradecylamine, n-pentadecanamine, n-hexadecylamine, n-heptadecylamine, and n-octadecylamine; unsaturated aliphatic amines, such as cis-9-enhexadecane-1-amine; the preferred initiator is a saturated monohydric amine with carbon atoms of C12-C18, and particularly preferred is n-dodecylamine as an initiator.

[0029] Further, component d) is a small molecule extended-chain alcohol containing at least two NCO reactive hydroxyl groups, preferably one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methylpentane-1,5-pentanediol, 1,6-hexanediol, neopentanediol, 1,4-cyclohexyldiethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-3-propylpentanediol, 2,2-dimethylpentanediol, diethylene glycol, glycerol, and trimethylolpropane, more preferably one or more of ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, diethylene glycol, and neopentanediol, and even more preferably diethylene glycol and / or neopentanediol.

[0030] Further, component e) is a hydrophilic compound containing a carboxylic acid group; preferably, the hydrophilic compound contains 2 to 3 NCO reactive functional groups; more preferably, component e) is one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, and dihydroxysuccinic acid; even more preferably, component e) is dimethylolpropionic acid;

[0031] Preferably, component f) is one or more of ammonia, ammonium carbonate, bicarbonate, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, or sodium carbonate, more preferably one or more of triethylamine, triethanolamine, dimethylethanolamine, sodium hydroxide, and potassium hydroxide;

[0032] Preferably, the component g) is selected from one or more of ethylenediamine, hydroxyethyl ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, hexylenediamine, and isophoronediamine; more preferably ethylenediamine and / or isophoronediamine.

[0033] Preferably, component h) is selected from 1-methyl-4-piperidinol, 1-ethyl-4-piperidinol, 1-methyl-4-piperidinol, 1-methyl-2-piperidinol, 1-methyl-2-piperidinol, 1-methyl-3-piperidinol, 1-ethyl-3-piperidinol, 1-methyl-3-piperidinol, 1-ethyl-3-piperidinol, 1-isopropyl-3-piperidinol, 1-isopropyl-3-piperidinol, 1-isopropyl-4-piperidinol, 1-isopropyl-4-piperidinol, hydroxyethylpiperidinol, pentamethylpiperidinol; more preferably 1-methyl-4-piperidinol and / or 1-methyl-4-piperidinol.

[0034] A method for preparing the polyurethane or polyurea aqueous dispersion described above includes the following steps:

[0035] 1) Components a), b), c), e), h), optional component d), and solvent are added to a reaction vessel under inert gas protection and reacted until the reaction mixture reaches the theoretical isocyanate content to obtain a prepolymer modified with aliphatic amine polyoxyethylene ether.

[0036] 2) Add solvent to dilute and cool the prepolymer, then add component f) to carry out a neutralization reaction;

[0037] 3) Add deionized water to the neutralization reaction solution under high-speed stirring to disperse it. Optionally, after dispersion, add component g) to continue the reaction. After the reaction, remove the solvent to obtain an aqueous dispersion. The amount of deionized water added is based on the solid content of the final aqueous dispersion being 25-65 wt%, preferably 40-55 wt%.

[0038] Further, step 1) is carried out in the presence of a catalyst, with a catalyst dosage of 50-1000 ppm, based on the total mass of the added solid components;

[0039] Preferably, the catalyst is one or more of triethylamine, 1,4-diazabicyclo-[2,2,2]octane, dibutyltin oxide, tin dioctanoate or dibutyltin dilaurate, bis-(2-ethylhexanoate)tin, bismuth neodecanoate, and bismuth 2-ethylhexanoate; preferably bismuth neodecanoate or bismuth 2-ethylhexanoate, more preferably bismuth neodecanoate;

[0040] Further, the reaction conditions in step 1) are: reaction temperature 50-150℃, preferably 60-90℃; reaction pressure 0-5MPa, preferably 0-1MPa.

[0041] Preferably, the solvent is selected from solvents that can be partially or completely removed by distillation during or after dispersion, preferably one or more of acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, and 1-methyl-2-pyrrolidone, more preferably acetone and butanone, and even more preferably acetone.

