CN112126037A - Phytic-based waterborne polyurethane and preparation method thereof - Google Patents
Phytic-based waterborne polyurethane and preparation method thereof Download PDFInfo
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses phytate-based waterborne polyurethane and a preparation method thereof, and belongs to the technical field of production of high polymer materials. The method comprises the following steps: preparing phytic acid derivative containing active group and terminal hydroxyl, utilizing the reaction of hydroxyl and isocyanate group contained in the aqueous polyurethane prepolymer, and adopting internal emulsification method to prepare phytic acid modified aqueous polyurethane material. The synthesis process is simple, easy to operate, safe and reliable, and promotes the development of sustainable and eco-friendly materials.
Description
Technical Field
The invention belongs to the technical field of production of high polymer materials, and particularly relates to phytate-based waterborne polyurethane and a preparation method thereof.
Background
With the increasing exhaustion of petrochemical resources and the stricter requirements on environmental protection, the research on biomass modified polyurethane has become a hot spot. The biomass material has a large number of active groups such as hydroxyl or amino, and the like, so that the biomass material is mainly used for modifying the waterborne polyurethane to prepare the polyurethane composite material by a blending, copolymerization or graft crosslinking method. The polyurethane is used as a matrix, and the graft crosslinking modification of the polyurethane by natural organic matters has better biocompatibility and wider use of base materials. The introduction of the biomass material improves the performance indexes of the polyurethane compound in many aspects, such as mechanical property, flame retardant property, thermodynamic stability and the like, and develops a new way for further research and application of polyurethane.
Phytic Acid (PA), also known as inositol phosphate, is a natural non-toxic extract that can be extracted from the fruits of plants. The natural environment-friendly phosphorus-containing organic compound has good biological activity and is a natural product with strong chelation. The phytic acid has the characteristics of greenness, renewability, phosphorus enrichment and the like. Based on the excellent characteristics of the phytic acid modified waterborne polyurethane, the phytic acid resources can be effectively utilized, the pollution is reduced, the biocompatibility and the like of the waterborne polyurethane are favorably improved, and the phytic acid modified waterborne polyurethane is an attractive natural product in the field of polyurethane modification. Therefore, the phytic acid is introduced into the aqueous polyurethane, so that the defects of inflammable and explosive organic solvent, high volatility, strong smell, serious pollution and the like of the solvent type polyurethane can be overcome; meanwhile, the modified polyurethane has the excellent performances of the phytic acid and the waterborne polyurethane, so that the application field of the polyurethane is widened.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the phytic acid-based waterborne polyurethane and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of phytate-based waterborne polyurethane, which comprises the following steps:
1) preparation of phytic acid derivatives
Mixing pentaerythritol and phytic acid, and reacting for 2-3 h at 110-130 ℃ under the stirring condition to prepare a hydroxyl-terminated phytic acid derivative;
2) preparation of polyurethane prepolymer
In the nitrogen atmosphere, fully stirring polytetrahydrofuran ether glycol and isophorone diisocyanate until the polytetrahydrofuran ether glycol and the isophorone diisocyanate are dissolved uniformly, adding a catalyst dibutyltin dilaurate for prepolymerization reaction, heating to continue reacting for a certain time, adding a micromolecular chain extender 1, 4-butanediol and a hydrophilic chain extender dimethylolpropionic acid, and performing chain extension reaction to obtain a waterborne polyurethane prepolymer;
3) preparation of phytic acid-based waterborne polyurethane
Dissolving the hydroxyl-terminated phytic acid derivative prepared in the step 1), then carrying out crosslinking reaction on the dissolved hydroxyl-terminated phytic acid derivative and a polyurethane prepolymer, and then carrying out neutralization, emulsification and dispersion treatment to obtain the phytic acid-based waterborne polyurethane.
Preferably, in step 1), the reaction of phytic acid and pentaerythritol is carried out at a molar ratio of 1: 3.
Preferably, in the step 2), the molar ratio of the isophorone diisocyanate to the polytetrahydrofuran ether glycol (3.5-5.5): 1.
preferably, in the step 2), the prepolymerization reaction temperature is 50 ℃ and the time is 30min, and then the temperature is raised to 70 ℃ to continue the reaction for 1.5 h.
Preferably, in the step 2), the amount of the added small molecular chain extender 1, 4-butanediol is 2% of the total mass of the isophorone diisocyanate and the polytetrahydrofuran ether glycol; the amount of the added hydrophilic chain extender bis-hydroxymethyl propionic acid is 4 to 8 percent of the total mass of the isophorone diisocyanate and the polytetrahydrofuran ether glycol.
Preferably, in the step 2), the reaction temperature of the chain extension reaction is 80 ℃ and the reaction time is 2 h.
