CN115368533B - Preparation method and application of aqueous polyurethane resin - Google Patents
Preparation method and application of aqueous polyurethane resin Download PDFInfo
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- 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
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- 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
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- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
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Abstract
The invention relates to a preparation method and application of waterborne polyurethane resin. The preparation method of the invention comprises the steps of polymerizing dihydric alcohol and diisocyanate in advance, taking sorbitol and oxalyl hydrazide as well as sodium hydroxysulfonate as a chain extender, and emulsifying to obtain the aqueous polyurethane resin emulsion, wherein the aqueous polyurethane resin emulsion has uniform and fine appearance, moderate viscosity and good stability. Meanwhile, the preparation method of the aqueous polyurethane resin has the advantages of simple and convenient operation, low cost and less three wastes. Therefore, it is an economically viable production method, suitable for industrial application.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method and application of waterborne polyurethane resin.
Background
The polyurethane is a polymer material prepared by taking a prepolymer containing isocyanate groups and formed by addition polymerization of isocyanate, polyether and the like as a main body and adding fillers and various auxiliary agents, and the main raw materials of the polyurethane comprise hard segments composed of diisocyanate, a small molecule chain extender and a crosslinking agent and soft segments composed of oligomer polyol. The polyurethane has excellent wear resistance, excellent adhesive force and good photo-thermal resistance. Polyurethanes can be classified into solvent-type polyurethane and aqueous polyurethane according to the type of dispersion medium. The solvent type polyurethane takes an organic solvent as a disperse phase, benzene, ketone, cyclic ether and the like are commonly used, and the solvent type polyurethane has environmental pollution and production safety hidden trouble caused by the organic solvent in the production process. The water-based polyurethane takes water as a dispersion medium, the production process is more environment-friendly, safe and easy to control compared with solvent-based polyurethane, the water-based polyurethane becomes a hot spot for polyurethane research, and a large amount of products are gradually applied to various fields instead of solvent-based polyurethane.
However, the aqueous polyurethane has the defects of poor water resistance, solvent resistance, fire resistance, insufficient thermal stability, poor mechanical properties and the like, and the application range of the aqueous polyurethane is limited, so that the performance of the aqueous polyurethane can be regulated and controlled by changing the composition, the proportion, the molecular weight and the like of a soft segment and a hard segment, or the aqueous polyurethane can be modified by adding various synthetic substances in the preparation process of the aqueous polyurethane. At present, the modification method of the water-based polyurethane mainly comprises the following steps: biomass modification, epoxy resin modification, organosilicon modification, acrylate modification, nanomaterial modification, and the like.
However, the aqueous polyurethane resin obtained by the modification method has the problems of poor comprehensive performance, complex modification, high preparation cost and the like, so that the need for developing more aqueous polyurethane resin preparation methods still exists.
Disclosure of Invention
In order to overcome the defect of poor performance of the existing aqueous polyurethane material, the invention provides a preparation method of aqueous polyurethane.
In one aspect of the present invention, the present invention provides a method for preparing an aqueous polyurethane resin, comprising:
reacting dehydrated dihydric alcohol, diisocyanate and a catalyst at 60-90 ℃ to generate prepolymer, and adding a proper amount of organic solvent according to the viscosity condition during the reaction to reduce the viscosity; when the content of isocyanate groups reaches a theoretical value, adding a dry sorbitol, an oxalyl dihydrazide crosslinking agent and a sodium hydroxysulfonate chain extender, continuously reacting for 0.5-4 h, and adding a proper amount of organic solvent in the reaction to control the viscosity of a reaction system; slowly adding deionized water for emulsification under vigorous stirring, standing for defoaming, and then distilling under reduced pressure to remove the organic solvent to obtain aqueous polyurethane resin emulsion;
wherein the diisocyanate is selected from the group consisting of Hexamethylene Diisocyanate (HDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI);
the sodium hydroxysulfonate has a structure represented by the following formula 1:
wherein L is 1 ～L 3 Each independently selected from-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -。
In one embodiment, the glycol is selected from at least one of a small molecule glycol, an oligomeric glycol. Preferably, the small molecule diol is selected from: at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, and ethanolamine; the low polymer dihydric alcohol is at least one selected from polyethylene glycol, polypropylene glycol, polycaprolactone dihydric alcohol and polytetrahydrofuran glycol, the molecular weight of the low polymer dihydric alcohol is 500-3000 g/mol, and the hydroxyl value is 30-100 mgKOH/g; preferably, the molecular weight of the oligomer dihydric alcohol is 800-2500 g/mol, and the hydroxyl value is 40-70 mgKOH/g.
