CN110862506A - Synthetic method of waterborne polyurethane primer - Google Patents

Synthetic method of waterborne polyurethane primer Download PDF

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Publication number
CN110862506A
CN110862506A CN201911036024.1A CN201911036024A CN110862506A CN 110862506 A CN110862506 A CN 110862506A CN 201911036024 A CN201911036024 A CN 201911036024A CN 110862506 A CN110862506 A CN 110862506A
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waterborne polyurethane
steps
synthesizing
following
method comprises
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赵雨花
王军威
亢茂青
冯月兰
殷宁
李其峰
张清运
梁辰
李晓云
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints

Abstract

The invention relates to a synthetic method of a waterborne polyurethane primer, belonging to the technical field of synthetic methods of waterborne polyurethane primers. The invention mainly solves the technical problems of poor stability, low bonding strength and the like of the existing waterborne polyurethane primer. A synthetic method of a waterborne polyurethane primer comprises the following steps: 1) adding dehydrated polyol, diol chain extender containing ionic group and diisocyanate into a reactor, adding a solvent-1 and a catalyst, continuing to react, then adding a micromolecular diol chain extender and a solvent-2, and adding a neutralizer for neutralization to obtain an intermediate; 2) adding an aqueous solution of a diamine chain extender containing sulfonic groups into the intermediate, then adding deionized water under rapid stirring for uniform dispersion, adding an aqueous solution of a coupling agent and a micromolecular diamine chain extender for chain extension reaction, and removing a solvent in vacuum to obtain an aqueous polyurethane dispersion liquid; 3) and (3) preparing the aqueous polyurethane dispersion liquid and the auxiliary agent into a primer with proper viscosity and wettability.

Description

Synthetic method of waterborne polyurethane primer
Technical Field
The invention belongs to the technical field of synthetic methods of waterborne polyurethane primers, and particularly relates to a synthetic method of a waterborne polyurethane primer.
Background
Waterborne Polyurethanes (WPU) are increasingly being used in a wide variety of applications such as coatings, adhesives, inks, etc. due to their environmentally friendly, low VOC emissions, and superior combination of properties comparable to solvent-based polyurethanes. However, there are many disadvantages such as poor chemical resistance, thermal stability, mechanical properties and hydrolytic stability, which limit the applications in various fields. Therefore, research on improving WPU performance has been a focus of research.
The organic siloxane resin has low surface tension, unique flexibility, low glass transition temperature, high-temperature stability, good water resistance, chemical resistance and electrical insulation, but has low cohesive energy density, poor adhesion, poor organic solvent resistance, low mechanical property and high price. The performance of the water-based polyurethane resin and the performance of the organic silicon material can be complementary, the heat resistance, the weather resistance, the hydrophobicity and the electrical insulation performance of the water-based polyurethane resin are far inferior to those of the organic silicon resin, and the adhesive force, the wear resistance, the mechanical performance and the construction performance of the water-based polyurethane resin are far superior to those of the organic silicon resin. Thus, studies on the use of silicones for improving WPU properties have been reported in recent years, but these reports have mainly focused on the water resistance and thermal stability of WPU films. And the prepared WPU dispersion is mostly used for coating to improve the surface property but is rarely used for adhesive. The silane modification method can be divided into physical modification and chemical modification. The physical modification is only simple physical mixing and no chemical bond is formed; the chemical modification method mainly comprises (1) forming Si-O-C bond by copolymerization reaction of silanol (which means that hydroxyl is directly connected with silicon atom) and isocyanate group; (2) the amino-terminated or hydroxyl-terminated polysiloxane and