Preferably, in the step 3), the amount of the terminal hydroxyl phytic acid derivative added is 1 to 5 percent of the total mass of the isophorone diisocyanate and the polytetrahydrofuran ether glycol.
Preferably, in step 3), the temperature of the crosslinking reaction is 85 ℃; the reaction time is 1-2 h.
The invention also discloses the phytic acid-based waterborne polyurethane prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of phytic acid-based waterborne polyurethane, which comprises the steps of firstly preparing a phytic acid derivative containing active group terminal hydroxyl, utilizing the reaction of hydroxyl and isocyanate groups contained in a waterborne polyurethane prepolymer, and preparing a phytic acid modified waterborne polyurethane material by adopting an internal emulsification method. According to the designability of polyurethane molecules, the invention develops the WPU by carrying out internal crosslinking modification around the self-made hydroxyl-terminated monomer, designs and synthesizes the biomass-based WPU with excellent comprehensive performance, and has the advantages that:
firstly, a biomass-based compound is introduced into waterborne polyurethane by an internal emulsification method, so that the defects of flammability, explosiveness, volatility, strong smell, serious pollution and the like of an organic solvent of solvent type polyurethane are overcome; meanwhile, the defects of poor water resistance, solvent resistance, mechanical property and the like of the traditional waterborne polyurethane film are avoided, the operation process is simple and convenient, and the cost is low;
second, phytic acid, as a natural, environmentally friendly organic compound containing phosphorus, has good biological activity. The phytic acid derivative is introduced into the waterborne polyurethane, so that the phytic acid resource is effectively utilized, the pollution is reduced, and the biocompatibility of the waterborne polyurethane is favorably improved;
thirdly, the invention provides the phytate-based waterborne polyurethane, which further improves the mechanical property and the thermal stability of the waterborne polyurethane through a crosslinking reaction and simultaneously enables the waterborne polyurethane with high solid content to be possible.
And fourthly, the waterborne polyurethane takes water as a dispersing agent, has low VOC, is nontoxic and pollution-free, is safe and environment-friendly, and promotes the development of sustainable and eco-friendly materials.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the phytic acid derivatives of the present invention.
FIG. 2 is a schematic diagram of the synthetic process of the phytic acid-based waterborne polyurethane.
FIG. 3 is an infrared image of the phytic acid derivative, the aqueous Polyurethane Prepolymer (PPU) and the phytic acid-based aqueous polyurethane obtained in example 1.
FIG. 4 is a graph showing thermal property analysis of the polyurethane before modification and the phytic acid-based aqueous polyurethane obtained in example 1; wherein a) is a TG spectrogram of WPU and PRPA modified WPU; b) the DTG spectrogram of WPU and PRPA modified WPU.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the invention discloses a preparation method of phytate-based waterborne polyurethane, which is developed by carrying out internal crosslinking modification on WPU around a self-made hydroxyl-terminated monomer mainly according to the designability of polyurethane molecules, and designs and synthesizes a biomass-based WPU with excellent comprehensive performance. Referring to fig. 1 and 2, firstly, pentaerythritol and phytic acid are used as main raw materials to synthesize phytic acid derivatives (PRPA), and then the PRPA is introduced into the aqueous polyurethane in a chemical crosslinking mode, so that the biomass-based aqueous polyurethane with excellent performance is prepared.
Example 1
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 120 ℃, reacting for 3 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 10g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of dibutyl tin dilaurate (DBTDL) serving as a catalyst are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h to prepare the polyurethane prepolymer. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.8g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) continuously adding 2% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups at the same temperature to perform a crosslinking reaction, after the reaction is performed for 1.5h, cooling, adding Triethylamine (TEA) with the ratio of DMPA being 1:1 to perform neutralization and salification for 0.5h, finally slowly adding distilled water under the condition of vigorous stirring, performing high-speed emulsification for 0.5h, and performing reduced pressure distillation to remove the acetone to obtain the phytic acid-based waterborne polyurethane (PRPA-WPU). FIG. 3 is an infrared image of the phytic acid derivative, the aqueous Polyurethane Prepolymer (PPU) and the phytic acid-based aqueous polyurethane obtained in example 1. As can be seen, 3530 and 1641cm of PRPA spectrum-1Due to stretching vibration of-OH and hydration of water molecules, the presence of polyhydroxy in PRPA was confirmed; 1158 and 998cm-1And stretching and contracting vibration of the P-O, O-P-C group. 2256cm in PPU spectrogram-1The stretching vibration peak at C ═ N is attributed to unreacted-NCO in IPDI. 1110cm in PPU and HPAE-WPU-1C-O-C vibration peaks appear at the positions, which are attributed to ether bonds in the long chain of the polyurethane; in HPAE-WPU, 2256cm-1The disappearance of the peak of stretching vibration at C ═ N indicates that in IPDIthe-NCO reaction was complete and was at 3336cm-1And 626cm-1N-H stretching vibration peaks appear in the compounds, which indicates that-NCO reacts with-OH to generate carbamate. The result shows that the phytic acid-based waterborne polyurethane is generated by the reaction.
