CN115044003A - Preparation method of fluorine-containing self-healing waterborne polyurethane artificial skin material - Google Patents

Preparation method of fluorine-containing self-healing waterborne polyurethane artificial skin material Download PDF

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CN115044003A
CN115044003A CN202210163139.2A CN202210163139A CN115044003A CN 115044003 A CN115044003 A CN 115044003A CN 202210163139 A CN202210163139 A CN 202210163139A CN 115044003 A CN115044003 A CN 115044003A
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healing
waterborne polyurethane
fluorine
chain extender
polyol
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CN115044003B (en
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戴家兵
王启东
李维虎
钦洋
吴旻晨
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Hefei Flexible Ketian Robot Material Co ltd
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Hefei Flexible Ketian Robot Material Co ltd
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    • 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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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of a fluorine-containing self-healing waterborne polyurethane artificial skin material, which relates to the technical field of waterborne polyurethane materials, and comprises the steps of firstly reacting isocyanate, macromolecular polyol, organosilicon polyether polyol, hydrophilic chain extender, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol and micromolecular chain extender under the action of a catalyst to prepare a prepolymer, then adding a neutralizer and a post chain extender to react to prepare the fluorine-containing self-healing waterborne polyurethane; the fluorine-containing waterborne polyurethane prepared by the invention has excellent self-healing capability, environmental protection performance, heat resistance and touch feeling similar to human skin, and fills the gap that materials with self-healing and hydrophilic performances are not developed at home and abroad.

Description

Preparation method of fluorine-containing self-healing waterborne polyurethane artificial skin material
The technical field is as follows:
the invention relates to the technical field of waterborne polyurethane materials, in particular to a preparation method of a fluorine-containing self-healing waterborne polyurethane artificial skin material.
Background art:
with the demand of intelligent wearable equipment becoming higher and higher, the market for preparing a material very similar to human skin is more and more urgent. At present, many scientific research institutions and colleges mainly focus on simulating human skin by using materials such as silicon rubber and the like, but the materials have insufficient hydrophilic performance, and human epidermis has hydrophilic performance, so that the materials and the human skin have larger performance in and out under a humid environment; researchers at home and abroad research artificial skin materials with hydrophilic performance, but the self-healing performance of the artificial skin materials is poor, and the skin of a human body has the self-healing performance. In conclusion, the material with self-healing and excellent hydrophilic performance is close to human skin.
The invention content is as follows:
the invention aims to solve the technical problem of providing a preparation method of fluorine-containing self-healing waterborne polyurethane, which has excellent self-healing capability, excellent hydrophilic property, good environmental protection property, good heat resistance, touch feeling close to human skin, and wide application prospect in the aspects of artificial skin, wearable equipment, artificial limb epidermis and the like.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides a preparation method of a fluorine-containing self-healing waterborne polyurethane artificial skin material, which comprises the steps of firstly reacting isocyanate, macromolecular polyol, organosilicon polyether polyol, hydrophilic chain extender, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol and micromolecular chain extender under the action of a catalyst to prepare a prepolymer, and then adding a neutralizer and a post chain extender to react to prepare the fluorine-containing self-healing waterborne polyurethane.
2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol is introduced into the waterborne polyurethane, and the substance endows the main chain of the waterborne polyurethane with a proper amount of fluorine functional groups, so that the waterborne polyurethane has a strong hydrogen bond effect and strong intermolecular force, and therefore, the material has excellent self-healing capability; due to the existence of the hydrophilic chain extender, the material has excellent hydrophilic performance and hydrophilic characteristic similar to epidermis; because the material takes water as a solvent, the material has excellent environmental protection performance; because fluorine exists in a molecular chain, the heat resistance of the material is excellent; because the silicone polyether polyol is introduced into the main chain of the waterborne polyurethane, the material has the touch feeling which is very close to the skin.
The isocyanate comprises one or more of isophorone diisocyanate (IPDI), 4-dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), toluene-2, 4-diisocyanate (TDI), and diphenylmethane diisocyanate (MDI).