polyester or polyether polyol are used as mixed soft segments to react with isocyanate groups to respectively form Si-C-N bonds and Si-C-O bonds; (3) the polyurethane prepolymer is modified through the end-capping reaction of functional organic silicon monomers containing different functional groups and the hydrolytic crosslinking action of end-capped siloxane; (4) method for modification of vinylsiloxanes. For example, the Han-Do Kim team (Journal of applied Polymer Science, 2012, Vol. 125, 88-96; J Appl Polym Sci 120: 212-219, 2011) adopts siloxane polyol namely Polydimethylsiloxane (PDMS) and polyester polyol namely polybutylene adipate (PTAd) or polytetramethylene ether glycol (PTMG) as mixed soft segments to synthesize the functional coating of the waterborne polyurethane (WBPU) by a prepolymer method, and aims to explore the potential application of PDMS to compensate the flexibility, water resistance and adhesion of WBPU. The effect of PDMS molecular weight and PDMS content (PDMS mol%) on water swelling (%), tensile strength, and bond strength of WBPU was investigated. CN 105330813 discloses a synthetic method of organic silicon modified waterborne polyurethane for leather making, which comprises the steps of carrying out stepwise polymerization reaction on low polymer dihydric alcohol, aliphatic diisocyanate, hydroxyl-terminated silicone oil and hydrophilic chain extenders (micromolecule dihydric alcohol and micromolecule dihydric alcohol containing carboxyl), synthesizing organic silicon modified hydrophilic polyurethane prepolymer with side chains containing carboxyl, neutralizing and dispersing by using polyamine, and then carrying out chain extension by using diamine to prepare organic silicon modified waterborne polyurethane emulsion. CN 108997918A invented a method for preparing an organosilicon modified waterborne polyurethane finish, which is to mix waterborne organosilicon resin, waterborne hydroxyl resin and various additives (including dispersant, PH regulator, thickener, film forming additive, pigment, filler, leveling agent and defoamer) at a high speed to obtain a component A, mix water dispersible isocyanate and cosolvent uniformly to obtain a component B, and then mix A, B two components uniformly according to a certain proportion to obtain the organosilicon modified two-component waterborne polyurethane finish with good hydrophobicity and weather resistance. S. Subramini (J applPolym Sci, 2005, 98: 620-. Research results show that the adhesive force and the thermal stability of the waterborne polyurethane coating can be improved, and the mechanical property, the wear resistance and the chemical resistance of the waterborne polyurethane coating can be improved through the hydrolytic crosslinking of the siloxane end group. The Roche army team (chemical development, 2006,25 (3): 319-; the fabric coating agent can be used for endowing fabric with softness and smoothness. The organosilicon material, such as Yangling, etc. (the organosilicon material, 2009,23 (5): 297) 301) uses toluene diisocyanate, hydroxyethyl acrylate and polyethylene glycol as raw materials to synthesize a polyurethane macromonomer, then the polyurethane macromonomer is mixed with methyl methacrylate and methacryloxy trimethoxy silane (DB-570), and the mixture is dripped into a seed emulsion of polyacrylate (BA) to prepare the organosilicon modified polyurethane-acrylate copolymer emulsion, and the particle size, the particle size distribution and the storage stability of the emulsion are studied in detail.
The primer should be attributed to the binder, but it acts not only as an adhesive for the substrate but also for the adhesive layer. Has the functions of both coupling agent and surfactant. Therefore, the adhesive belongs to a special adhesive, and is used for improving the bonding performance and playing a role of a bridging agent between a substrate and the adhesive. Because the oil content of the oil skin is high, although the oil skin contains an amino acid structure, the existence and the migration of the oil directly influence the bonding effect of the leather and the adhesive.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a synthetic method of a waterborne polyurethane primer, and solves the technical problems of poor stability, low bonding strength and the like of the conventional waterborne polyurethane primer.
