CN111662423A - Preparation method of hydroxyl functionalized waterborne polyurethane - Google Patents

Preparation method of hydroxyl functionalized waterborne polyurethane Download PDF

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Publication number
CN111662423A
CN111662423A CN202010548808.9A CN202010548808A CN111662423A CN 111662423 A CN111662423 A CN 111662423A CN 202010548808 A CN202010548808 A CN 202010548808A CN 111662423 A CN111662423 A CN 111662423A
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China
Prior art keywords
waterborne polyurethane
hydroxyl
reaction
glycol
carboxyl
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CN202010548808.9A
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Chinese (zh)
Inventor
王军威
李晓云
亢茂青
李其峰
赵雨花
梁辰
冯月兰
殷宁
张清运
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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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Priority to CN202010548808.9A priority Critical patent/CN111662423A/en
Publication of CN111662423A publication Critical patent/CN111662423A/en
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Abstract

The invention belongs to the technical field of preparation methods and applications of waterborne polyurethane, and particularly relates to a preparation method of hydroxyl functionalized waterborne polyurethane. Dehydrating a polyol polymer and a carboxyl-containing hydrophilic agent, adding the dehydrated polyol polymer and the carboxyl-containing hydrophilic agent into a reactor, uniformly stirring, adding an isocyanate compound, and reacting to obtain a waterborne polyurethane prepolymer; then adding micromolecular dihydric alcohol and a solvent into the waterborne polyurethane prepolymer for continuous reaction, and cooling to room temperature; and finally, adding a salt forming agent into the reaction product, stirring at room temperature for reaction, then dropwise adding deionized water for emulsification, then adding a chain extender and a hydroxyl functional monomer, strongly stirring and heating for reaction. And after the reaction is finished, removing the solvent through reduced pressure distillation to obtain the hydroxyl functional waterborne polyurethane. The invention is environment-friendly, nontoxic and high in economy, and the hydroxyl functional monomer is introduced into the waterborne polyurethane, so that the hydrogen bond function in a polyurethane system can be improved by utilizing the hydroxyl; hydroxyl as an active group can react with other compounds to modify the waterborne polyurethane through crosslinking, grafting and the like.

Description

Preparation method of hydroxyl functionalized waterborne polyurethane
Technical Field
The invention belongs to the technical field of preparation methods and applications of waterborne polyurethane, and particularly relates to a preparation method of hydroxyl functionalized waterborne polyurethane.
Background
Polyurethanes are polymers containing repeated carbamate groups (-NHCOO-) in the molecular structure, are generally produced by polyaddition of polyols, isocyanate compounds and small molecular chain extenders, and are widely used as coatings, adhesives, foams, fibers and the like due to excellent comprehensive properties. Currently, most of polyurethane coatings and adhesives applied in a large number are solvent-based, but due to the high toxicity of organic solvents, adverse effects on the health of personnel and the environmental safety can be brought in the production and product application processes; on the other hand, the use of organic solvent will cause the product cost to rise, which is not favorable for its application and popularization. In recent years, with the increasing strictness of environmental regulations, aqueous polyurethanes using water as a dispersion medium have been regarded as important because of their low VOC emission, non-toxicity and non-flammability.
Aqueous polyurethanes can be classified into ionic and nonionic types according to their structure, with ionic aqueous polyurethanes being more commonly used. Along with the continuous expansion of the application field of the waterborne polyurethane, the requirements on the performance of the waterborne polyurethane are higher and higher. In order to better improve the comprehensive performance of the waterborne polyurethane and meet the application requirements, the functionalized waterborne polyurethane becomes a research hotspot in recent years, and the exploration for the functionalized waterborne polyurethane at home and abroad mainly comprises several aspects of molecular structure functionalization, copolymerization functionalization, blending functionalization and the like.
GE and the like react with modified hydrophilic diisocyanate to prepare the organic silicon functional two-component waterborne polyurethane by utilizing the hydroxy-terminated polydimethylsiloxane, and the obtained polyurethane has good thermal stability and remarkably improved heat resistance due to the introduction of a Si-O-Si cross-linked network structure. (Ge Zhen, Luo Yunjun, progress in Organic Coatings,2013,76(11):1522-
MA and the like firstly use polypropylene carbonate as a soft segment to synthesize a waterborne polyurethane precursor, and then combine a polyacrylate monomer with the waterborne polyurethane precursor to prepare the acrylate functionalized waterborne polyurethane, so that the adhesive force, pencil hardness, water resistance and thermal property of the polyurethane film are obviously improved. (Ma Le, Song Lina, Li Fang, et al, colloid & Polymer science,2017,295(12):2299-
A functional water-base polyurethane as nano material is a new functional method by mixing, and the nano material mainly contains (1) nano mineral clay including montmorillonite and nano SiO2Attapulgite, and the like; (2) nano carbon materials mainly including graphene, carbon nanotubes, carbon black and the like; (3) the nanometer metal oxide material comprises nanometer ZnO and nanometer Fe3O4TiO 2 nanoparticles2Nano silver, etc. DU, etc. prepares the carbon black modified by sodium poly-4-styrene sulfonate and reacts with water under the condition that the pH value is 5And (3) preparing the nano carbon black functionalized waterborne polyurethane by polyurethane emulsion polymerization. The influence of the carbon black dosage on the structure and the performance of the nano carbon black functionalized waterborne polyurethane is discussed, the physical and chemical properties of the hybrid membrane are researched by SEM and the like, and the experimental result shows that the carbon black has good dispersibility in the waterborne polyurethane emulsion, and the thermal stability and the mechanical property of the nano carbon black functionalized waterborne polyurethane are obviously improved compared with the pure waterborne polyurethane. (Di Yufan, Shi Pengwei, Li Qiaying, et al.colloids and surfaces: physiochemical and engineering products, 2014,454:1-7.)