In one embodiment, the molar ratio of Hexamethylene Diisocyanate (HDI) to 4,4' -dicyclohexylmethane diisocyanate (HMDI) is: 1 to 4:1, preferably 1 to 2:1.
in one embodiment, the mass ratio of the dihydric alcohol to the diisocyanate is 2-7: 1, preferably 3 to 6:1, more preferably 4 to 6:1. and, the R value of the reaction system (i.e., the ratio of the molar amount of isocyanate groups n (-NCO) to the molar amount of hydroxyl groups n (-OH)) is controlled to be 1.5 to 3:1, preferably 1.8 to 2.3:1, more preferably 1.8 to 2.2:1.
in one embodiment, the catalyst is not limited and may be selected from conventional catalysts in polyurethane preparation, such as at least one of organobismuth, organotin, organozirconium, or titanate. Preferably, the catalyst may be dibutyltin dilaurate (DBTDL).
In one embodiment, sorbitol is used in an amount of 0.5 to 2.5%, preferably 0.8 to 2.0% of the total mass of diol and diisocyanate.
In one embodiment, the amount of oxalyl dihydrazide is 0.3 to 2.0%, preferably 0.8 to 1.6% of the total mass of diol and diisocyanate.
In one embodiment, L in the sodium hydroxysulfonate represented by the formula 1 1 ～L 3 Are all selected from-CH 2 CH 2 -。
Thus, the sodium hydroxysulfonate is preferably selected from:
in one embodiment, the method for preparing sodium hydroxysulfonate represented by formula 1 comprises:
dissolving the free acid form of the compound of the formula I in ethanol, adding potassium carbonate or cesium carbonate, vigorously stirring to form a suspension, heating the mixture to 50-70 ℃, adding the compound of the formula II in batches, and continuing stirring reaction at the temperature after the addition; then, heating to reflux and stirring for reaction; cooling the reaction mixture to room temperature, removing the solvent by decompression, dissolving with deionized water, regulating the pH to 1-2 with concentrated hydrochloric acid, generating precipitate, filtering, collecting, washing, redissolving in ethanol, dripping sodium hydroxide solution, filtering, collecting the precipitated precipitate, washing, and drying to obtain a product;
wherein L is 1 ～L 3 As defined herein; x is selected from chlorine or bromine.
In one embodiment, the sodium hydroxysulfonate is used in an amount of 1.0 to 4.8%, preferably 1.5 to 4.0%, more preferably 1.8 to 3.6% of the total mass of diol and diisocyanate. If the amount of sodium hydroxysulphonate is increased, the reaction will result in gel formation and no emulsion.
In one embodiment, the reaction temperature to form the prepolymer is from 80 to 85 ℃.
In one embodiment, the organic solvent is selected from at least one of acetone, butanone.
Preferably, the organic solvent is selected from butanone during the formation of the prepolymer; during crosslinking and chain extension, the organic solvent is selected from the group consisting of acetone.
In one embodiment, the reaction time for crosslinking and chain extension is 1 to 3 hours.
In one embodiment, the deionized water is added in an amount such that the solids content of the final emulsion is 40 to 55%, preferably 45 to 53%.
In one embodiment, the temperature of emulsification is from 20 to 40 ℃, preferably at room temperature; the emulsification time is 10 to 90min, preferably 20 to 40min.
In a second aspect of the present invention, there is provided an aqueous polyurethane resin prepared by the above-described preparation method of the present invention.
Preferably, the aqueous polyurethane resin is an aqueous polyurethane resin emulsion.
In a third aspect of the invention, the invention also provides the use of the aqueous polyurethane resin, wherein the aqueous polyurethane resin is used as a paint, an adhesive, a fabric coating and finishing agent, a leather finishing agent, a paper surface treatment agent or a fiber surface treatment agent.