The invention is realized by the following technical scheme:
a synthetic method of a waterborne polyurethane primer comprises the following steps:
1) adding dehydrated polyol, a glycol chain extender containing an ionic group and diisocyanate into a reactor, heating to 70-90 ℃ in the stirring process, keeping the temperature for reaction for 1-2 hours, adding a solvent-1 and a catalyst, continuing the reaction for 1-2 hours, then adding a micromolecule glycol chain extender and a solvent-2, reacting for 1-2 hours at 50-80 ℃, analyzing the NCO% content by a di-n-butylamine back titration method to reach a theoretical value, cooling to 50-60 ℃, adding a neutralizer for neutralization for 15-30 minutes, and cooling to 40-45 ℃ to obtain an intermediate;
wherein, the ratio of polyhydric alcohol: ionic group-containing glycol chain extender: diisocyanate: solvent-1: small molecule diol chain extender: solvent-2: neutralizing agent (0.02-0.03 mol): (0.02-0.03 mol): (0.10-0.15 mol): (20-50 g): (0.01-0.02 mol): (20-50 g): (0.02-0.03 mol);
the addition amount of the catalyst is 0.001-0.5 wt% of the total amount of reactants; the reactor is provided with a stirrer, a thermometer and a condenser;
2) adding 50 wt% of water solution containing a sulfonic group diamine chain extender into the intermediate, rapidly stirring for 5-20 min, slowly adding deionized water metered according to solid content, coupling agents metered according to different molar ratios and small-molecule diamine chain extender water solution (the concentration is 10-20 wt%) under rapid stirring, uniformly stirring, heating to 50-60 ℃, carrying out heat preservation reaction for 30-60 min, and removing the solvent in vacuum to obtain milky waterborne polyurethane dispersion;
wherein, the diamine chain extender containing sulfonic group: intermediate: coupling agent: micromolecule diamine chain extender = (0.02-0.03 mol): (100-200 g): (0.012-0.024 mol): 0.012-0.018 mol);
the solid content is 40-50%;
3) aiming at different substrates, the waterborne polyurethane dispersion liquid and the auxiliary agent are prepared into a primer with proper viscosity and wettability, and then the synthesis of the waterborne polyurethane primer can be completed;
the auxiliary agent comprises a thickening agent and a substrate wetting agent; the addition amount of the thickening agent is 0.1-0.2 wt% of the amount of the aqueous polyurethane dispersion liquid; the addition amount of the base material wetting agent is 0.1-0.5 wt% of the amount of the aqueous polyurethane dispersion.
Further, the polyol in the step 1) is polyether glycol and/or polyester glycol;
the polyether glycol is one or more of PTMG-1000, PTMG-2000 and PTMG-2900 of polytetramethylene ether glycol;
the polyester diol is one or more of poly adipate, poly epsilon-caprolactone diol and polycarbonate diol, and the molecular weight range is 1000-3000.
Further, the polyadipate is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol adipate-propylene glycol, polyethylene glycol adipate-butylene glycol, polyethylene glycol adipate and polyethylene glycol adipate-neopentyl glycol, and the molecular weight range is 1000-3000.
Further, the molecular weight range of the polyadipates is 2000-3000.
Further, the molecular weight range of the polyester diol is 2000-3000.
Further, the glycol chain extender containing the ionic group in the step 1) is dimethylolpropionic acid (DMPA) or dimethylolbutyric acid containing a carboxylic acid group.
Further, the glycol chain extender containing the ionic group is dimethylolpropionic acid (DMPA) containing a carboxylic acid group.
Further, the diisocyanate in step 1) is an aromatic diisocyanate or an aliphatic diisocyanate.
Further, the aromatic compound IIThe isocyanate comprises Toluene Diisocyanate (TDI) or 4, 4' -diphenylmethane diisocyanate (MDI); the aliphatic diisocyanate includes 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4, 4' -dicyclohexylmethane diisocyanate (H)12MDI)。
Further, the aliphatic diisocyanate is 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).
Further, the small-molecule glycol chain extender in the step 1) is Ethylene Glycol (EG), 1, 2-propylene glycol, 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO), 1, 5-pentanediol, neopentyl glycol (NPG) or diethylene glycol (DEG).
Further, the small-molecule glycol chain extender is 1, 4-Butanediol (BDO).
Further, in the step 1), the solvent-1 is one or a combination of more of acetone, butanone, Dimethylformamide (DMF) and N-methylpyrrolidone (NMP);
the solvent-2 is one or a combination of more of acetone, butanone, Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
Further, the neutralizing agent in the step 1) is one of NaOH, KOH, ammonia water or triethylamine.
Further, the neutralizing agent is triethylamine.
Further, the catalyst in the step 1) is one of dibutyltin dilaurate (T-12), stannous octoate (T-9) and triethylene diamine; the addition amount of the catalyst is 0.005-0.01 wt% of the total amount of reactants. A
Further, the catalyst was dibutyltin dilaurate (T-12).
Further, the diamine chain extender containing sulfonic groups in the step 2) is ethylenediamine sodium ethanesulfonate or diaminobenzene sodium sulfonate.
Further, the diamine chain extender containing sulfonic groups is ethylenediamine ethanesulfonic acid sodium salt.
Further, in the step 2), the coupling agent is one or a mixture of 3-aminopropyltriethoxysilane (KH 550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), 3-mercaptopropyltrimethoxysilane (KH-580), N (-2-aminoethyl) -3-aminopropylmethyldimethoxysilane (KH-602) and N-2-aminoethyl-3-aminopropyltrimethoxysilane (KH-792).