At present, researches on functionalized waterborne polyurethane mainly focus on enhancing and toughening, improving heat resistance and water resistance, and endowing materials with electric, optical, magnetic and other properties, and a plurality of methods are reported, but in order to improve crosslinking degree and mechanical properties during polyurethane preparation, an excessive isocyanate method is mostly adopted, the hydroxyl content in the whole system is very low or even no hydroxyl is contained, and few reports on hydroxyl functionalized waterborne polyurethane exist. The invention aims to provide a preparation method of hydroxyl functional waterborne polyurethane through the reaction of a hydroxyl functional monomer and different raw material systems, on one hand, the hydroxyl can be utilized to improve the hydrogen bond effect in a polyurethane system, and further improve the cohesion, the impermeability, the water resistance, the adhesive property and the like of the waterborne polyurethane; on the other hand, hydroxyl as an active group can further participate in the reaction to facilitate the modification of the waterborne polyurethane.
Disclosure of Invention
The object of the present invention is to provide hydroxyl-functionalized aqueous polyurethanes, the hydroxyl groups being capable of imparting new properties to the aqueous polyurethane, and furthermore the reactive groups hydroxyl groups being capable of reacting with other compounds such as: urea-formaldehyde resins, melamine-formaldehyde resins, dialdehydes (glyoxal, glutaraldehyde) and inorganic salts such as: boride (boric acid and sodium borate) and inorganic substances containing titanium, zirconium, vanadium, chromium and the like are subjected to crosslinking reaction to further modify the polyurethane.
In order to achieve the purpose, the invention adopts the following technical scheme: hydroxyl functional waterborne polyurethane is prepared by introducing a hydroxyl functional monomer, and the functional hydroxyl groups are used for endowing the waterborne polyurethane with new performance and reaction activity:
a preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, dehydrating polymer polyol and a carboxyl-containing hydrophilic agent, adding the dehydrated polymer polyol and the carboxyl-containing hydrophilic agent into a reactor, uniformly stirring the dehydrated polymer polyol and the carboxyl-containing hydrophilic agent, adding an isocyanate compound into the reactor, and reacting the mixture to obtain a waterborne polyurethane prepolymer;
step 2, adding micromolecular dihydric alcohol and a solvent into the waterborne polyurethane prepolymer, continuing to react, and cooling to room temperature;
and 3, adding a salt forming agent into the reaction system obtained in the step 2, stirring at room temperature for reaction, adding deionized water for emulsification, adding a chain extender and a hydroxyl functional monomer, heating for reaction after strong stirring, and removing the solvent through reduced pressure distillation after the reaction is finished to obtain the hydroxyl functional waterborne polyurethane.
Because the polyurethane is a block polymer with soft and hard segments which are connected with each other, the hard segment in the molecular structure of the hydroxyl functional waterborne polyurethane mainly comprises an isocyanate compound, a chain extender and a hydroxyl functional monomer, the soft segment comprises polymer polyol, and the molecular structures, the crosslinking degree and the like of the hard segment and the soft segment have obvious influence on the performance of the waterborne polyurethane. Therefore, the structure, the molecular weight and the proportion of the polymer polyol, the isocyanate, the chain extender and the hydroxyl functional monomer can be adjusted, so that the structure of the waterborne polyurethane can be adjusted, and different properties of the waterborne polyurethane material can be endowed to meet various application requirements.
Further, in the step 1, the polymer polyol is one or more of polyester diol, polyether diol or polycarbonate diol, and is mixed according to any ratio. The crystallinity of the polyester diol is good, and the obtained waterborne polyurethane has high bonding strength and tensile strength; the polyether glycol ether bond cohesive energy is lower, the rotation is easy, and the flexibility and the hydrolysis resistance of the obtained waterborne polyurethane are high; the polycarbonate diol contains carbonate groups, so that the cohesive energy is high, and the obtained waterborne polyurethane has good mechanical strength and oil resistance; the mixing of polymer polyols with different structures has different influences on the structure and the performance of the waterborne polyurethane.
The polyester diol is one or more of polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol-neopentyl glycol adipate and poly-caprolactone diol which are mixed according to any ratio, and the polyester diols with different structures have different influences on the structure and the performance of the waterborne polyurethane;
the polyether glycol is one or a mixture of more of polypropylene oxide glycol, polyethylene glycol ether, polypropylene glycol ether, polytetramethylene ether glycol, polyethylene oxide glycol, polybutadiene polyol and the like according to any ratio, and polyether glycols with different structures have different influences on the structure and the performance of the waterborne polyurethane;
the polycarbonate diol is one or a mixture of more of poly (hexamethylene carbonate), poly (pentylene carbonate) and poly (butylene carbonate) in any ratio, and the polycarbonate diols with different structures have different influences on the structure and the performance of the waterborne polyurethane.