[0042] Further, in step 2), after adding solvent to dilute, the temperature is first lowered to below 45°C, and then component f) is added to continue the reaction for 5-10 minutes.

[0043] Preferably, the total amount of solvent used in steps 1) and 2) is 0.3-1.5 times the total mass of the added solids, more preferably 0.5-1.0 times.

[0044] Furthermore, in step 3), the stirring rate is 800-1500 r / min, and the stirring time is 5-15 min.

[0045] Further, after the dispersion in step 3) is completed, the optional added component g) continues to react for 5-15 min, and then the solvent is removed by vacuum distillation.

[0046] The polyurethane or polyurea aqueous dispersion prepared by the above method has a solid content of 35-65 wt%, preferably 40-55 wt%. The pH value of the aqueous dispersion is 4-11, preferably 5-10; the average particle size is typically 80-600 nm, preferably 150-400 nm.

[0047] This invention also provides an application of the aqueous dispersion described herein in the fields of leather and synthetic leather. The dispersion of this invention can be used to prepare leather and synthetic leather through physical foaming.

[0048] This invention introduces piperidinol, containing both tertiary amine and hydroxyl groups, directly into the polyurethane molecular chain segment by adding the tertiary amine group on the piperidinium ring. This neutralizes the carboxylic acid group, slowing down the surface skinning rate of the foam layer during drying and improving the overall drying speed. Simultaneously, by adding aliphatic amine polyoxyethylene ether with a nonionic surfactant structure, two polyethoxyl segments and one aliphatic segment are directly introduced, giving the polyurethane or polyurea molecules adjacent hydrophilic and hydrophobic groups. This improves the foam stability of the dispersion and enhances the foam strength. Furthermore, the long side-chain structure of the aliphatic segment increases the entanglement between polyurethane molecules, improving the resin strength and the flexibility of the foam layer. This solves the problem of indentation in water-based PU leather, and the resulting synthetic leather is soft to the touch, breathable, resistant to bending, and has high peel strength. Detailed Implementation

[0049] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0050] The main reagents used in the examples are as follows:

[0051] PPG4000, polyether diol, hydroxyl value 28 mg KOH / g: Wanhua Chemical Group

[0052] PPG2000, polyether diol, hydroxyl value 56 mg KOH / g: Wanhua Chemical Group

[0053] PPG1000, polyether diol, hydroxyl value 112 mg KOH / g: Wanhua Chemical Group

[0054] 4,4-Dicyclohexylmethane diisocyanate (HMDI): (Wanhua Chemical Group Co., Ltd.)

[0055] Isoflurone diisocyanate (IPDI): (Wanhua Chemical Group Co., Ltd.)

[0056] Hexamethylene diisocyanate (HDI): (Wanhua Chemical Group Co., Ltd.)

[0057] N-Methyl-4-piperidinol (Anhui Dexinjia Biomedical Co., Ltd.)

[0058] N-Methyl-4-piperidinemethanol (Anhui Dexinjia Biomedical Co., Ltd.)

[0059] AC1210 (Dodecylamine polyoxyethylene ether, EO number 10, Guoli Chemical Co., Ltd.)

[0060] AC1215 (Dodecylamine polyoxyethylene ether, EO number 15, Guoli Chemical Co., Ltd.)

[0061] AC1810 (Octadecylamine polyoxyethylene ether, EO number 10, Guoli Chemical Co., Ltd.)

[0062] AC1820 (octadecylamine polyoxyethylene ether, EO number 20, Guoli Chemical Co., Ltd.)

[0063] Dimethylolpropionic acid (DMPA), Pastoria, Sweden

[0064] Neopentyl Glycol (NPG), Wanhua Chemical Group Co., Ltd.

[0065] Isophorone diamine, IPDA (industrial grade, Wanhua Chemical Group Co., Ltd.)

[0066] 8108, Bismuth neodecanoate catalyst, from a leading US chemical company.

[0067] A801 (Thickener, Wanhua Chemical Group Co., Ltd.)