Further, the coupling agent is 3-aminopropyltriethoxysilane (KH 550) or 3-mercaptopropyltrimethoxysilane (KH-580).
Further, the micromolecule diamine chain extender in the step 2) comprises one or more of Ethylenediamine (EDA), Diethylenetriamine (DETA), hexamethylenediamine and piperazine.
Further, the micromolecule diamine chain extender is piperazine.
Further, the auxiliary agent in the step 3) is limited to the primer for dermal adhesion.
Further, the thickener in the step 3) is acrylate modified polyurethane or polyurethane liquid aqueous thickener.
Further, the substrate wetting agent in the step 3) is one of an auxiliary agent low-foam super wetting agent, an auxiliary agent low-foam dynamic wetting agent, an osmotic wetting agent, a wetting dispersant or a substrate wetting agent.
Further, the substrate wetting agent is wetting dispersant CA-168.
The silane coupling agent is mainly used for preparing composite materials of high polymer materials and different types of fillers. Generally, one end contains organic functional groups with different structures, and the other end is inorganic siloxane. Therefore, the organic functional group in the composite material is combined with the high polymer material, and the inorganic siloxane at the other end is combined with the inorganic filler or various fibers to play a role of a bridge so as to improve the dispersibility and the interface bonding force of the inorganic filler or the fibers in the organic high polymer material. Considering that silane coupling agents (such as amino, sulfydryl, epoxy and the like) containing different functional groups are extremely easy to chemically react with isocyanate groups of synthetic waterborne polyurethane, silane chain segments can be introduced into the WPU main chain by partially replacing diamine chain extenders in the chain extension step of the coupling agents containing different functional groups for chain extension, so that the water resistance and the heat resistance of the WPU are improved, and simultaneously, the siloxane crosslinking can improve the wettability of a substrate (such as leather) and play a role of an anchoring agent to improve the bonding performance (bonding strength) of the substrate and an adhesive layer. The invention utilizes the hydrolytic crosslinking of siloxane to moderately improve the crosslinking density of WPU, improve the water resistance and heat resistance, improve the wettability of the WPU to a base material (such as leather and the like) and improve the bonding strength of the base material and an adhesive.
Compared with the prior art, the invention has the following advantages:
1. the raw materials are easy to obtain, and the cost is low;
2. the introduction of the silane coupling agent enables the synthesized waterborne polyurethane primer to improve the water resistance, the damp-heat resistance and the aging resistance of the waterborne polyurethane primer through siloxane hydrolytic crosslinking, and also can improve the wettability of the base material and play a role of an anchoring agent so as to improve the bonding performance between the base material and the adhesive;
3. The adhesive has the advantages of high solid content (more than or equal to 45 wt%), average particle size of less than 300nm, viscosity of less than 250mPaS, good dispersion stability (more than or equal to 180 days), good damp-heat aging resistance (the retention rate of adhesive strength is more than or equal to 65%), and wide applicability of base materials.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the emulsion obtained had a solids content of 46.0%, an average particle diameter of 185nm, a viscosity of 45mPaS and was stable on storage at room temperature for 200 days without demixing.
3) The waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.18N/mm, the adhesion strength at 24h was measured to be 1.20N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 3.21N/mm.
Example 2
1) 50g of dehydrated polycarbonate diol (molecular weight 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate were added into a reactor, heated to 85 ℃ while stirring and kept warm to react for 1 hour, 20g of acetone and 0.03g of dibutyltin dilaurate (T-12) as a catalyst were added and then the reaction was continued for 1 hour, 2.36g of diethylene glycol (DEG) and 20g of acetone were added and the reaction was continued for 2 hours at 60 ℃, after the content of NCO% reached the theoretical value as determined by back titration with di-n-butylamine, the temperature was reduced to 50 ℃, 1.69g of triethylamine was added and the reaction was continued for 20 minutes while the temperature was reduced to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 2.7g of 3-aminopropyltriethoxysilane (KH 550) and 16g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the emulsion obtained had a solids content of 45.8%, an average particle diameter of 204nm, a viscosity of 195 mPaS and was stable on storage at room temperature for 185 days without delamination.
3) The waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.05N/mm.24h and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 1.85N/mm, and 3.09N/mm.