Further, the molecular weight of the polyester diol, polyether diol or polycarbonate diol is optimized to be 1000-2000. The molecular weight of the polymer polyol is too high, the content of the soft segment of the obtained waterborne polyurethane is more, and the tensile strength is poorer; the molecular weight is low, and the obtained waterborne polyurethane is relatively brittle and has poor elongation.
Further, in the step 1, the carboxyl-containing hydrophilic agent is one or more of 2, 2-dimethylolpropionic acid, dihydroxy half ester and diaminobenzoic acid which are mixed according to any ratio, and carboxyl is used as a hydrophilic group to improve the dispersibility of the aqueous polyurethane in water.
Further, in the step 1, the isocyanate compound is one or more of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylene bis (cyclohexyl isocyanate) and m-tetramethylene xylene diisocyanate, and the isocyanate compounds with different structures have different influences on the structure and the performance of the waterborne polyurethane.
Further, in the step 2, the small molecule dihydric alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol and diethylene glycol, and the small molecule dihydric alcohol can increase the content of the hard segment of the waterborne polyurethane and change the structure and the performance of the waterborne polyurethane.
Furthermore, in the step 2, the solvent is one or more of acetone, butanone, N-dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone and ethylene glycol monobutyl ether which are mixed according to any ratio, and the solvent is favorable for reducing the viscosity of the waterborne polyurethane so as to increase the dispersing performance of the waterborne polyurethane.
Further, in the step 3, a salt forming agent is one or more of triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water which are mixed according to any ratio, and the salt forming agent is used for neutralizing the hydrophilic agent so as to further increase the stability of the aqueous polyurethane emulsion.
Further, in the step 3, the chain extender is one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol and N, N-bis (2-hydroxyethyl) ethylenediamine, and the chain extenders with different structures have different influences on the structure and performance of the waterborne polyurethane.
Further, the hydroxyl functional monomer in step 3 is one or more of polyhydroxy polyamine alcohol amine compound or polyhydroxy compound containing hydroxyl and primary amino in the structure, and the structural general formula is as follows:
Figure BDA0002541700720000051
the hydroxyl functional monomer can participate in the chain extension reaction of the waterborne polyurethane prepolymer and be connected to the main chain of the waterborne polyurethane molecule, and can provide functional group hydroxyl so as to change the performance and the reaction activity of the waterborne polyurethane.
Further, the polyhydroxy polyamine alcohol amine compound or polyhydroxy compound containing hydroxyl and primary amine in the structure is one or more of 2-hydroxy-1, 3-propane diamine, 3' -dihydroxy benzidine, tetrahydroxy adipamide, 1, 6-dihydro-1-hydroxy-pyrrolo [2,3-b ] pyrrole-2, 3-diamine, glycerol, or cyclic carbonate and excessive amine to generate polyhydroxy polyamine alcohol amine compound containing beta-hydroxyl, urethane and amine groups by ring-opening reaction.
The ring-opening reaction is as follows:
Figure BDA0002541700720000061
hydroxyl functional monomers with different structures have different influences on the structure and the performance of the waterborne polyurethane.
Further, in the step 1, the molar ratio of the polymer polyol to the carboxyl-containing hydrophilic agent is 0.5-2: 1, and the molar ratio of the isocyanate compound to the total molar number of the polymer polyol and the carboxyl-containing hydrophilic agent is 1.8-3.5: 1. The proportion of the soft and hard sections of the obtained waterborne polyurethane is proper, a certain degree of microphase separation exists between the hard sections, and the obtained waterborne polyurethane adhesive film has good performances such as tensile strength, elongation at break, water resistance, bonding strength and the like.
Further, the amount of the small molecular diol used in the step 2 is 0.6-0.8 times of the molar amount of the excessive isocyanate compound in the step 1; the solvent accounts for 15 to 30 percent of the total mass of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol. The hard segment of the obtained waterborne polyurethane is increased, and the performance is improved; the viscosity is moderate, and the dispersion in water is facilitated.
Further, the molar ratio of the using amount of the salt forming agent in the step 3 to the carboxyl-containing hydrophilic agent is 1: 1; the dosage of the deionized water is calculated according to the solid content, and the solid content is controlled to be 20-45 percent; the total usage amount of the chain extender and the hydroxyl functional monomer is the same as the mole number of the residual isocyanate groups after the reaction in the step, wherein the mole ratio of the chain extender to the hydroxyl functional monomer is 0-99: 100-1. The excessive use amount of the salt forming agent can catalyze side reactions in the film forming process of the waterborne polyurethane, so that the activation period and the appearance of a glue film are influenced, and the poor stability of the obtained waterborne polyurethane emulsion is caused by the excessive use amount of the salt forming agent.
Further, the dehydration condition of the polymer polyol in the step 1 is that the polymer polyol is dehydrated for 2-4 hours at the temperature of 100-140 ℃ under reduced pressure, and the dehydration condition of the carboxyl-containing hydrophilic agent is that the polymer polyol is dried in a drying oven at the temperature of 100-140 ℃ for 10-14 hours; the reaction temperature is 70-95 ℃, and the reaction time is 2-5 h.