[0068] RT120 (Fiber Powder Filler) Xinji Rongda Kun Wood Powder Co., Ltd.

[0069] Black paste (WH-902, Shanghai Fukonai Industrial Co., Ltd.)

[0070] CX-100 (Curing agent, Guangzhou Yangsong Trading Co., Ltd.)

[0071] Methods for evaluating the performance of aqueous dispersions:

[0072] The preparation method of synthetic leather is as follows: using the dispersion as the base material, add 0.3% by mass of black pigment, pH adjuster, and aziridine curing agent. After stirring evenly in a disperser, add filler (20% fiber powder) and stir evenly in a disperser until the surface of the slurry is smooth and delicate. Add 6% foam stabilizer and mechanically foam at a speed of 2500 r / min, with a foaming ratio of 2.3 times. Add thickener A801 ​​dropwise until the viscosity is about 35000. Use 50 wire rods to coat it onto release paper and dry it. Use 50 wire rods to coat the foam material again on the dried foam layer. Then cover the foam material with base fabric and dry it to obtain synthetic leather.

[0073] Indentation resistance test: Fold the prepared synthetic leather sample in half, press the sample with a 3Kg weight, and place it at 70℃ and 80℃ for 3 hours respectively. Open the sample, press the crease with an iron for 10 seconds, and observe the recovery of the crease.

[0074] Drying test: Apply the prepared foaming slurry to the release paper using a 100# wire rod, place it in an 80℃ oven, and take it out every 30 seconds to observe the surface skin formation (touch). The later the skin appears, the better.

[0075]

Example 1

[0076] 204g of dehydrated PPG2000, 3g of DMPA, 3g of AC1210, 2g of neopentyl glycol, 3g of N-methyl-4-piperidinol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.46wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 45°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 343g of water under high-speed stirring. After dispersion, 6g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solid content of 50wt%, an average particle size of 245nm, and a pH of 8.1.

[0077]

Example 2

[0078] 204g of dehydrated PPG2000, 8g of DMPA, 5g of AC1215, 4g of N-methyl-4-piperidinemethanol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.37wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 45°C. 6.04g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 347g of water under high-speed stirring. After dispersion, 3g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solids content of 50wt%, an average particle size of 175nm, and a pH of 8.0.

[0079]

Example 3

[0080] 204g of dehydrated PPG2000, 3g of DMPA, 10g of AC1810, 4.5g of N-methyl-4-piperidinemethanol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.35wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 45°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 347g of water under high-speed stirring. After dispersion, 6g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solids content of 50wt%, an average particle size of 296nm, and a pH of 7.9.

[0081]

Example 4

[0082] 102g of dehydrated PPG1000, 1.5g of DMPA, 1g of AC1210, 9g of neopentyl glycol, 1g of N-methyl-4-piperidinol, 60g of HMDI, 20g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 0.82wt%. 105g of acetone was added for dilution, and the mixture was cooled to below 40°C. 1.13g of triethylamine was added for neutralization for 10 minutes, and then the mixture was dispersed by adding 215g of water under high-speed stirring. The acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solids content of 50wt%, an average particle size of 203nm, and a pH of 8.1.

[0083]

Example 5

[0084] 408g of dehydrated PPG4000, 3g of DMPA, 3g of AC1210, 3g of N-methyl-4-piperidinol, 50g of HMDI, 50g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 0.6wt%. 300g of acetone was added for dilution, and the mixture was cooled to below 40°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 580g of water under high-speed stirring. After dispersion, 5g of isophorone diamine was added and stirring was continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solid content of 50wt%, an average particle size of 312nm, and a pH of 8.1.

[0085]

Example 6

[0086] 204g of dehydrated PPG2000, 3g of DMPA, 15g of AC1820, 6g of N-methyl-4-piperidinol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.01wt%. 170g of acetone was added for dilution, and the mixture was cooled to below 40°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 360g of water under high-speed stirring. After dispersion, 4g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solid content of 50wt%, an average particle size of 250nm, and a pH of 8.1.