Example 3
1) 50g of dehydrated polycarbonate diol (molecular weight 2000), 2.24g of dimethylolpropionic acid containing carboxylic acid groups, 26.7g of 4, 4' -dicyclohexylmethane diisocyanate (H)12MDI) and 2.67g of 1, 6-hexamethylene diisocyanate are added into a reactor, the mixture is heated to 85 ℃ and kept for reaction for 1 hour in the stirring process, 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12) are added for continuous reaction for 1 hour, then 2.63g of 1, 6-Hexanediol (HDO) and 20g of acetone are added for reaction for 2 hours at 60 ℃, the temperature is reduced to 50 ℃ after the content of NCO% reaches the theoretical value by using a dibutylamine back titration method, 1.69g of triethylamine is added for neutralization for 20 minutes, and the temperature is reduced to 40 ℃ at the same time, so as to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 3.54g of 3-aminopropyltriethoxysilane (KH 550) and 13.8g of 10% piperazine aqueous solution with rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky aqueous polyurethane dispersion; the emulsion obtained had a solids content of 46.8%, an average particle diameter of 190nm, a viscosity of 67.5 mPaS and was stable on storage at room temperature for 210 days without demixing.
3) The waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.45N/mm, the adhesion strength at 24h was measured to be 2.15N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 3.41N/mm.
Example 4
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the NCO content reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.7g of 3-mercaptopropyltrimethoxysilane (KH-580) and 11g of 10% aqueous solution of piperazine under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 45.2%, an average particle size of 200nm, a viscosity of 82.5 mPaS, and is stable to store at room temperature for 225 days without delamination;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.15N/mm.24h and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 2.01N/mm, 2.80N/mm.
Example 5
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.0g N (-2-aminoethyl) -3-aminopropylmethyldimethoxysilane (KH-602) and 7g of 10% piperazine aqueous solution with rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has the solid content of 48.1 percent, the average particle size of 242nm and the viscosity of 162.5mPas, and is stably stored for 180 days without delamination at room temperature;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.03N/mm.24h adhesion strength is measured to be 1.25N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 2.65N/mm.
Example 6
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.3g of N-2-aminoethyl-3-aminopropyltrimethoxysilane (KH-792) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 45.3%, an average particle size of 251nm, a viscosity of 82.5 mPaS, and is stable to store at room temperature for 195 days without delamination;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.12N/mm.24h adhesion strength is measured to be 1.42N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 2.53N/mm.
Example 7
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 45.5%, an average particle size of 280nm, a viscosity of 182.5 mPaS, and is stable to store at room temperature for 185 days without delamination;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.22N/mm, the adhesion strength at 24h was measured to be 1.35N/mm, and the adhesion strength at 70 ℃ after aging at 95% relative humidity for 7 days was measured to be 2.35N/mm.
Example 8
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, reacting for 30min under a heat preservation condition, and removing the solvent in vacuum to obtain a milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 47.5%, an average particle size of 219nm, a viscosity of 90mPaS, and is stable to store at room temperature for 205 days without delamination;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.39N/mm.24h and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 2.45N/mm.
Example 9
1) Adding 50g of dehydrated polycarbonate diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ while stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, quickly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-mercaptopropyltrimethoxysilane (KH-580) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has the solid content of 45.9 percent, the average particle size of 251nm and the viscosity of 190mPas, and can be stably stored at room temperature for 218 days without delamination;
3) the waterborne polyurethane dispersion (WPU) is directly used as a primer of the oil skin, and the oil skin is subjected to an adhesion test according to a sample preparation method for an adhesion strength test. The initial adhesion strength at 5min was measured to be 1.56N/mm, the adhesion strength at 24h was 2.08N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was 3.15N/mm.
Example 10
1) Adding 25g of dehydrated polycarbonate diol (molecular weight 2000), 25g of 1, 4-butanediol adipate (molecular weight 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and carrying out heat preservation reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a dibutylamine back titration method, adding 1.69g of triethylamine to neutralize for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the obtained emulsion has a solid content of 45.4%, an average particle diameter of 189nm, a viscosity of 142.5 mPaS, and is stable to store at room temperature for 187 days without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N is added into 100g of the prepared waterborne polyurethane dispersion (WPU), 0.2 g of a substrate wetting agent is a wetting dispersant CA-168 of Guangzhou Xuanning engineering and technology Limited company, and the mixture is stirred and mixed uniformly to obtain the waterborne polyurethane primer, and the bonding test is carried out on the leather according to a sample preparation method for the bonding strength test. The initial adhesion strength at 5min was measured to be 1.68N/mm, the adhesion strength at 24h was 2.86N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was 1.85N/mm.