Further, the temperature for the continuous reaction in the step 2 is 50-65 ℃ and the time is 2-5 h.
Further, in the step 3, the stirring reaction time at room temperature is 0.5-1 h, the intensive stirring reaction time is 0.1-0.5 h, the heating reaction temperature is 40-55 ℃, and the heating reaction time is 0.5-1 h.
The aqueous polyurethane material obtained was tested according to the following criteria.
Performance test standard:
(1) water and solvent resistance test
Soaking the prepared polyurethane material in deionized water at 25 ℃, weighing the mass change condition of the sample, and calculating the swelling degree of the sample according to the following formula when the sample is constant in weight:
Figure BDA0002541700720000071
s represents the degree of swelling, m0Denotes the initial mass, m1Is the weight that reaches a constant weight after swelling.
(2) Mechanical Properties
Dumbbell-shaped specimens were prepared and tested as specified in standard GB1039-92, tensile strength being in accordance with GB/T528-1998 and elongation at break being in accordance with GB528-82, under the following test conditions: room temperature 25 ℃ and humidity 55%.
(3) Adhesive property
The adhesive strength is tested according to the national standard GB/T2791-1995, and the test conditions are as follows: room temperature 25 ℃ and humidity 55%.
(4) Storage stability
And (3) placing the aqueous polyurethane emulsion in a sealed container at room temperature, observing the change of the dispersion liquid, and obtaining the product with good storage stability without layering and solidification.
Compared with the prior art, the invention has the following advantages:
1. obtaining novel functional waterborne polyurethane, namely hydroxyl functional waterborne polyurethane, and improving the cohesion, the impermeability, the water resistance, the bonding property and the like of the waterborne polyurethane;
2. the obtained hydroxyl functionalized waterborne polyurethane contains active group hydroxyl, and can further generate crosslinking reaction with other compounds to modify the waterborne polyurethane;
3. the preparation process is simple, the operation is easy, and the storage stability of the product is good.
Detailed Description
Example 1
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, performing reduced pressure dehydration on 10g of polybutylene adipate (Mn is 1000) at 140 ℃ for 2h, drying 0.67g of dimethylolpropionic acid in a drying oven at 140 ℃ for 10h, dehydrating, adding into a reactor, uniformly stirring, adding 4.70g of toluene diisocyanate, and reacting at 70 ℃ for 4h to obtain an aqueous polyurethane prepolymer, wherein the excessive toluene diisocyanate is 2.09 g;
step 2, adding 1, 4-butanediol and 15% acetone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 3.5h at 50 ℃, and cooling to room temperature;
and 3, adding 0.51g of triethylamine into the reaction product to neutralize dimethylolpropionic acid, stirring at room temperature for 0.5h, dropwise adding deionized water according to the solid content of 20% to emulsify, then adding 0.43g of hydroxyl functional monomer 2-hydroxy-1, 3-propane diamine, stirring strongly for 6min, and heating to 40 ℃ to react for 1 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 29.5MPa, the elongation at break is 565 percent, the swelling degree after the glue film is soaked in water to reach the swelling balance is 12.03 percent, and the 24-hour final adhesive strength to a base material PVC is 2.75N/mm.
Example 2
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, dehydrating 20g of polytetramethylene ether glycol (Mn ═ 2000) under reduced pressure at 100 ℃ for 4h, drying 1.52g of diaminobenzoic acid in a drying oven at 100 ℃ for 14h, dehydrating, adding into a reactor, stirring uniformly, adding 15.54g of isophorone diisocyanate, and reacting at 75 ℃ for 3.5h to obtain a waterborne polyurethane prepolymer, wherein the excessive isophorone diisocyanate is 11.10 g;
2, adding 2.48g of ethylene glycol and 30% of solvent butanone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 2.5h at 55 ℃, and then cooling to room temperature;
and 3, adding 1.43g of tripropylamine to the reaction product to neutralize diaminobenzoic acid, stirring at room temperature for 0.6h, dropwise adding deionized water according to the solid content of 45% for emulsification, then adding 0.30g of chain extender propylene glycol and 1.30g of hydroxyl functional monomer 3, 3' -dihydroxybenzidine, stirring strongly for 30min, and heating to 50 ℃ for reaction for 0.7 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 25.0MPa, the elongation at break is 756%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 11.25%, and the 24-hour final adhesion strength to a base material PVC is 2.68N/mm.
Example 3
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, performing reduced pressure dehydration on 15g of poly (hexamethylene carbonate) (Mn is 1500) at 120 ℃ for 3h, drying 0.94g of dimethylolpropionic acid in a drying oven at 120 ℃ for 12h, dehydrating, adding into a reactor, stirring uniformly, adding 10.63g of diphenylmethane diisocyanate, and reacting at 80 ℃ for 2.5h to obtain an aqueous polyurethane prepolymer, wherein the excessive diphenylmethane diisocyanate is 6.38 g;
step 2, adding 1.36g of 1, 2-propylene glycol and 21 percent of solvent ethylene glycol monobutyl ether (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecule dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 2 hours at 65 ℃, and cooling to room temperature;
and 3, adding 1.30g of tributylamine into the reaction product to neutralize dimethylolpropionic acid, stirring for 1 hour at room temperature, dropwise adding deionized water according to the solid content of 35% to emulsify, then adding 0.32g of chain extender glycol, 0.55g of hydroxy functional monomer 3, 3' -dihydroxybenzidine and 1.08g of 2-hydroxy-1, 3-propane diamine, stirring strongly for 10 minutes, and heating to 55 ℃ to react for 0.5 hour. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 30.2MPa, the elongation at break is 555 percent, the swelling degree after the glue film is soaked in water to reach the swelling balance is 13.79 percent, and the 24-hour final adhesive strength to a base material PVC is 3.05N/mm.
