CN115044003B - Preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material - Google Patents

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

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CN115044003B
CN115044003B CN202210163139.2A CN202210163139A CN115044003B CN 115044003 B CN115044003 B CN 115044003B CN 202210163139 A CN202210163139 A CN 202210163139A CN 115044003 B CN115044003 B CN 115044003B
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chain extender
fluorine
healing
aqueous polyurethane
catalyst
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CN115044003A (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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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material, which relates to the technical field of aqueous polyurethane materials, and comprises the steps of preparing a prepolymer by reacting isocyanate, macromolecular polyol, organosilicon polyether polyol, hydrophilic chain extender, 2,3, 4-hexafluoro-1, 5-pentanediol and micromolecular chain extender under the action of a catalyst, and then adding a neutralizer and a post-chain extender for reaction to prepare the fluorine-containing self-healing aqueous polyurethane; the fluorine-containing waterborne polyurethane prepared by the invention has very excellent self-healing capacity, environment-friendly performance, heat resistance and touch feeling similar to human skin, and fills the gap that no material with self-healing and hydrophilic performance is developed at home and abroad.

Description

Preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material
Technical field:
the invention relates to the technical field of aqueous polyurethane materials, in particular to a preparation method of a fluorine-containing self-healing aqueous polyurethane artificial skin material.
The background technology is as follows:
as the demand for intelligent wearable devices increases, the market for preparing a material very similar to human skin is becoming more and more urgent. At present, a plurality of scientific research institutions and universities are mainly focused on simulating human skin by using materials such as silicone rubber, 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 in a humid environment; scientific researchers also research an artificial skin material with hydrophilic performance at home and abroad, but the self-healing performance is poor, and the human skin has the self-healing performance. In summary, materials with self-healing and excellent hydrophilic properties will closely approximate human skin.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing a preparation method of fluorine-containing self-healing aqueous polyurethane, which has the advantages of excellent self-healing capacity, excellent hydrophilic performance, good environmental protection performance, good heat resistance and touch feeling close to human skin, and has wide application prospect in the aspects of artificial skin, wearable equipment, artificial limb epidermis and the like.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the invention provides a preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material, which comprises the steps of preparing a prepolymer by reacting isocyanate, macromolecular polyol, organic silicon polyether polyol, a hydrophilic chain extender, 2,3, 4-hexafluoro-1, 5-pentanediol and a small molecular chain extender under the action of a catalyst, and then adding a neutralizing agent and a rear chain extender to react.
2,3, 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 stronger hydrogen bonding effect and strong intermolecular force, and therefore, the material has excellent self-healing capacity; due to the existence of the hydrophilic chain extender, the material has excellent hydrophilic performance and skin-like hydrophilic property; because the material takes water as a solvent, the material has excellent environmental protection performance; because fluorine element exists in a molecular chain, the heat resistance of the material is excellent; because the organic silicon polyether polyol is introduced into the main chain of the water-based polyurethane, the material has touch feeling very close to 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 polyols (PPG series), polytetrahydrofuran polyols (PTMG series), polyester polyols and polycarbo polyols.
The hydrophilic chain extender comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid and sulfonate type hydrophilic chain extender.
The small molecule chain extender comprises one or more of 2-methyl-1, 3-propanediol (MPO), 1, 4-Butanediol (BDO), cyclohexanedimethanol (CHDM) and Trimethylolpropane (TMP).
The rear chain extender comprises one or more of ethylenediamine, hexamethylenediamine, isophorone diamine and 1, 4-cyclohexanediamine.
The catalyst comprises one or more of an organobismuth catalyst, a zirconium catalyst and a manganese catalyst.
The neutralizing agent comprises one or more of triethylamine, ammonia water, triethanolamine and sodium hydroxide.
The 2,3, 4-hexafluoro-1, 5-pentanediol accounts for 1-10% of the mass of the waterborne polyurethane prepolymer.