Example 11
1) Adding 35g of dehydrated polycarbonate diol (molecular weight 2000), 15g of polyhexamethylene adipate (molecular weight 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing the content of NCO% by a di-n-butylamine back titration method to reach a theoretical value, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-mercaptopropyltrimethoxysilane (KH-580) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 45.7%, an average particle size of 193nm, a viscosity of 140 mPaS, and is stable to store at room temperature for 195 days without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was 2.68N/mm, the adhesion strength at 24h was 2.92N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was 2.13N/mm.
Example 12
1) Adding 50.8g of dehydrated polytetramethylene ether glycol (molecular weight is 2900), 15g of polyhexamethylene adipate (molecular weight is 2000), 2.24g of carboxylic acid group-containing dimethylolpropionic acid, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and carrying out heat preservation reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12) and then continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after the NCO content reaches the theoretical value by using a di-n-butylamine back titration analysis, adding 1.69g of triethylamine to neutralize for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.7g of 3-mercaptopropyltrimethoxysilane (KH-580) and 7g of 10% aqueous solution of ethylenediamine, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain milky aqueous polyurethane dispersion; the obtained emulsion has a solid content of 45.1%, an average particle size of 230nm, a viscosity of 185 mPaS, and is stable to store at room temperature for 188 days without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was 2.45N/mm, the adhesion strength at 24h was 2.68N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was 1.82N/mm.
Example 13
1) Adding 25g of dehydrated polycarbonate diol (molecular weight is 2000)/36g of polytetramethylene ether glycol (molecular weight is 2900), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12) and continuing to react for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, cooling to 50 ℃ after analyzing that the content of NCO% reaches a theoretical value by a dibutylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and cooling to 40 ℃ at the same time to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the obtained emulsion has a solid content of 47.3%, an average particle size of 175nm, a viscosity of 227mPaS, and is stable to store at room temperature for 210 days without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was 2.12N/mm, the adhesion strength at 24h was 2.48N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was 1.93N/mm.
Example 14
1) Adding 25g of dehydrated polycarbonate diol (molecular weight is 2000), 25g of polycaprolactone diol (molecular weight is 2000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring, keeping the temperature for reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing the reaction for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 60 ℃, reducing the temperature to 50 ℃ after analyzing that the NCO% content reaches a theoretical value by a di-n-butylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the obtained emulsion has the solid content of 48.3 percent, the average particle size of 180nm and the viscosity of 203mPaS, and can be stably stored for 220 days at room temperature without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was measured to be 1.85N/mm, the adhesion strength at 24h was measured to be 2.26N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 1.58N/mm.
Example 15
1) Adding 50g of dehydrated polycarbonate diol (with the molecular weight of 3000) and 25g of polybutylene adipate (with the molecular weight of 3000), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and carrying out heat preservation reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing the reaction for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 80 ℃, reducing the temperature to 60 ℃ after analyzing that the content of NCO% reaches a theoretical value by a dibutylamine back titration method, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the obtained emulsion has a solid content of 45.6%, an average particle size of 220nm, a viscosity of 175mPaS, and is stable for 200 days at room temperature without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was measured to be 3.05N/mm, the adhesion strength at 24h was measured to be 3.26N/mm, and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 2.25N/mm.