Advantageous effects
The invention provides a preparation method of waterborne polyurethane resin and also provides the waterborne polyurethane resin prepared by the preparation method. The aqueous polyurethane resin emulsion prepared by the preparation method has milky white, uniform and fine appearance, moderate viscosity and good stability; the surface of the aqueous polyurethane adhesive film prepared from the aqueous polyurethane resin emulsion is smooth and flat, the water absorption rate is low, and the aqueous polyurethane adhesive film has excellent water resistance; meanwhile, the alloy also has higher tensile strength and elongation at break, which indicates that the alloy has better mechanical properties. In addition, the preparation method of the aqueous polyurethane resin has the advantages of simple and convenient operation, low cost and less three wastes. Therefore, the preparation method of the aqueous polyurethane resin is an economically feasible production method and is suitable for industrial application.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the present invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications.
Preparation example 1: synthesis of chain extenders
33.8g of 2- ((2-hydroxyethyl) amino) ethane-1-sulfonic acid are dissolved in 500ml of ethanol, 55g of potassium carbonate are added, the mixture is stirred vigorously to form a suspension, the mixture is heated to 60 ℃, 21.0g of 1, 4-bis (2-chloroethyl) piperazine are then added in portions, and stirring is continued at this temperature for 3 hours after the addition; subsequently, the temperature was raised to reflux and stirring was continued for 4h. The reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, then 1L of deionized water was added for dissolution, the pH was adjusted to 1 to 2 with concentrated hydrochloric acid, white precipitate was formed, after filtration and collection, it was again washed 3 times with deionized water, redissolved in ethanol, 1M sodium hydroxide solution was added dropwise, stirring was carried out for 1h, the precipitated precipitate was collected by filtration, washed twice with ethanol, and dried at 60℃to give 46.3g of the product in 89% yield.
IR (KBr pellet): 3396. 2938, 2880, 1490, 1452, 1345, 1186, 1043, 938, 879cm -1 。
Elemental analysis: theoretical value C,36.92; h,6.58; n,10.76; o,24.59; s,12.32; actual measurement value: c,36.97; h,6.61; n,10.72; o,24.51; s,12.38.
1 H NMR(400MHz,D 2 O)δ3.66(t,J＝7.5Hz,4H),3.32(t,J＝7.6Hz,4H),2.90(t,J＝7.6Hz,4H),2.81-2.63(m,20H)。
13 C NMR(100MHz,D 2 O)δ59.81,57.21,55.27,53.58,52.89,51.83,50.97。
Example 1:
weighing a certain amount of polycaprolactone diol PCL-220N (molecular weight 2000, hydroxyl value 57+/-2 mgKOH/g, the same applies below) which is dehydrated in advance, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein the amounts of the components are as follows (amounts of crosslinking agent and chain extender are the same as below based on the total mass of diol and diisocyanate):
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 1.8%
Example 2:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:12.6g
4,4' -dicyclohexylmethane diisocyanate HMDI:19.7g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 1.8%
Comparative example 1:
weighing a certain amount of PCL-220N and hexamethylene diisocyanate HDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyl tin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain yellowish aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:25.2g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 1.8%
Comparative example 2:
weighing a certain amount of PCL-220N, 4' -dicyclohexylmethane diisocyanate HMDI which is dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyl tin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring for emulsification for 30min, standing for defoaming, and then distilling under reduced pressure to remove the organic solvent, thus obtaining yellowish aqueous polyurethane resin emulsion with a small amount of precipitation. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
4,4' -dicyclohexylmethane diisocyanate HMDI:39.3g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 1.8%
Example 3:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.5%
Oxalyl hydrazide: 1.2%
Chain extender: 1.8%
Example 4:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 2.0%
Oxalyl hydrazide: 0.8%
Chain extender: 1.8%
Comparative example 3:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding the chain extender prepared in the preparation example 1 after the theoretical value is reached, continuing to react for 2 hours, and adding a proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring for emulsification for 30min, standing for defoaming, and then distilling under reduced pressure to remove the organic solvent, thereby obtaining the milky aqueous polyurethane resin emulsion with a small amount of precipitation. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Chain extender: 1.8%