The macromolecular polyol comprises one or more of polyether polyol (PPG series), polytetrahydrofuran polyol (PTMG series), polyester polyol and polycarbonate polyol.
The hydrophilic chain extender comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid and sulfonate type hydrophilic chain extenders.
The chain extender comprises one or more of 2-methyl-1, 3-propanediol (MPO), 1, 4-Butanediol (BDO), Cyclohexanedimethanol (CHDM) and Trimethylolpropane (TMP).
The post-chain extender comprises one or more of ethylenediamine, hexamethylenediamine, isophorone diamine and 1, 4-cyclohexanedimethylamine.
The catalyst comprises one or more of an organic bismuth catalyst, a zirconium catalyst and a manganese catalyst.
The neutralizing agent comprises one or more of triethylamine, ammonia water, triethanolamine and sodium hydroxide.
The content of the 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol accounts for 1-10% of the mass of the waterborne polyurethane prepolymer.
The proportion of the organic silicon polyether glycol is 5-35% of the mass of the waterborne polyurethane prepolymer.
The proportion of the catalyst is 0.1-0.3% of the mass of the waterborne polyurethane prepolymer.
The invention also uses the fluorine-containing self-healing waterborne polyurethane artificial skin material in preparation of wearable equipment and artificial limb epidermis.
The invention has the beneficial effects that: the fluorine-containing self-healing waterborne polyurethane is prepared by reacting isocyanate, macromolecular polyol, organic silicon polyether polyol, hydrophilic chain extender and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol according to a certain proportion at a certain temperature to form a prepolymer, emulsifying, opening, adding and then chain extending; because the 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol, the organic silicon polyether polyol and the hydrophilic chain extender are introduced into the waterborne polyurethane, the material has very excellent self-healing capability, environmental protection performance, heat resistance and touch feeling similar to human skin, and the invention fills the gap that the material with self-healing and hydrophilic performances is not developed at home and abroad.
Description of the drawings:
FIG. 1 is an optical microscope image of the specimens with self-healing changes at different time periods.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
The following examples and comparative examples all raw materials except the catalyst were purchased from Delaunax Chemicals, Inc.
Example 1
A preparation method of fluorine-containing self-healing waterborne polyurethane comprises the following steps:
weighing 90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of organosilicon polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate, adding into a three-neck flask, and stirring at 90 ℃ for reacting for 2 hours; then 4.9g dimethylolpropionic acid, 8g 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol, 0.1g trimethylolpropane and 15g acetone were added to the three-necked flask, and the reaction was continued with stirring at 80 ℃ for 2 hours; then adding 0.3g of organic bismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; and then adding 120g of acetone, cooling the obtained prepolymer to 50 ℃, adding 3.69g of triethylamine for reaction for 3min, cooling the prepolymer to 10 ℃, discharging the prepolymer to a plum barrel, adding 307g of distilled water into a dispersion machine, emulsifying and opening the mixture, wherein the rotation speed of the dispersion machine is 2800r/min, finally adding 2.81g of 1, 4-cyclohexyldimethylamine for post-chain extension reaction, standing for 8h, and removing acetone to obtain the fluorine-containing self-healing waterborne polyurethane.
Example 2
A preparation method of fluorine-containing self-healing waterborne polyurethane comprises the following steps:
weighing 90g of polyether polyol PPG-3000 (molecular weight 3000), 18g of organic silicon polyether polyol (molecular weight 1800) and 31.97g of isophorone diisocyanate, adding into a three-neck flask, and stirring and reacting for 2 hours at 90 ℃; then 4.9g dimethylolpropionic acid, 8g 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol, 0.1g trimethylolpropane and 15g acetone were added to the three-necked flask, and the reaction was continued with stirring at 80 ℃ for 2 hours; then adding 0.3g of organic bismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; and then adding 120g of acetone, cooling the obtained prepolymer to 50 ℃, adding 3.69g of triethylamine to react for 3min, cooling the prepolymer to 10 ℃, then discharging the prepolymer to a plum blossom barrel, adding 296g of distilled water to a dispersion machine to emulsify and open, wherein the rotating speed of the dispersion machine is 2800r/min, finally adding 2.81g of 1, 4-cyclohexanediamine to perform post-chain extension reaction, standing for 8h, and removing acetone to obtain the fluorine-containing self-healing waterborne polyurethane.