Example 16
1) Adding 50g of dehydrated polycarbonate diol (with the molecular weight of 3000), 20g of polyhexamethylene adipate (with the molecular weight of 2500), 2.24g of dimethylolpropionic acid containing a carboxylic acid group, 22.64g of isophorone diisocyanate (IPDI) and 2.67g of 1, 6-hexamethylene diisocyanate into a reactor, heating to 85 ℃ during stirring and carrying out heat preservation reaction for 1 hour, adding 20g of acetone and 0.03g of catalyst dibutyltin dilaurate (T-12), continuing the reaction for 1 hour, then adding 2.0g of 1, 4-Butanediol (BDO) and 20g of acetone, reacting for 2 hours at 80 ℃, reducing the temperature to 60 ℃ after analyzing the content of NCO% by a dibutylamine back titration method to reach a theoretical value, adding 1.69g of triethylamine for neutralization for 20 minutes, and reducing the temperature to 40 ℃ at the same time to obtain an intermediate;
2) adding 9.8g of 50 wt% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt into the intermediate, rapidly stirring for 10min, slowly adding deionized water with a solid content of 45 wt%, 5.4g of 3-aminopropyltriethoxysilane (KH 550) and 10g of 10% piperazine aqueous solution under rapid stirring, uniformly stirring, heating to 50 ℃, carrying out heat preservation reaction for 30min, and removing the solvent in vacuum to obtain a milky-white waterborne polyurethane dispersion; the obtained emulsion has a solid content of 46.2%, an average particle size of 218nm, a viscosity of 190mPaS, and is stable to store at room temperature for 225 days without delamination;
3) 0.2 g of acrylate modified polyurethane thickener L-75N and 0.2 g of substrate wetting agent CA-168 of Guangzhou Xuanning engineering technology ltd are added into 100g of the prepared waterborne polyurethane dispersion (WPU), and the waterborne polyurethane primer is obtained after stirring and mixing uniformly, and the bonding test is carried out on the leather according to the sample preparation method of the bonding strength test. The initial adhesion strength at 5min was measured to be 2.95N/mm.24h and the adhesion strength after aging at 70 ℃ under 95% relative humidity for 7 days was measured to be 3.12N/mm, 2.32N/mm.
As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims (27)

1. The synthetic method of the waterborne polyurethane primer is characterized by comprising the following steps: the method comprises the following steps:
adding dehydrated polyol, a glycol chain extender containing an ionic group and diisocyanate into a reactor, heating to 70-90 ℃ in the stirring process, keeping the temperature for reaction for 1-2 hours, adding a solvent-1 and a catalyst, continuing the reaction for 1-2 hours, then adding a micromolecule glycol chain extender and a solvent-2, reacting for 1-2 hours at 50-80 ℃, analyzing the NCO% content by a di-n-butylamine back titration method to reach a theoretical value, cooling to 50-60 ℃, adding a neutralizer for neutralization for 15-30 minutes, and cooling to 40-45 ℃ to obtain an intermediate;
wherein, the ratio of polyhydric alcohol: ionic group-containing glycol chain extender: diisocyanate: solvent-1: small molecule diol chain extender: solvent-2: 0.02-0.03 mol of neutralizer: 0.02-0.03 mol: 0.10-0.15 mol: 20-50 g: 0.01-0.02 mol: 20-50 g: 0.02-0.03 mol;
the addition amount of the catalyst is 0.001-0.5 wt% of the total amount of reactants; the reactor is provided with a stirrer, a thermometer and a condenser;
adding 50 wt% of water solution of diamine chain extender containing sulfonic group into the intermediate, rapidly stirring for 5-20 min, slowly adding deionized water metered according to solid content, coupling agent metered according to different molar ratios and small molecule diamine chain extender with the concentration of 10-20wt% into the intermediate under rapid stirring, uniformly stirring, heating to 50-60 ℃, carrying out heat preservation reaction for 30-60 min, and removing the solvent in vacuum to obtain milky waterborne polyurethane dispersion;
wherein, the diamine chain extender containing sulfonic group: intermediate: coupling agent: small molecule diamine chain extender = 0.02-0.03 mol, 100-200 g: 0.012-0.024 mol, 0.012-0.018 mol;
the solid content is 40-50%;
aiming at different substrates, the waterborne polyurethane dispersion liquid and the auxiliary agent are prepared into a primer with proper viscosity and wettability, and then the synthesis of the waterborne polyurethane primer can be completed;
the auxiliary agent comprises a thickening agent and a substrate wetting agent; the addition amount of the thickening agent is 0.1-0.2 wt% of the amount of the aqueous polyurethane dispersion liquid; the addition amount of the base material wetting agent is 0.1-0.5 wt% of the amount of the aqueous polyurethane dispersion.
2. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the polyol in the step 1) is polyether glycol and/or polyester glycol;
the polyether glycol is one or more of PTMG-1000, PTMG-2000 and PTMG-2900 of polytetramethylene ether glycol;
the polyester diol is one or more of poly adipate, poly epsilon-caprolactone diol and polycarbonate diol, and the molecular weight range is 1000-3000.
3. The method for synthesizing the waterborne polyurethane primer according to claim 2, wherein the method comprises the following steps: the polyadipate is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol adipate-propylene glycol, polyethylene glycol adipate-butylene glycol, polyethylene glycol adipate and polyethylene glycol adipate-neopentyl glycol, and the molecular weight range is 1000-3000.