Comparative example 4:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol cross-linking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 2.7%
Chain extender: 1.8%
Comparative example 5:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the theoretical value is reached, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain yellowish aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Oxalyl hydrazide: 2.7%
Chain extender: 1.8%
Example 5:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 2.5%
Example 6:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 3.4%
Comparative example 6:
weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and the chain extender prepared in preparation example 1 after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain polyurethane gel.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 5.5%
Comparative example 7: preparation of polyurethane emulsion
Weighing a certain amount of PCL-220N, hexamethylene diisocyanate HDI and 4,4' -dicyclohexylmethane diisocyanate HMDI which are dehydrated in advance, adding into a reactor, adding 2-3 drops of dibutyltin dilaurate DBTDL catalyst, reacting for 1.5 hours at 80-85 ℃, and adding a proper amount of butanone solvent according to the viscosity condition during the reaction to reduce the viscosity; determining the content of isocyanate groups by adopting a di-n-butylamine method, adding a dried sorbitol and oxalyl dihydrazide crosslinking agent and a 2- (bis (2-hydroxyethyl) amino) ethane-1-sodium sulfonate chain extender after the content reaches a theoretical value, continuing to react for 2 hours, and adding proper amount of acetone in the reaction to control the viscosity of a reaction system; slowly adding deionized water (with the final solid content of 50%) under vigorous stirring, emulsifying for 30min, standing for defoaming, and distilling under reduced pressure to remove the organic solvent to obtain milky aqueous polyurethane resin emulsion. And (3) forming a film on the prepared aqueous polyurethane resin emulsion at room temperature by using a tape casting method, naturally drying for 1 day, and then drying in a baking oven at 40 ℃ until the weight is constant.
Wherein, the dosage of each component is as follows:
polycaprolactone diol PCL-220N:150g
Hexamethylene diisocyanate HDI:16.8g
4,4' -dicyclohexylmethane diisocyanate HMDI:13.1g
R value: 2.0
Sorbitol: 1.2%
Oxalyl hydrazide: 1.5%
Chain extender: 1.8%
Performance measurement:
1. appearance of emulsion
The sample was placed in a transparent container and visually inspected for emulsion color, transparency, flocculation or sedimentation.
2. Emulsion stability test
(1) Mechanical stability test
Storage stability was simulated by a centrifugal acceleration sedimentation test, with reference to GB/T11175-2002 method for testing synthetic resin emulsions. Taking 10mL of sample emulsion in a centrifuge tube, centrifuging for 15min at a speed of 3000r/min by a high-speed centrifuge at room temperature, taking out, observing whether the emulsion in the centrifuge tube has layering or precipitation, and if no obvious layering or precipitation exists, considering that the emulsion can be stably stored for 6 months.
(2) Dilution stability test
Referring to GB/T11175-2002 test method for synthetic resin emulsion, diluting the emulsion to be tested to 3% of solid content, standing for 72h at room temperature, observing whether layering or precipitation exists in the period, and if no obvious layering or precipitation exists, considering that the emulsion has good dilution stability.
3. Emulsion viscosity test
The viscosity of the emulsion of the sample was measured at 60r/min on a model NDJ-5S viscometer at room temperature, and the sample was read after stabilization, and each sample was tested 3 times in parallel.
4. Water absorption rate test for adhesive film
Cutting the dried aqueous polyurethane adhesive film into sample pieces with the size of 20mm multiplied by 20mm, and weighing the mass m 1 Then placing the film sample into 50mL deionized water, soaking for 24h at room temperature, and sucking the water on the surface of the film with filter paper to obtain a film sample with a mass of m 2 The water absorption p of the film was calculated according to the following formula:
p＝(m 2 -m 1 )/m 1 ×100％
5. mechanical property test of adhesive film
Referring to national standard GB/T1040.1-2018 "determination of Plastic tensile Property", a film was cut into 75mm by 10mm strips, and the tensile strength and elongation at break of the strips were tested at a tensile speed of 100mm/min using a universal tensile tester, 3 strips per group were tested in parallel, and the average value was taken.