The organosilicon polyether polyol accounts for 5-35% of the mass of the waterborne polyurethane prepolymer.
The catalyst accounts for 0.1 to 0.3 percent of the mass of the waterborne polyurethane prepolymer.
The fluorine-containing self-healing aqueous polyurethane artificial skin material is also used for preparing wearable equipment and artificial limb epidermis.
The beneficial effects of the invention are as follows: the fluorine-containing self-healing water-based polyurethane is prepared by reacting isocyanate, macromolecular polyol, organic silicon polyether polyol, a hydrophilic chain extender and 2,3, 4-hexafluoro-1, 5-pentanediol according to a certain proportion at a certain temperature to form a prepolymer, and then emulsifying, opening and adding the prepolymer to chain extend; 2,3, 4-hexafluoro-1, 5-pentanediol, organic silicon polyether polyol and hydrophilic chain extender are introduced into the waterborne polyurethane, so that the material has very excellent self-healing capacity, environment-friendly performance, heat resistance and touch feeling similar to human skin, and fills the gap that no self-healing and hydrophilic material is developed at home and abroad.
Description of the drawings:
FIG. 1 is an optical microscope image of the self-healing variation of a spline over different time periods.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The following examples and comparative examples were purchased from ala Ding Shiji, inc except that the catalyst was purchased from Yu Deyin chemistry.
Example 1
The preparation method of the fluorine-containing self-healing aqueous polyurethane comprises the following steps:
90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of silicone polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate are weighed into a three-neck flask, and stirred at 90 ℃ for reaction for 2 hours; then, 4.9g of dimethylolpropionic acid, 8g of 2,3, 4-hexafluoro-1, 5-pentanediol, 0.1g of trimethylolpropane and 15g of acetone are respectively added into a three-neck flask, and the mixture is continuously stirred at 80 ℃ for reaction for 2 hours; then adding 0.3g of organobismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then 120g of acetone is added, the obtained prepolymer is cooled to 50 ℃, 3.69g of triethylamine is added for reaction for 3min, the prepolymer is cooled to 10 ℃, then the prepolymer is discharged to a plum blossom barrel, 307g of distilled water is added into a dispersing machine for emulsification and opening, the rotating speed of the dispersing machine is 2800r/min, finally 2.81g of 1, 4-cyclohexanediamine is added for post-chain extension reaction, and the acetone is removed after the mixture is placed for 8h, thus obtaining the fluorine-containing self-healing aqueous polyurethane.
Example 2
The preparation method of the fluorine-containing self-healing aqueous polyurethane comprises the following steps:
90g of polyether polyol PPG-3000 (molecular weight 3000), 18g of silicone polyether polyol (molecular weight 1800) and 31.97g of isophorone diisocyanate are weighed into a three-neck flask, and stirred at 90 ℃ for reaction for 2 hours; then, 4.9g of dimethylolpropionic acid, 8g of 2,3, 4-hexafluoro-1, 5-pentanediol, 0.1g of trimethylolpropane and 15g of acetone are respectively added into a three-neck flask, and the mixture is continuously stirred at 80 ℃ for reaction for 2 hours; then adding 0.3g of organobismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then 120g of acetone is added, the obtained prepolymer is cooled to 50 ℃, 3.69g of triethylamine is added for reaction for 3min, the prepolymer is cooled to 10 ℃, then the prepolymer is discharged to a plum blossom barrel, 296g of distilled water is added into a dispersing machine for emulsification and opening, the rotating speed of the dispersing machine is 2800r/min, and finally 2.81g of 1, 4-cyclohexanediamine is added for post-chain extension reaction, and acetone is removed after the mixture is placed for 8h, thus obtaining the fluorine-containing self-healing aqueous polyurethane.