Example 4
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
10g of poly-caprolactone diol (Mn is 1000) is dehydrated under reduced pressure at 115 ℃ for 3.1h, 0.91g of diaminobenzoic acid is dried in a drying oven at 125 ℃ for 11.6h and then added into a reactor, after uniform stirring, 4.2g of hexamethylene diisocyanate and 5.11g of isophorone diisocyanate are added, and the mixture reacts at 95 ℃ for 2h to obtain an aqueous polyurethane prepolymer, wherein the total amount of the excessive hexamethylene diisocyanate and the isophorone diisocyanate is 0.032 mol;
2, adding 2.16g of neopentyl glycol and 25% of solvent N, N-dimethylformamide (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 4 hours at 55 ℃, and then cooling to room temperature;
and 3, adding 0.41mL of ammonia water into the reaction product to neutralize diaminobenzoic acid, stirring at room temperature for 0.7h, dropwise adding deionized water according to the solid content of 26% for emulsification, then adding 0.30g of chain extender diethylene glycol, 0.17g of ethylenediamine, 2.30g of hydroxyl functional monomer ethylene glycol diglycidyl ether cyclic carbonate and excessive propylenediamine aminolysis product, stirring strongly for 15min, and heating to 45 ℃ for reaction for 0.61 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 28.9MPa, the elongation at break is 658%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 13.25%, and the 24-hour final adhesion strength to the base material PVC is 2.86N/mm.
Example 5
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 5g of polybutylene adipate (Mn 1000) and 5g of polyhexamethylene carbonate (Mn 1000) are dehydrated under reduced pressure at 107 ℃ for 3.9h, 0.61g of diaminobenzoic acid and 0.54g of dimethylolpropionic acid are dried in a drying oven at 118 ℃ for 10.9h, the dehydrated products are added into a reactor, 6.26g of toluene diisocyanate is added after uniform stirring, and the reaction is carried out at 90 ℃ for 2.1h to obtain an aqueous polyurethane prepolymer, wherein the excessive toluene diisocyanate is 3.13 g;
step 2, adding 1.16g of diethylene glycol, 12 percent of solvent acetone and 10 percent of butanone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuing to react for 2 hours at 65 ℃, and cooling to room temperature;
and 3, adding 0.81g of triethylamine to the reaction product to neutralize diaminobenzoic acid and dimethylolpropionic acid, stirring for 1h at room temperature, dropwise adding deionized water according to the solid content of 32% to emulsify, then adding 0.41g of chain extender 1, 6-hexanediol, 1.44g of hydroxyl functional monomer 1, 4-butanediol diglycidyl ether cyclic carbonate and excessive ethylenediamine aminolysis product, stirring vigorously for 27min, and heating to 55 ℃ to react for 0.7 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 29.5MPa, the elongation at break is 602%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 12.98%, and the 24-hour final adhesion strength to a base material PVC is 2.92N/mm.
Example 6
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 10g of polybutylene adipate (Mn is 1000) is dehydrated under reduced pressure at 135 ℃ for 2h, 1g of dihydroxy half-ester is dried in a drying oven at 100 ℃ for 12h and then is added into a reactor, 25.15g of 4,4 '-methylene bis (cyclohexyl isocyanate) is added after uniform stirring, and the mixture reacts at 85 ℃ for 2.7h to obtain an aqueous polyurethane prepolymer, wherein 17.29g of excessive 4, 4' -methylene bis (cyclohexyl isocyanate) is added;
step 2, adding 1.8g of 1, 4-butanediol, 1.22g of ethylene glycol and 18% of solvent acetone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 2.8h at 56 ℃, and then cooling to room temperature;
and 3, adding 1.52g of triethylamine and 0.34mL of ammonia water into the reaction product to neutralize the dihydroxy half ester, stirring at room temperature for 0.8h, dropwise adding deionized water according to the solid content of 35% to emulsify, then adding 1.34g of chain extender diethylenetriamine and 4.29g of hydroxyl functional monomer tetrahydroxy adipamide, stirring vigorously for 9min, and heating to 55 ℃ to react for 0.8 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 29.6MPa, the elongation at break is 587%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 13.56%, and the 24-hour final adhesive strength to a base material PVC is 2.99N/mm.