[0087] Comparative Example 1

[0088] 204g of dehydrated PPG2000, 3g of DMPA, 3g of AC1210, 5g of neopentyl glycol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.39 wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 40°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 343g of water under high-speed stirring. After dispersion, 6g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solid content of 50 wt%, an average particle size of 260 nm, and a pH of 8.1.

[0089] Comparative Example 2

[0090] 204g of dehydrated PPG2000, 3g of DMPA, 2g of neopentyl glycol, 3g of N-methyl-4-piperidinol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.34wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 40°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 343g of water under high-speed stirring. After dispersion, 6g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solids content of 50wt%, an average particle size of 245nm, and a pH of 8.1.

[0091] Comparative Example 3

[0092] 204g of dehydrated PPG2000, 3g of DMPA, 5g of neopentyl glycol, 60g of HMDI, 38.5g of acetone, and 0.08g of catalyst 8108 were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.53wt%. 158g of acetone was added for dilution, and the mixture was cooled to below 40°C. 2.27g of triethylamine was added for neutralization for 10 minutes. The mixture was then dispersed by adding 343g of water under high-speed stirring. After dispersion, 6g of isophorone diamine was added, and stirring continued for 5 minutes. Acetone was then separated by distillation to obtain a solvent-free aqueous dispersion with a solids content of 50wt%, an average particle size of 243nm, and a pH of 8.1.

[0093] Performance evaluation of aqueous dispersions:

[0094] The aqueous dispersions obtained in the various embodiments and comparative examples were formulated into slurries according to the methods provided in the specific embodiments of the present invention, and then mechanically foamed to obtain water-based PU leather. Performance tests were performed on all water-based PU leathers, and the test results are shown in Table 1.

[0095] Table 1

[0096]

[0097] Note: The feel test rating is 5 points for best and 0 points for worst.

[0098] The test results show that the aqueous dispersion prepared according to this invention has excellent anti-indentation effect and a slow surface skinning speed, while the emulsion prepared in Comparative Example 1 cannot achieve a slow surface skinning speed, and the emulsion prepared in Comparative Example 2 cannot achieve a good anti-indentation effect. Therefore, the PU garment leather prepared from the foamed waterborne polyurethane emulsion prepared according to this invention has excellent anti-indentation effect, and the prepared waterborne PU leather has a slow surface drying speed, which can improve vehicle speed to a certain extent.

[0099] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A self-foaming polyurethane or polyurea aqueous dispersion, characterized in that, It is prepared by a reaction comprising the following components: Component a) at least one polyether polyol, Component b) at least one polyisocyanate, Component c) At least one aliphatic amine polyoxyethylene ether reactive to isocyanates. Component d) Optional, small molecule chain-extending alcohol, Component e) at least one hydrophilic compound, Component f) At least one neutralizing agent containing a tertiary amine group, Component g) optionally, a low-molecular-weight compound containing at least two NCO-reactive amino groups. Component h) at least one piperidine alcohol containing a tertiary amine group and at least one hydroxyl group; The initiator of the fatty amine polyoxyethylene ether is a monodimeric fatty amine with carbon atoms of C12-C18; Component e) is a hydrophilic compound containing a carboxylic acid group.

2. The aqueous dispersion according to claim 1, characterized in that, The amounts of each component in the aqueous dispersion are as follows: Component a) 50-90 wt% Component b) 8-45 wt% Component c) 0.5-5 wt% Component d) 0-5wt% Component e) 0.5-3 wt%; Component f) 0.4-3 wt% Component (g) 0-3wt% Component (h) 0.5-2wt%; The total mass of the above components is taken as 100%.

3. The aqueous dispersion according to claim 2, characterized in that, The amounts of each component in the aqueous dispersion are as follows: Component a) 60-80 wt% Component b) 15-30 wt% Component c) 1-3 wt% Component d) 1-4 wt% Component e) 0.5-2 wt%; Component f) 0.4-1.5 wt%; Component (g) 1-2.5wt%; Component (h) 0.6-1.5 wt%; The total mass of the above components is taken as 100%.

4. The aqueous dispersion according to claim 1, characterized in that, Component a) is a polyether polyol with a number average molecular weight of 1000-15000.