FIG. 4 shows thermogravimetric analysis TG and DTG spectra of unmodified waterborne polyurethane and the phytic acid-based waterborne polyurethane obtained in example 1. As can be seen from the DTG graph, the polyurethane adhesive film generates mass loss from about 260 ℃, and the mass loss is mainly caused by the decomposition of hard urethane groups in polyurethane; the next stage produces a mass loss from around 350 ℃, this range corresponding mainly to the decomposition of the soft blocks in the polyurethane. The thermal decomposition data of WPU and PRPA-WPU adhesive films obtained from the TG curve chart are shown in the following table 1, and the thermal decomposition temperature of PRPA-WPU is higher under the same mass loss. The decomposition temperatures of WPU and PRPA-WPU were 267.3 ℃ and 286.2 ℃ respectively at a mass loss of 10%, and 332.9 ℃ and 339.9 ℃ respectively at a mass loss of 30%, 371.8 ℃ and 381.8 ℃ respectively at a mass loss of 50%, and 393.7 ℃ and 402.7 ℃ respectively at a mass loss of 70%. Therefore, after the WPU is modified by the PRPA, the heat-resistant stability of the PRPA-WPU adhesive film is obviously improved.
TABLE 1 WPU and PRPA-WPU thermogram
Example 2
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 130 ℃, reacting for 2 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 11g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of dibutyl tin dilaurate (DBTDL) serving as a catalyst are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h to prepare the polyurethane prepolymer. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.87g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) continuously adding 2% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups at the same temperature to perform a crosslinking reaction, after the reaction is performed for 1.5h, cooling, adding Triethylamine (TEA) with the ratio of DMPA being 1:1 to perform neutralization and salification for 0.5h, finally slowly adding distilled water under the condition of vigorous stirring, performing high-speed emulsification for 0.5h, and performing reduced pressure distillation to remove the acetone to obtain the phytic acid-based waterborne polyurethane (PRPA-WPU).
Example 3
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 130 ℃, reacting for 2 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 8.9g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of catalyst dibutyl tin dilaurate (DBTDL) are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h, so that the polyurethane prepolymer is prepared. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.73g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) continuously adding 2% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups at the same temperature for crosslinking reaction, cooling and adding Triethylamine (TEA) with the ratio of DMPA being 1:1 for neutralization and salification for 0.5h after reaction for 2h, finally slowly adding distilled water under the condition of vigorous stirring, emulsifying at high speed for 0.5h, and removing the acetone through reduced pressure distillation to obtain the phytic acid-based waterborne polyurethane (PRPA-WPU).
Example 4
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 120 ℃, reacting for 3 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 10g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of dibutyl tin dilaurate (DBTDL) serving as a catalyst are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h to prepare the polyurethane prepolymer. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.8g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) at the same temperature, continuously adding 3% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups for a crosslinking reaction, after the reaction is carried out for 1.5h, cooling, adding Triethylamine (TEA) with the ratio of DMPA being 1:1 for neutralization and salification for 0.5h, finally slowly adding distilled water under the condition of vigorous stirring, carrying out high-speed emulsification for 0.5h, and carrying out reduced pressure distillation to remove the acetone, thus obtaining the phytic acid-based waterborne polyurethane (PRPA-WPU).
Example 5
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 120 ℃, reacting for 3 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 10g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of dibutyl tin dilaurate (DBTDL) serving as a catalyst are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h to prepare the polyurethane prepolymer. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.8g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) continuously adding 4% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups at the same temperature for crosslinking reaction, cooling and adding Triethylamine (TEA) with the ratio of DMPA being 1:1 for neutralization and salification for 0.5h after reaction for 1h, finally slowly adding distilled water under the condition of vigorous stirring, emulsifying at high speed for 0.5h, and removing the acetone through reduced pressure distillation to obtain the phytic acid-based waterborne polyurethane (PRPA-WPU).
Example 6
A preparation method of phytate-based waterborne polyurethane comprises the following steps:
step (1): preparation of phytic acid derivative (PRPA)
Weighing Pentaerythritol (PER) and Phytic Acid (PA) according to a molar ratio of 3:1, adding the Pentaerythritol (PER) and the Phytic Acid (PA) into a three-neck flask, uniformly stirring and mixing, heating to 130 ℃, reacting for 3 hours to obtain a crude product, and finally performing vacuum filtration and freeze drying to obtain the hydroxyl-terminated phytic acid derivative (PRPA).