Example 3
The preparation method of the fluorine-containing self-healing aqueous polyurethane comprises the following steps:
90g of a polycarbon polyol PCD-3000 (molecular weight: 3000), 18g of a silicone polyether polyol (molecular weight: 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate were weighed into a three-necked flask, and reacted at 90℃with stirring for 2 hours; then, 4.9g of dimethylolpropionic acid, 8g of 2,3, 4-hexafluoro-1, 5-pentanediol, 0.1g of trimethylolpropane and 15g of acetone are respectively added into a three-neck flask, and the mixture is continuously stirred at 80 ℃ for reaction for 2 hours; then adding 0.3g of organobismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then 120g of acetone is added, the obtained prepolymer is cooled to 50 ℃, 3.69g of triethylamine is added for reaction for 3min, the prepolymer is cooled to 10 ℃, then the prepolymer is discharged to a plum blossom barrel, 307g of distilled water is added into a dispersing machine for emulsification and opening, the rotating speed of the dispersing machine is 2800r/min, finally 2.81g of 1, 4-cyclohexanediamine is added for post-chain extension reaction, and the acetone is removed after the mixture is placed for 8h, thus obtaining the fluorine-containing self-healing aqueous polyurethane.
Comparative example 1
The preparation method of the fluorine-containing self-healing aqueous polyurethane comprises the following steps:
90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of silicone polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate are weighed into a three-neck flask, and stirred at 90 ℃ for reaction for 2 hours; then, 4.9g of dimethylolpropionic acid, 3.97g 2,2,3,3,4,4-hexafluoro-1, 5-pentanediol, 0.84g of trimethylolpropane and 15g of acetone are respectively added into the three-neck flask, and the mixture is continuously stirred at 80 ℃ for reaction for 2 hours; then adding 0.29g of organobismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then 120g of acetone is added, the obtained prepolymer is cooled to 50 ℃, 3.69g of triethylamine is added for reaction for 3min, the prepolymer is cooled to 10 ℃, then the prepolymer is discharged to a plum blossom barrel, 303g of distilled water is added into a dispersing machine for emulsification and opening, the rotating speed of the dispersing machine is 2800r/min, finally 4.12g of 1, 4-cyclohexanediamine is added for post-chain extension reaction, and acetone is removed after the mixture is placed for 8h, thus obtaining the fluorine-containing self-healing aqueous polyurethane.
Comparative example 2
The preparation method of the conventional aqueous polyurethane comprises the following steps:
90g of polytetrahydrofuran polyol (molecular weight 3000), 18g of silicone polyether polyol (molecular weight 1800) and 37.73g of 4, 4-dicyclohexylmethane diisocyanate are weighed into a three-neck flask, and stirred at 90 ℃ for reaction 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 stirring reaction is continued for 2 hours at 80 ℃; then adding 0.29g of organobismuth catalyst DY-20 and 10g of acetone, cooling the reaction temperature to 70 ℃, and continuing the reaction for 3 hours; then 120g of acetone is added, the obtained prepolymer is cooled to 50 ℃, 3.69g of triethylamine is added for reaction for 3min, the prepolymer is cooled to 10 ℃, then the prepolymer is discharged to a plum blossom barrel, 299g of distilled water is added into a dispersing machine for emulsification and opening, the rotating speed of the dispersing machine is 2800r/min, finally 4.12g of 1, 4-cyclohexanediamine is added for post-chain extension reaction, and acetone is removed after the reaction is placed for 8h, thus obtaining the waterborne polyurethane.
The content of 2,3, 4-hexafluoro-1, 5-pentanediol in the prepolymer in the above examples 1, 2,3, 4-hexafluoro-1, 5-pentanediol in the comparative example 1, 2, 5, 2.5 and 0%, respectively forming the resins prepared in the examples 1, 2,3, 1 and 2 into films, and then respectively taking 2 pieces of 10cm 1cm 0.1cm sample bars from each group, wherein one group directly performs mechanical property test to obtain an original mechanical property test result; and the other group of cracks with the width of 2mm are cut, then the cracks are put into a baking oven with the temperature of 150 ℃ for heating for 1 hour, the self-healing condition is observed, and finally the mechanical property test is carried out, so that the mechanical property test result of the notch self-healing sample is obtained. The mechanical property test standard is referred to GB/T1040-1992. 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 spline in different time periods.