Example 7
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 4g of polytetramethylene ether glycol (Mn ═ 2000), 3g of polypropylene glycol ether (Mn ═ 1000) and 5g of polyoxypropylene glycol (Mn ═ 1000) are dehydrated under reduced pressure at 126 ℃ for 3h, 1.11g of dimethylolpropionic acid is dried in a drying oven at 131 ℃ for 10.8h and then added into a reactor, 10.16g of isophorone diisocyanate is added after uniform stirring, and the reaction is carried out at 70 ℃ for 5h to obtain an aqueous polyurethane prepolymer, wherein the excess isophorone diisocyanate is 6.09 g;
step 2, adding 1.71g of neopentyl glycol and 28.2% of methyl ethyl ketone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 5 hours at 50 ℃, and then cooling to room temperature;
and 3, adding 0.33g of sodium hydroxide into the reaction product to neutralize dimethylolpropionic acid, stirring at room temperature for 0.65h, dropwise adding deionized water according to the solid content of 31.8% to emulsify, then adding 0.12g of chain extender ethylenediamine, 0.10g of diethylenetriamine and 0.72g of hydroxyl functional monomer 2-hydroxy-1, 3-propanediamine, stirring strongly for 12min, and heating to 42 ℃ to react for 0.99 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 26.1MPa, the elongation at break is 721%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 12.51%, and the 24-hour final adhesive strength to a base material PVC is 2.72N/mm.
Example 8
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 10.5g of poly (hexamethylene carbonate) (Mn is 1500) and 3g of polytetramethylene ether glycol (Mn is 1000) are dehydrated under reduced pressure at 103 ℃ for 3.6h, 1.14g of diaminobenzoic acid is dried in a drying oven at 128 ℃ for 12.3h and then added into a reactor, 7.84g of p-phenylene diisocyanate is added after uniform stirring, and the mixture reacts at 79 ℃ for 4.5h to obtain an aqueous polyurethane prepolymer, wherein 5.04g of excessive p-phenylene diisocyanate;
step 2, adding 2.60g of 1, 6-hexanediol and 19.3% acetone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 4.6h at 53 ℃, and then cooling to room temperature;
and 3, adding 0.76g of triethylamine into the reaction product to neutralize diaminobenzoic acid, stirring at room temperature for 0.75h, dropwise adding deionized water according to the solid content of 31.8% to emulsify, then adding 0.20g of chain extender ethylene glycol, 0.32g of diethylene glycol and 0.30g of hydroxyl functional monomer 2-hydroxy-1, 3-propane diamine, stirring strongly for 13.6min, and heating to 53 ℃ to react for 0.75 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 27.6MPa, the elongation at break is 626%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 12.96%, and the 24-hour final adhesive strength to a base material PVC is 2.89N/mm.
Example 9
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 10g of polybutylene carbonate (Mn ═ 1000) is dehydrated under reduced pressure at 113 ℃ for 3.2h, 0.85g of dihydroxy half-ester is dried in a drying oven at 108 ℃ for 11.3h, then the dehydrated polybutylene carbonate is added into a reactor, after the dehydration, 8.70g of toluene diisocyanate and 5.73g of diphenylmethane diisocyanate are added after the uniform stirring, the reaction is carried out at 80 ℃ for 3h, and then the aqueous polyurethane prepolymer is obtained, wherein the total amount of the excessive toluene diisocyanate and the diphenylmethane diisocyanate is 0.0459 mol;
step 2, adding 1, 6-hexanediol of 4.25g, ethylene glycol of 0.04g and butanone of 22.5 percent solvent (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the small molecular weight dihydric alcohol) into the waterborne polyurethane prepolymer, continuing to react for 3 hours at 60 ℃, and then cooling to room temperature;
and 3, adding 1.01mL of ammonia water and 0.08g of sodium hydroxide into the reaction product to neutralize the dihydroxy half ester, stirring at room temperature for 0.86h, dropwise adding deionized water according to the solid content of 40.2% to emulsify, adding 1.98g of hydroxy functional monomer 3, 3' -dihydroxybenzidine, strongly stirring for 18min, and heating to 48 ℃ to react for 0.6 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 29.4MPa, the elongation at break is 557%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 13.42%, and the 24-hour final adhesion strength to a base material PVC is 2.95N/mm.
Example 10
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 10g of polybutadiene polyol (Mn is 1000) is dehydrated under reduced pressure at 132 ℃ for 2h, 0.40g of dimethylolpropionic acid and 0.59g of diaminobenzoic acid are dried in a drying oven at 135 ℃ for 11h, then the mixture is added into a reactor after dehydration, after uniform stirring, 12.37g of m-tetramethylene xylene diisocyanate is added, and the mixture reacts at 82 ℃ for 2.6h to obtain an aqueous polyurethane prepolymer, wherein 8.25g of excess m-tetramethylene xylene diisocyanate;
step 2, adding 1.18g of 1, 6-hexanediol, 1.06g of ethylene glycol and 17.9% of solvent ethylene glycol monobutyl ether (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the small molecular weight dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 3.1h at 58 ℃, and then cooling to room temperature;
and 3, adding 0.20g of triethylamine and 0.70g of tripropylamine into the reaction product to neutralize dimethylolpropionic acid and diaminobenzoic acid, stirring for 0.78h at room temperature, dropwise adding deionized water according to the solid content of 36.7% to emulsify, then adding 2.77g of hydroxyl functional monomer 1, 4-butanediol diglycidyl ether cyclic carbonate and excessive ethylenediamine aminolysis product, stirring strongly for 21min, and heating to 55 ℃ to react for 0.51 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 30.1MPa, the elongation at break is 521%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 11.98%, and the 24-hour final adhesion strength to a base material PVC is 2.72N/mm.