Example 3
The preparation method of the fluorine-containing self-healing waterborne polyurethane comprises the following steps:
weighing 90g of polycarbonate polyol PCD-3000 (molecular weight is 3000), 18g of organic silicon polyether polyol (molecular weight is 1800) and 37.73g of 4, 4-dicyclohexyl methane diisocyanate, adding into a three-neck flask, and stirring and reacting for 2h at 90 ℃; then 4.9g dimethylolpropionic acid, 8g 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol, 0.1g trimethylolpropane and 15g acetone were added to the three-necked flask, and the reaction was continued with stirring at 80 ℃ for 2 hours; then adding 0.3g of organic bismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; and then adding 120g of acetone, cooling the obtained prepolymer to 50 ℃, adding 3.69g of triethylamine to react for 3min, cooling the prepolymer to 10 ℃, discharging the prepolymer to a plum blossom barrel, adding 307g of distilled water to a dispersion machine, emulsifying and opening, wherein the rotating speed of the dispersion machine is 2800r/min, finally adding 2.81g of 1, 4-cyclohexanediamine to perform post-chain extension reaction, standing for 8h, and removing acetone to obtain the fluorine-containing self-healing waterborne polyurethane.
Comparative example 1
A preparation method of fluorine-containing self-healing waterborne polyurethane comprises the following steps:
weighing 90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of organosilicon polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate, adding into a three-neck flask, and stirring at 90 ℃ for reacting for 2 hours; then, 4.9g of dimethylolpropionic acid, 3.97g of 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol, 0.84g of trimethylolpropane and 15g of acetone were added to the three-necked flask, and the reaction was continued with stirring at 80 ℃ for 2 hours; then adding 0.29g of organic bismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; and then adding 120g of acetone, cooling the obtained prepolymer to 50 ℃, adding 3.69g of triethylamine to react for 3min, cooling the prepolymer to 10 ℃, discharging the prepolymer to a plum blossom barrel, adding 303g of distilled water to a dispersion machine, emulsifying and opening, wherein the rotating speed of the dispersion machine is 2800r/min, finally adding 4.12g of 1, 4-cyclohexanediamine to perform post-chain extension reaction, standing for 8h, and removing acetone to obtain the fluorine-containing self-healing waterborne polyurethane.
Comparative example 2
A preparation method of conventional waterborne polyurethane comprises the following steps:
weighing 90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of organosilicon polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate, adding into a three-neck flask, and stirring at 90 ℃ for reacting for 2 hours; then 4.9g of dimethylolpropionic acid, 1.66g of 1, 4-butanediol, 0.84g of trimethylolpropane and 15g of acetone are respectively added into the three-neck flask, and the mixture is stirred and reacted for 2 hours at the temperature of 80 ℃; then adding 0.29g of organic bismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then adding 120g of acetone, cooling the obtained prepolymer to 50 ℃, adding 3.69g of triethylamine to react for 3min, cooling the prepolymer to 10 ℃, then discharging the prepolymer to a plum blossom barrel, adding 299g of distilled water to a dispersion machine to emulsify and open, wherein the rotating speed of the dispersion machine is 2800r/min, finally adding 4.12g of 1, 4-cyclohexanediamine to carry out post-chain extension reaction, standing for 8h, and removing acetone to obtain the waterborne polyurethane.