TABLE 1
From the above test, it was found that the notched bars of example 1, example 2, example 3 and comparative example 1 were substantially self-healing after heating in an oven, and the better the healing effect, the less healed, comparative example 2. The notched bars of example 1, example 2, example 3 and comparative example 1 are substantially identical in mechanical properties to the notched but self-healing bars, whereas the notched bars of comparative example 2 are not self-healing and the notched bar mechanical data is not available and the tensile machine breaks directly immediately after application of force during the test.
The invention utilizes small molecular fluorine-containing dihydric alcohol (2, 3, 4-hexafluoro-1, 5-pentanediol) as a waterborne polyurethane chain extender to prepare the material with self-healing function, and the main chain of the material contains fluorine functional groups which have stronger hydrogen bonding effect, so that the intermolecular acting force is strong, thereby endowing the material with excellent self-healing performance; due to the existence of the hydrophilic chain extender, the material has excellent hydrophilic performance and skin-like hydrophilic property; because the material takes water as a solvent, the material has excellent environmental protection performance; because fluorine element exists in a molecular chain, the heat resistance of the material is excellent; because the organic silicon polyether polyol is introduced into the main chain of the water-based polyurethane, the material has touch feeling very close to skin. Based on the excellent performance of the material, the material has wide application prospect in the aspects of artificial skin, wearable equipment, prosthetic epidermis and the like.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. 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 aqueous polyurethane artificial skin material is characterized by comprising the following steps: the preparation method comprises the steps of reacting isocyanate, macromolecular polyol, organic silicon polyether polyol, hydrophilic chain extender, 2,3, 4-hexafluoro-1, 5-pentanediol and micromolecular chain extender under the action of a catalyst to prepare a prepolymer, and then adding a neutralizing agent and a post-chain extender to react to prepare the fluorine-containing self-healing aqueous polyurethane.
2. The method of manufacturing according to claim 1, characterized in that: 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 manufacturing according to claim 1, characterized in that: the macromolecular polyol comprises one or more of polyether polyol, polytetrahydrofuran polyol, polyester polyol and polycarbo polyol.
4. The method of manufacturing according to claim 1, characterized in that: the hydrophilic chain extender comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid and sulfonate type hydrophilic chain extender.
5. The method of manufacturing according to claim 1, characterized in that: the small molecule chain extender comprises one or more of 2-methyl-1, 3-propanediol, 1, 4-butanediol, cyclohexanedimethanol and trimethylolpropane.
6. The method of manufacturing according to claim 1, characterized in that: the rear chain extender comprises one or more of ethylenediamine, hexamethylenediamine, isophorone diamine and 1, 4-cyclohexanediamine.
7. The method of manufacturing according to claim 1, characterized in that: the catalyst comprises one or more of an organobismuth catalyst, a zirconium catalyst and a manganese catalyst.
8. The method of manufacturing according to claim 1, characterized in that: the neutralizing agent comprises one or more of triethylamine, ammonia water, triethanolamine and sodium hydroxide.
9. The method of manufacturing according to claim 1, characterized in that: the 2,3, 4-hexafluoro-1, 5-pentanediol accounts for 1-10% of the mass of the waterborne polyurethane prepolymer; the organosilicon polyether polyol accounts for 5-35% of the mass of the waterborne polyurethane prepolymer; the catalyst accounts for 0.1 to 0.3 percent of the mass of the waterborne polyurethane prepolymer.
10. Use of the fluorine-containing self-healing aqueous polyurethane artificial skin material according to any of claims 1-9 for the preparation of wearable devices and prosthetic skins.
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