Step (2): preparation of phytic acid derivative modified waterborne polyurethane (PRPA-WPU)
Under the protection of nitrogen, 20g of dried polytetrahydrofuran ether glycol (PTMG, Mn ═ 2000) and 10g of isophorone diisocyanate (IPDI) are added into a three-neck flask, stirred at normal temperature until the materials are uniformly dissolved, 2-3 drops of dibutyl tin dilaurate (DBTDL) serving as a catalyst are dropped into the flask, the mixture reacts for 30min at 50 ℃, and the temperature is increased to 70 ℃ to continue the reaction for 1.5h to prepare the polyurethane prepolymer. Then 2% of micromolecular chain extender 1, 4-Butanediol (BDO) and 1.5g of hydrophilic chain extender bis-hydroxymethyl propionic acid (DMPA) are added for chain extension reaction, and the temperature is raised to 80 ℃ for reaction for 2 hours. And (2) continuously adding 2% of (PRPA) phytic acid derivative (dissolved in acetone) obtained in the step (1) and isocyanate groups at the same temperature to perform a crosslinking reaction, after the reaction is performed for 1.5h, cooling, adding Triethylamine (TEA) with the ratio of DMPA being 1:1 to perform neutralization and salification for 0.5h, finally slowly adding distilled water under the condition of vigorous stirring, performing high-speed emulsification for 0.5h, and performing reduced pressure distillation to remove the acetone to obtain the phytic acid-based waterborne polyurethane (PRPA-WPU).
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. The preparation method of the phytate-based waterborne polyurethane is characterized by comprising the following steps:
1) preparation of phytic acid derivatives
Mixing pentaerythritol and phytic acid, and reacting for 2-3 h at 110-130 ℃ under the stirring condition to prepare a hydroxyl-terminated phytic acid derivative;
2) preparation of polyurethane prepolymer
In the nitrogen atmosphere, fully stirring polytetrahydrofuran ether glycol and isophorone diisocyanate until the polytetrahydrofuran ether glycol and the isophorone diisocyanate are dissolved uniformly, adding a catalyst dibutyltin dilaurate for prepolymerization reaction, heating to continue reacting for a certain time, adding a micromolecular chain extender 1, 4-butanediol and a hydrophilic chain extender dimethylolpropionic acid, and performing chain extension reaction to obtain a waterborne polyurethane prepolymer;
3) preparation of phytic acid-based waterborne polyurethane
Dissolving the hydroxyl-terminated phytic acid derivative prepared in the step 1), then carrying out crosslinking reaction on the dissolved hydroxyl-terminated phytic acid derivative and a polyurethane prepolymer, and then carrying out neutralization, emulsification and dispersion treatment to obtain the phytic acid-based waterborne polyurethane.
2. The method for preparing the phytic acid-based waterborne polyurethane as claimed in claim 1, wherein in the step 1), the reaction of the phytic acid and the pentaerythritol is carried out at a molar ratio of 1: 3.
3. The method for preparing the phytic acid-based aqueous polyurethane according to claim 1, wherein in the step 2), the molar ratio of the isophorone diisocyanate to the polytetrahydrofuran ether glycol (3.5-5.5): 1.
4. the method for preparing the phytic acid-based waterborne polyurethane as claimed in claim 1, wherein in the step 2), the prepolymerization reaction temperature is 50 ℃ for 30min, and then the temperature is raised to 70 ℃ for further reaction for 1.5 h.
5. The method for preparing the phytic acid-based waterborne polyurethane as claimed in claim 1, wherein in the step 2), the amount of the added small molecular chain extender 1, 4-butanediol is 2% of the total mass of the isophorone diisocyanate and the polytetrahydrofuran ether glycol; the amount of the added hydrophilic chain extender bis-hydroxymethyl propionic acid is 4 to 8 percent of the total mass of the isophorone diisocyanate and the polytetrahydrofuran ether glycol.
6. The method for preparing the phytic acid-based waterborne polyurethane as claimed in claim 1, wherein in the step 2), the reaction temperature of the chain extension reaction is 80 ℃ and the reaction time is 2 hours.
7. The method for preparing the phytic acid-based waterborne polyurethane as claimed in claim 1, wherein the amount of the hydroxy-terminated phytic acid derivative added in the step 3) is 1 to 5% of the total mass of isophorone diisocyanate and polytetrahydrofuran ether glycol.
8. The method for preparing the phytic acid-based aqueous polyurethane as claimed in claim 1, wherein, in the step 3), the temperature of the crosslinking reaction is 85 ℃; the reaction time is 1-2 h.
9. The phytic acid-based waterborne polyurethane prepared by the preparation method of any one of claims 1 to 8.
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| CN112126037B (en) | 2022-02-11 |
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