The results are reported in table 1 below:
table 1:
as shown in table 1 above, the aqueous polyurethane resin emulsion of the present invention is finer in appearance, has an appropriate viscosity range, and has very outstanding mechanical stability and dilution stability, as compared with the emulsions of comparative examples 1 to 7; meanwhile, the polyurethane adhesive film prepared from the aqueous polyurethane resin emulsion has smooth and flat surface and good film forming property; the water absorption is remarkably lower, which indicates that the paint has better water resistance; meanwhile, the alloy also has higher tensile strength and elongation at break, and thus has better mechanical properties.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. A preparation method of aqueous polyurethane resin comprises the following steps:
reacting dehydrated dihydric alcohol, diisocyanate and a catalyst at 60-90 ℃ to generate prepolymer, and adding a proper amount of organic solvent according to the viscosity condition during the reaction to reduce the viscosity; when the content of isocyanate groups reaches a theoretical value, adding a dry sorbitol, an oxalyl dihydrazide crosslinking agent and a sodium hydroxysulfonate chain extender, continuously reacting for 0.5-4 h, and adding a proper amount of organic solvent in the reaction to control the viscosity of a reaction system; slowly adding deionized water for emulsification under vigorous stirring, standing for defoaming, and then distilling under reduced pressure to remove the organic solvent to obtain aqueous polyurethane resin emulsion;
wherein the diisocyanate is selected from the group consisting of Hexamethylene Diisocyanate (HDI) and 4,4 '-dicyclohexylmethane diisocyanate (HMDI), the molar ratio of Hexamethylene Diisocyanate (HDI) to 4,4' -dicyclohexylmethane diisocyanate (HMDI) being: 1 to 4:1, a step of;
the sodium hydroxysulfonate has a structure represented by the following formula 1:
wherein L is 1 ～L 3 Each independently selected from-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -；
The dihydric alcohol is selected from oligomer dihydric alcohol; the low polymer dihydric alcohol is at least one selected from polyethylene glycol, polypropylene glycol, polycaprolactone dihydric alcohol and polytetrahydrofuran glycol, the molecular weight of the low polymer dihydric alcohol is 500-3000 g/mol, and the hydroxyl value is 30-100 mgKOH/g;
the mass and use ratio of the dihydric alcohol to the diisocyanate is 2-7: 1, a step of; and, the R value of the reaction system is controlled to=1.5 to 3:1, a step of;
the consumption of sorbitol is 0.5-2.5% of the total mass of dihydric alcohol and diisocyanate; the consumption of the oxalyl dihydrazide is 0.3-2.0% of the total mass of the dihydric alcohol and the diisocyanate;
the dosage of the sodium hydroxysulfonate is 1.5 to 3.6 percent of the total mass of the dihydric alcohol and the diisocyanate.
2. The process according to claim 1, wherein the molar ratio of Hexamethylene Diisocyanate (HDI) to 4,4' -dicyclohexylmethane diisocyanate (HMDI) is: 1-2: 1.
3. the method according to claim 1, wherein the R value of the reaction system is controlled to be 1.8 to 2.3:1.
4. the method according to claim 1, wherein the R value of the reaction system is controlled to be 1.8 to 2.2:1.
5. the preparation method according to claim 1, wherein the amount of sorbitol is 0.8 to 2.0% of the total mass of the diol and the diisocyanate; the consumption of the oxalyl dihydrazide is 0.8-1.6% of the total mass of the dihydric alcohol and the diisocyanate.
6. The method of preparation of claim 1, wherein the sodium hydroxysulfonate is selected from the group consisting of:
7. the preparation method according to claim 1, wherein the preparation method of sodium hydroxysulfonate represented by formula 1 comprises:
dissolving the free acid of the compound of the formula I in ethanol, adding potassium carbonate or cesium carbonate, vigorously stirring to form a suspension, heating the mixture to 50-70 ℃, adding the compound of the formula II in batches, and continuing stirring reaction at the temperature after adding; then, heating to reflux and stirring for reaction; cooling the reaction mixture to room temperature, removing the solvent by decompression, dissolving with deionized water, regulating the pH to 1-2 with concentrated hydrochloric acid, generating precipitate, filtering, collecting, washing, redissolving in ethanol, dripping sodium hydroxide solution, filtering, collecting the precipitated precipitate, washing, and drying to obtain a product;
wherein L is 1 ～L 3 As defined in claim 1; x is selected from chlorine or bromine.
8. The preparation method according to claim 1, wherein the amount of the sodium hydroxysulfonate is 1.8 to 3.6% of the total mass of the diol and the diisocyanate.
9. An aqueous polyurethane resin prepared by the preparation method according to any one of claims 1 to 7.
10. The use of the aqueous polyurethane resin according to claim 9, wherein the aqueous polyurethane resin is used as a paint, an adhesive, a fabric coating and finishing agent, a leather finishing agent, a paper surface treatment agent or a fiber surface treatment agent.
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