4. The method for synthesizing the waterborne polyurethane primer according to claim 3, wherein the method comprises the following steps: the molecular weight range of the polyadipates is 2000-3000.
5. The method for synthesizing the waterborne polyurethane primer according to claim 2, wherein the method comprises the following steps: the molecular weight range of the polyester diol is 2000-3000.
6. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the glycol chain extender containing the ionic group in the step 1) is dimethylolpropionic acid or dimethylolbutyric acid containing a carboxylic acid group.
7. The method for synthesizing the waterborne polyurethane primer according to claim 6, wherein the method comprises the following steps: the glycol chain extender containing the ionic group is dimethylolpropionic acid containing a carboxylic acid group.
8. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the diisocyanate in step 1) is an aromatic diisocyanate or an aliphatic diisocyanate.
9. The method for synthesizing the waterborne polyurethane primer according to claim 8, wherein the method comprises the following steps: the aromatic diisocyanate comprises toluene diisocyanate or 4, 4' -diphenylmethane diisocyanate; the aliphatic diisocyanate includes 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, or 4, 4' -dicyclohexylmethane diisocyanate.
10. The method for synthesizing the waterborne polyurethane primer according to claim 9, wherein the method comprises the following steps: the aliphatic diisocyanate is 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
11. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: in the step 1), the micromolecular diol chain extender is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 5-pentanediol, neopentyl glycol or diethylene glycol.
12. The method for synthesizing the waterborne polyurethane primer according to claim 11, wherein the method comprises the following steps: the micromolecular diol chain extender is 1, 4-butanediol.
13. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: in the step 1), the solvent-1 is one or a combination of more of acetone, butanone, dimethylformamide and N-methylpyrrolidone;
the solvent-2 is one or a combination of more of acetone, butanone, dimethylformamide and N-methylpyrrolidone.
14. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the neutralizing agent in the step 1) is one of NaOH, KOH, ammonia water or triethylamine.
15. The method for synthesizing the waterborne polyurethane primer according to claim 14, wherein the method comprises the following steps: the neutralizing agent is triethylamine.
16. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the catalyst in the step 1) is one of dibutyltin dilaurate, stannous octoate and triethylene diamine; the addition amount of the catalyst is 0.001-0.5 wt% of the total amount of the reactants.
17. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the catalyst was dibutyltin dilaurate.
18. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the diamine chain extender containing sulfonic groups in the step 2) is ethylenediamine sodium ethanesulfonate or diaminobenzene sodium sulfonate.
19. The method for synthesizing the waterborne polyurethane primer according to claim 18, wherein the method comprises the following steps: the diamine chain extender containing sulfonic group is ethylenediamine sodium ethanesulfonate.
20. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: in the step 2), the coupling agent is one or a mixture of 3-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N (-2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2-aminoethyl-3-aminopropyltrimethoxysilane.
21. The method for synthesizing the waterborne polyurethane primer according to claim 20, wherein the method comprises the following steps: the coupling agent is 3-aminopropyl triethoxysilane or 3-mercaptopropyl trimethoxysilane.
22. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the micromolecule diamine chain extender in the step 2) comprises one or more of ethylenediamine, diethylenetriamine, hexamethylenediamine and piperazine.
23. The method for synthesizing the waterborne polyurethane primer according to claim 22, wherein the method comprises the following steps: the micromolecule diamine chain extender is piperazine.
24. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the auxiliary agent in the step 3) is limited to the primer for bonding the dermis.
25. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the thickening agent in the step 3) is acrylate modified polyurethane or polyurethane liquid water-based thickening agent.
26. The method for synthesizing the waterborne polyurethane primer according to claim 1, wherein the method comprises the following steps: the base material wetting agent in the step 3) is one of an auxiliary agent low-foam super wetting agent, an auxiliary agent low-foam dynamic wetting agent, a penetrating wetting agent, a wetting dispersing agent or a base material wetting agent.
27. The method for synthesizing the waterborne polyurethane primer according to claim 26, wherein the method comprises the following steps: the substrate wetting agent is wetting dispersant CA-168.
CN201911036024.1A 2019-10-29 2019-10-29 Synthetic method of waterborne polyurethane primer Pending CN110862506A (en)

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