Example 11
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 8.2g of poly (hexanediol adipate) (Mn is 1000) and 1.8g of poly (ethylene glycol-propylene glycol adipate) (Mn is 1000) are dehydrated under reduced pressure at 138 ℃ for 2.1h, 0.84g of diaminobenzoic acid is dried in a drying oven at 128 ℃ for 12.1h and then is added into a reactor, 8.33g of hexamethylene diisocyanate is added after uniform stirring, and the mixture is reacted at 92 ℃ for 2.1h to obtain a waterborne polyurethane prepolymer, wherein the excessive hexamethylene diisocyanate is 5.73 g;
step 2, adding 1.13g of 1, 4-butanediol, 1.33g of 1, 6-hexanediol and 18.9% of solvent acetone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the small molecular weight dihydric alcohol) into the waterborne polyurethane prepolymer, continuing to react at 63 ℃ for 3.5 hours, and cooling to room temperature;
and 3, adding 0.33g of tripropylamine and 0.59g of tributylamine into the reaction product to neutralize diaminobenzoic acid, stirring at room temperature for 0.51h, dropwise adding deionized water according to the solid content of 29.9% to emulsify, then adding 1.50g of chain extender N, N-bis (2-hydroxyethyl) ethylenediamine and 0.009g of hydroxyl functional monomer glycerol, stirring strongly for 25min, and heating to 51 ℃ to react for 0.6 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted, and then is subjected to performance test, the tensile strength of a glue film is 28.7MPa, the elongation at break is 603%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 13.87%, and the 24-hour final adhesive strength to a base material PVC is 3.02N/mm.
Example 12
A preparation method of hydroxyl functionalized waterborne polyurethane comprises the following steps:
step 1, 9g of polyethylene glycol ether (Mn is 1000) and 1g of polypropylene glycol ether (Mn is 1000) are dehydrated under reduced pressure at 128 ℃ for 2.5h, 1.03g of diaminobenzoic acid is dried in a drying oven at 135 ℃ for 10.5h and then added into a reactor, 1.88g of hexamethylene diisocyanate and 5.47g of m-tetramethylxylene diisocyanate are added after being uniformly stirred, and the mixture is reacted at 90 ℃ for 2.5h to obtain an aqueous polyurethane prepolymer, wherein the total content of the excessive hexamethylene diisocyanate and the excessive m-tetramethylxylene diisocyanate is 0.0168 mol;
step 2, adding 1, 2-propylene glycol and 23.4% butanone (accounting for the total mass fraction of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol) into the waterborne polyurethane prepolymer, continuously reacting for 3 hours at 60 ℃, and then cooling to room temperature;
and 3, adding 1.26g of tributylamine to the reaction product to neutralize diaminobenzoic acid, stirring at room temperature for 0.99h, dropwise adding deionized water according to the solid content of 30.7% to emulsify, then adding 1.02g of hydroxyl functionalized monomer 1, 6-dihydro-1-hydroxy-pyrrolo [2,3-b ] pyrrole-2, 3-diamine, stirring strongly for 10min, and heating to 50 ℃ to react for 0.76 h. And after the reaction is finished, removing the added solvent through reduced pressure distillation to obtain the hydroxyl functionalized aqueous polyurethane emulsion.
The emulsion is not layered after being stored for one year at room temperature, the obtained waterborne polyurethane emulsion is dried and tabletted to be subjected to performance test, the tensile strength of a glue film is 26.3MPa, the elongation at break is 679%, the swelling degree after the glue film is soaked in water to reach the swelling balance is 12.05%, and the 24-hour final adhesion strength to a base material PVC is 2.56N/mm.

Claims (18)

1. A preparation method of hydroxyl functionalized waterborne polyurethane is characterized by comprising the following steps:
step 1, dehydrating polymer polyol and a carboxyl-containing hydrophilic agent, adding the dehydrated polymer polyol and the carboxyl-containing hydrophilic agent into a reactor, uniformly stirring the dehydrated polymer polyol and the carboxyl-containing hydrophilic agent, adding an isocyanate compound into the reactor, and reacting the mixture to obtain a waterborne polyurethane prepolymer;
step 2, adding micromolecular dihydric alcohol and a solvent into the waterborne polyurethane prepolymer, continuing to react, and cooling to room temperature;
and 3, adding a salt forming agent into the reaction system obtained in the step 2, stirring at room temperature for reaction, adding deionized water for emulsification, adding a chain extender and a hydroxyl functional monomer, heating for reaction after strong stirring, and removing the solvent through reduced pressure distillation after the reaction is finished to obtain the hydroxyl functional waterborne polyurethane.
2. The method for preparing hydroxyl functional waterborne polyurethane as claimed in claim 1, wherein the polymer polyol in step 1 is one or more of polyester diol, polyether diol or polycarbonate diol, and the polymer polyol is mixed according to any ratio.