The content of 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol in the above examples 1, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol in the comparative examples 1, 2 is 5%, 2.5%, 0% of the prepolymer, respectively, the resins prepared in examples 1, 2,3, 1, 2 are formed into films, then 2 pieces of 10cm by 1cm by 0.1cm of sample strips are taken for each group, one group is directly tested for mechanical properties, and the original mechanical property test result is obtained; and cutting another group of cracks with the width of 2mm, then putting the cracks into a drying oven with the temperature of 150 ℃ for heating for 1 hour, observing the self-healing condition, and finally carrying out mechanical property test to obtain the mechanical property test result of the notch self-healing sample. The mechanical property test standard is referred to GB/T1040-. The mechanical property test results are shown in table 1, and fig. 1 is an optical microscope image of the self-healing change condition of the sample strip at different time periods.
TABLE 1
Figure BDA0003514838760000051
Figure BDA0003514838760000061
As can be seen from the above tests, the notched bars of examples 1, 2,3 and 1 were substantially self-healing after heating in an oven, and the healing effect was better as the fluorine-containing group content increased, and comparative example 2 did not heal. The mechanical properties of the unnotched sample strips of example 1, example 2, example 3 and comparative example 1 and the sample strips after the self-healing are basically consistent, while the notched sample strips of comparative example 2 can not self-heal, the notched sample strips cannot obtain the mechanical data, and the notched sample strips are directly fractured after being applied with force by a tensile machine in the testing process.
The material with the self-healing function is synthesized and prepared by using micromolecular fluorine-containing dihydric alcohol (2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol) as a waterborne polyurethane chain extender, wherein the main chain of the material contains a fluorine functional group and has a strong hydrogen bond effect, so that the intermolecular force is strong, and the material has very excellent self-healing performance; due to the existence of the hydrophilic chain extender, the material has excellent hydrophilic performance and hydrophilic characteristic similar to epidermis; because the material takes water as a solvent, the material has excellent environmental protection performance; because fluorine exists in a molecular chain, the heat resistance of the material is excellent; because the silicone polyether polyol is introduced into the main chain of the waterborne polyurethane, the material has the touch feeling which is very close to the skin. Based on the excellent performance of the material, the material has wide application prospect in the aspects of artificial skin, wearable equipment, artificial limb epidermis and the like.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A preparation method of a fluorine-containing self-healing waterborne polyurethane artificial skin material is characterized by comprising the following steps: isocyanate, macromolecular polyol, organosilicon polyether polyol, a hydrophilic chain extender, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol and a micromolecular chain extender react under the action of a catalyst to prepare a prepolymer, and then a neutralizer and a post chain extender are added to react to prepare the fluorine-containing self-healing waterborne polyurethane.
2. The method of claim 1, wherein: the isocyanate comprises one or more of isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, toluene-2, 4-diisocyanate and diphenylmethane diisocyanate.
3. The method of claim 1, wherein: the macromolecular polyol comprises one or more of polyether polyol, polytetrahydrofuran polyol, polyester polyol and polycarbonate polyol.
4. The method of claim 1, wherein: the hydrophilic chain extender comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid and sulfonate type hydrophilic chain extenders.
5. The method of claim 1, wherein: the small molecular chain extender comprises one or more of 2-methyl-1, 3-propanediol, 1, 4-butanediol, cyclohexanedimethanol and trimethylolpropane.
6. The method of claim 1, wherein: the post-chain extender comprises one or more of ethylenediamine, hexamethylenediamine, isophorone diamine and 1, 4-cyclohexanedimethylamine.
7. The method of claim 1, wherein: the catalyst comprises one or more of an organic bismuth catalyst, a zirconium catalyst and a manganese catalyst.
8. The method of claim 1, wherein: the neutralizing agent comprises one or more of triethylamine, ammonia water, triethanolamine and sodium hydroxide.
9. The method of claim 1, wherein: the proportion of the 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol is 1-10% of the mass of the aqueous polyurethane prepolymer; the proportion of the organic silicon polyether polyol is 5-35% of the mass of the waterborne polyurethane prepolymer; the proportion of the catalyst is 0.1-0.3% of the mass of the waterborne polyurethane prepolymer.
10. The fluorine-containing self-healing waterborne polyurethane artificial skin material according to any one of claims 1 to 9 is used for preparing wearable equipment and artificial limb skins.
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