5. The aqueous dispersion according to claim 4, characterized in that, Component a) is a polyether diol and / or triol and / or tetraol with a number average molecular weight of 1000 to 5000.

6. The aqueous dispersion according to claim 5, characterized in that, Component a) is one or more of polyoxypropylene ether diol and polytetrahydrofuran ether diol with a number average molecular weight of 1000-5000.

7. The aqueous dispersion according to claim 1, characterized in that, Component b) is an aliphatic, alicyclic, and aromatic polyisocyanate.

8. The aqueous dispersion according to claim 7, characterized in that, Component b) is one or more aliphatic or alicyclic isocyanates having two isocyanate groups.

9. The aqueous dispersion according to claim 7, characterized in that, Component b) is diisocyanate Y(NCO)2, wherein Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms, a divalent aromatic hydrocarbon group containing 6-15 carbon atoms, or a divalent aromatic aliphatic hydrocarbon group containing 7-15 carbon atoms.

10. The aqueous dispersion according to claim 1, characterized in that, Component b) is one or more of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate, and terephthalic diisocyanate.

11. The aqueous dispersion according to claim 1, characterized in that, Component c) is a fatty amine polyoxyethylene ether containing two terminal hydroxyl groups.

12. The aqueous dispersion according to claim 1, characterized in that, The component c) has a molar mass of 200-800 and is a fatty amine polyoxyethylene ether with ethylene oxide as the polymer unit, wherein the number of ethylene oxide molecules in each molecule is 3-20.

13. The aqueous dispersion according to claim 12, characterized in that, The component c) has a molar mass of 300-500 and is a fatty amine polyoxyethylene ether with ethylene oxide as the polymer unit, wherein the number of ethylene oxide molecules in each molecule is 3-20.

14. The aqueous dispersion according to claim 12 or 13, characterized in that, In fatty amine polyoxyethylene ethers, the number of ethylene oxide molecules in each molecule is 3 to 9.

15. The aqueous dispersion according to claim 1, characterized in that, The initiator of the fatty amine polyoxyethylene ether is n-dodecylamine, 2-dodecylamine, n-tetrazine, n-tetradecylamine, n-pentadecanylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, or cis-9-enhexadecyl-1-amine.

16. The aqueous dispersion according to claim 1, characterized in that, The initiator for the fatty amine polyoxyethylene ether is n-dodecylamine.

17. The aqueous dispersion according to claim 1, characterized in that, The component d) is a small molecule extended chain alcohol containing at least two NCO reactive hydroxyl groups.

18. The aqueous dispersion according to claim 17, characterized in that, Component d) is one or more of the following: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, 1,4-cyclohexyldiethanol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-3-propyl-1,5-pentanediol, 2,2-dimethyl-1,5-pentanediol, diethylene glycol, glycerol, and trimethylolpropane.

19. The aqueous dispersion according to claim 18, characterized in that, Component d) is one or more of ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, diethylene glycol, and neopentyl glycol.

20. The aqueous dispersion according to claim 1, characterized in that, In component e), the hydrophilic compound contains 2 to 3 NCO reactive functional groups.

21. The aqueous dispersion according to claim 20, characterized in that, Component e) is one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, and dihydroxysuccinic acid.

22. The aqueous dispersion according to claim 21, characterized in that, Component e) is dihydroxymethylpropionic acid.

23. The aqueous dispersion according to claim 1, characterized in that, The component f) is one or more of trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, and triethanolamine.

24. The aqueous dispersion according to claim 23, characterized in that, The component f) is one or more of triethylamine, triethanolamine, and dimethylethanolamine.

25. The aqueous dispersion according to claim 1, characterized in that, The component g) is selected from one or more of ethylenediamine, hydroxyethyl ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine and isophoronediamine.

26. The aqueous dispersion according to claim 25, characterized in that, The component g) is selected from ethylenediamine and / or isophorone diamine.