3. The preparation method of hydroxyl functional waterborne polyurethane as claimed in claim 2, wherein the polyester diol is one or more of polyethylene glycol adipate, polybutylene adipate, polyethylene glycol-propylene glycol adipate, polyethylene glycol-butylene glycol adipate, polyethylene glycol neopentyl glycol adipate and polyethylene-caprolactone diol mixed according to any ratio;
the polyether glycol is one or a mixture of a plurality of polyoxypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, polytetramethylene ether glycol, polyoxyethylene glycol, polybutadiene polyhydric alcohol and the like according to any ratio;
the polycarbonate diol is one or a plurality of polycarbonate hexanediol, polycarbonate pentanediol and polycarbonate butanediol which are mixed according to any ratio.
4. The method of claim 3, wherein the polyester diol, polyether diol or polycarbonate diol has a molecular weight of 1000 to 2000.
5. The method for preparing hydroxyl functional waterborne polyurethane as claimed in claim 1, wherein the hydrophilic agent containing carboxyl in step 1 is one or more of 2, 2-dimethylolpropionic acid, dihydroxy half ester and diaminobenzoic acid, which are mixed according to any ratio.
6. The method of claim 1, wherein the isocyanate compound in step 1 is one or more selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and m-tetramethylenexylylene diisocyanate, and the mixture thereof is mixed in any ratio.
7. The method for preparing hydroxyl-functionalized waterborne polyurethane as claimed in claim 1, wherein the small molecule diol in step 2 is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol, and diethylene glycol, which are mixed in any ratio.
8. The method of claim 1, wherein the solvent in step 2 is one of acetone, methyl ethyl ketone, N-dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, and ethylene glycol monobutyl ether.
9. The method for preparing hydroxyl functional waterborne polyurethane as claimed in claim 1, wherein the salt forming agent in step 3 is one or more of triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water, and the salt forming agent is mixed in any ratio.
10. The method for preparing hydroxyl-functionalized waterborne polyurethane as claimed in claim 1, wherein the chain extender in step 3 is one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine, ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol, and N, N-bis (2-hydroxyethyl) ethylenediamine, which are mixed in any ratio.
11. The method of claim 1, wherein the hydroxyl functional monomer in step 3 is one or more of polyhydroxy polyamine alcohol amine compound or polyhydroxy compound containing hydroxyl and primary amine group in the structure, and the structural formula is as follows:
Figure FDA0002541700710000031
12. the method of claim 11 wherein the polyhydroxylated polyamino alcohol amine compound or polyhydroxylated compound containing hydroxyl groups and primary amine groups in the structure is one or more of 2-hydroxy-1, 3-propanediamine, 3' -dihydroxybenzidine, tetrahydroxyadipamide, 1, 6-dihydro-1-hydroxy-pyrrolo [2,3-b ] pyrrole-2, 3-diamine, glycerol, or cyclic carbonate and excess amine are subjected to ring-opening reaction to form the polyhydroxylated polyamino alcohol amine compound containing β -hydroxyl groups, urethane groups and amine groups, in any ratio.
13. The method of claim 1, wherein in step 1, the molar ratio of the polymer polyol to the hydrophilic agent containing carboxyl groups is 0.5-2: 1, and the molar ratio of the isocyanate compound to the total molar amount of the polymer polyol and the hydrophilic agent containing carboxyl groups is 1.8-3.5: 1.
14. The method for preparing hydroxyl-functionalized waterborne polyurethane according to claim 1, wherein the amount of the small molecular diol used in the step 2 is 0.6 to 0.8 times of the molar amount of the excessive isocyanate compound in the step 1; the solvent accounts for 15 to 30 percent of the total mass of the polymer polyol, the carboxyl-containing hydrophilic agent, the isocyanate compound and the micromolecular dihydric alcohol.
15. The method for preparing hydroxyl-functionalized waterborne polyurethane as claimed in claim 1, wherein the molar ratio of the salt forming agent to the carboxyl-containing hydrophilic agent in the step 3 is 1: 1; the dosage of the deionized water is calculated according to the solid content, and the solid content is controlled to be 20-45 percent; the total usage amount of the chain extender and the hydroxyl functional monomer is the same as the mole number of the residual isocyanate groups after the reaction in the step, wherein the mole ratio of the chain extender to the hydroxyl functional monomer is 0-99: 100-1.
16. The preparation method of hydroxyl functional waterborne polyurethane as claimed in claim 1, wherein the dehydration condition of the polymer polyol in the step 1 is that the polymer polyol is dehydrated for 2-4 h at 100-140 ℃ under reduced pressure, and the dehydration condition of the carboxyl-containing hydrophilic agent is that the polymer polyol is dehydrated for 10-14 h after being dried in a drying oven at 100-140 ℃; the reaction temperature is 70-95 ℃, and the reaction time is 2-5 h.
17. The method for preparing hydroxyl-functionalized waterborne polyurethane according to claim 1, wherein the reaction is continued in the step 2 at a temperature of 50-65 ℃ for 2-5 hours.
18. The preparation method of the hydroxyl functional waterborne polyurethane as claimed in claim 1, wherein the stirring reaction time in step 3 is 0.5-1 h at room temperature, the intensive stirring reaction time is 0.1-0.5 h, the heating reaction temperature is 40-55 ℃, and the heating reaction time is 0.5-1 h.
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