27. The aqueous dispersion according to claim 1, characterized in that, The component h) is selected from 1-methyl-4-piperidinol, 1-ethyl-4-piperidinol, 1-methyl-4-piperidinol, 1-methyl-2-piperidinol, 1-methyl-2-piperidinol, 1-methyl-3-piperidinol, 1-ethyl-3-piperidinol, 1-methyl-3-piperidinol, 1-ethyl-3-piperidinol, 1-isopropyl-3-piperidinol, 1-isopropyl-3-piperidinol, 1-isopropyl-4-piperidinol, 1-isopropyl-4-piperidinol, hydroxyethylpiperidinol, and pentamethylpiperidinol.

28. The aqueous dispersion according to claim 27, characterized in that, The component h) is 1-methyl-4-piperidinol and / or 1-methyl-4-piperidinol.

29. The aqueous dispersion according to claim 1, characterized in that, The pH value of the aqueous dispersion is 4 to 11; the average particle size is 80 to 600 nm.

30. The aqueous dispersion according to claim 29, characterized in that, The pH value of the aqueous dispersion is 5-10; the average particle size is 150-400 nm.

31. A method for preparing the polyurethane or polyurea aqueous dispersion according to claim 1, characterized in that, Includes the following steps: Step 1) Components a), b), c), e), h), optional component d), and solvent are added to the reactor under inert gas protection and reacted until the reaction mixture reaches the theoretical isocyanate content to obtain a prepolymer modified with fatty amine polyoxyethylene ether. Step 2) Add solvent to dilute and cool the prepolymer, then add component f) to carry out a neutralization reaction; Step 3) Add deionized water to the neutralization reaction solution under high-speed stirring to disperse it. Optionally, after dispersion, add component g) to continue the reaction. After the reaction, remove the solvent to obtain an aqueous dispersion.

32. The method according to claim 31, characterized in that, The amount of deionized water added should be based on the final solid content of the aqueous dispersion being 25-65 wt%.

33. The method according to claim 32, characterized in that, The amount of deionized water added should be based on the final solid content of the aqueous dispersion being 40-55 wt%.

34. The method according to claim 31, characterized in that, Step 1) is carried out in the presence of a catalyst, with a catalyst dosage of 50-1000 ppm, based on the total mass of the added solid components.

35. The method according to claim 34, characterized in that, The catalyst is one or more of the following: triethylamine, 1,4-diazabicyclo-[2,2,2]octane, dibutyltin oxide, tin dioctanoate or dibutyltin dilaurate, bis-(2-ethylhexanoate)tin, bismuth neodecanoate, and bismuth 2-ethylhexanoate.

36. The method according to claim 35, characterized in that, The catalyst is selected from bismuth neodecanoate and bismuth 2-ethylhexanoate.

37. The method according to claim 31, characterized in that, The reaction conditions in step 1) are: reaction temperature 50-150℃; reaction pressure 0-5MPa.

38. The method according to claim 37, characterized in that, The reaction conditions in step 1) are: reaction temperature 60-90℃; reaction pressure 0-1MPa.

39. The method according to claim 31, characterized in that, The solvent is selected from solvents that can be partially or completely removed by distillation during or after dispersion.

40. The method according to claim 39, characterized in that, The solvent is selected from one or more of acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether, and 1-methyl-2-pyrrolidone.

41. The method according to claim 40, characterized in that, The solvent is selected from acetone and butanone.

42. The method according to claim 39, characterized in that, Step 2) After adding solvent to dilute, first cool down to below 45℃, then add component f) and continue the reaction for 5-10 minutes.

43. The method according to claim 31, characterized in that, In steps 1) and 2), the total amount of solvent used is 0.3-1.5 times the total mass of the added solids.

44. The method according to claim 43, characterized in that, In steps 1) and 2), the total amount of solvent used is 0.5-1.0 times the total mass of the added solids.

45. The application of an aqueous dispersion according to any one of claims 1-30 or an aqueous dispersion prepared by any one of claims 31-44 in the field of leather and synthetic leather.

46. ​​The application according to claim 45, characterized in that, The aqueous dispersion is used to prepare leather and synthetic leather through physical foaming.

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