CN114213615B - Swelling-resistant phosphorylcholine modified polyurethane material and preparation method thereof - Google Patents
Swelling-resistant phosphorylcholine modified polyurethane material and preparation method thereof Download PDFInfo
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- CN114213615B CN114213615B CN202111648192.3A CN202111648192A CN114213615B CN 114213615 B CN114213615 B CN 114213615B CN 202111648192 A CN202111648192 A CN 202111648192A CN 114213615 B CN114213615 B CN 114213615B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a swelling-resistant phosphorylcholine modified polyurethane material which comprises the following components in parts by mass: 24-72 parts of micromolecular diol and 90-235 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 20-41 parts of diisocyanate. Compared with the prior art, the swelling-resistant phosphorylcholine modified polyurethane material provided by the invention can effectively ensure key performances such as mechanical strength, swelling resistance and the like, and has very strong application value and significance; the low polymer polyol is not used in the components, the content of functional group phosphorylcholine of the material can be greatly improved, and the expression of the functional group is obvious. The polyurethane material can effectively balance the steric hindrance and the water absorption of phosphorylcholine, so that strong hydrogen bonds are formed among the polyurethane materials, the polyurethane material with high content of phosphorylcholine is obtained, and the hydrophilicity, the mechanical modulus response characteristic and the swelling resistance of the polyurethane material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a swelling-resistant phosphorylcholine modified polyurethane material and a preparation method thereof.
Background
The hydrophilic functional chain segment is bonded into the polyurethane chain segment, which is a common modified polyurethane construction method, and in order to have a good hydrophilic effect, a functional chain segment with a high proportion generally needs to be keyed in, but in practice, the addition of the hydrophilic chain segment is found to influence the mechanical property of a bulk material, the mechanical property of the material is reduced due to swelling of the material, the material is degraded with the lapse of time, and the above problems become more obvious with the increase of the proportion of the hydrophilic chain segment.
In the prior art, glycerophosphorylcholine is generally used as a modifier to synthesize hydrophilic polyurethane, although the initial mechanical property of the material is good, the problem that the mechanical property is greatly reduced after the material is soaked in water for a long time is solved, and the application of the material is limited. Researchers have proposed methods such as introducing fluorocarbon chains and replacing the types of oligomer polyols to construct phosphorylcholine-type modified polyurethane, but the method still has difficulty to be overcome in the aspect of long-term stability of the material.
The patent name is a polyether polyurethane material containing phosphorylcholine groups on side chains and a preparation method thereof, the publication number is CN 106674484A, the patent name is a high-biocompatibility phosphorylcholine modified polyurethane material and a preparation method thereof, the patent with the publication number of CN 106589290A discloses phosphorylcholine polyurethane synthesized by introducing phosphorylcholine as a chain extender into polymer molecular chain side groups and other forms, in order to ensure mechanical properties, oligomer polyol is used, the content of the functional group phosphorylcholine is directly lower, the general knowledge in the industry is that the density of the functional group can directly influence the function expression effect of the material, the introduction of the oligomer polyol can reduce the expression chance of the functional group phosphorylcholine at an interface, and the problem of function modification reduction is caused.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the swelling-resistant phosphorylcholine modified polyurethane material, compared with the prior art, the swelling-resistant phosphorylcholine modified polyurethane material can effectively ensure the key performances such as mechanical strength, swelling resistance and the like, and has strong application value and significance; and the components do not use oligomer polyol, so that the content of functional group phosphorylcholine of the material can be greatly improved, and the expression of the functional group is obvious. In addition, the swelling-resistant phosphorylcholine modified polyurethane material can effectively balance the steric hindrance and the water absorbability of phosphorylcholine, so that strong hydrogen bonds are formed among polyurethane materials, the polyurethane material with high phosphorylcholine content is obtained, and the hydrophilicity, the mechanical modulus response characteristic and the swelling resistance of the polyurethane material are effectively improved. The invention also provides a preparation method of the swelling-resistant phosphorylcholine modified polyurethane material, which is characterized in that a polyurethane material is synthesized by directly adopting a method of polymerizing a micromolecule chain extender and polyisocyanate under the condition of not depending on oligomer polyol; the swelling problem of phosphorylcholine modified polyurethane in the prior art is solved, the obtained material has high content of phosphorylcholine, good hydrophilicity and good mechanical modulus response characteristic, is stable for a long time after water absorption balance, and does not change the water absorption rate and the swelling property; and the mechanical property is stable, and the degradation does not occur in the environment of water or simulated body fluid.
The technical effect to be achieved by the invention is realized by the following technical scheme:
the swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 24-72 parts of micromolecular diol and 90-235 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 20-41 parts of diisocyanate; wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol.
As a preferable scheme, the composition comprises the following components in parts by mass: 48-72 parts of micromolecular diol and 235 parts of diisocyanate 176-; and (B) component: 100 parts of glycerophosphorylcholine and 20-26 parts of diisocyanate; wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing a preset amount of the component A dried as above into a solvent, and reacting for a period of time under a preset temperature condition;
s02, adding a preset amount of the dried component B for reaction overnight;
s03, precipitating or evaporating the reacted product to dryness, and vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
As one preferable example, in the S01 step, the solvent is a mixed solvent including one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
As a preferable scheme, in the S01 step, the component A with the expected dry amount is mixed in the solvent and reacted for 0.5h to 8h under the temperature condition of 30 ℃ to 80 ℃.
As one of the preferable schemes, in the step S02, the time for the reaction to stay overnight after the component B is added is 8h-10 h.
In a preferable scheme, in the step S03, the reacted product is precipitated in ether, washed for multiple times, and vacuum dried at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
As a preferable mode, in the S03 step, the volume of the ether is 3-10 times that of the product.
In a preferred embodiment, in step S03, the precipitated product is washed with one or a mixture of water and ethanol.
In summary, the invention has at least the following advantages:
1. compared with the prior art, the swelling-resistant phosphorylcholine modified polyurethane material can effectively ensure the key performances such as mechanical strength, swelling resistance and the like, and has very strong application value and significance; and the components do not use oligomer polyol, so that the content of functional group phosphorylcholine of the material can be greatly improved, and the expression of the functional group is obvious.
2. The swelling-resistant phosphorylcholine modified polyurethane material can effectively balance the steric hindrance and the water absorption of phosphorylcholine, so that strong hydrogen bonds are formed among polyurethane materials, the polyurethane material with high phosphorylcholine content is obtained, and the hydrophilicity, the mechanical modulus response characteristic and the swelling resistance of the polyurethane material are effectively improved.
3. The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material directly adopts a method of polymerizing a micromolecule chain extender and polyisocyanate to synthesize the polyurethane material under the condition of not depending on oligomer polyol; the swelling problem of phosphorylcholine modified polyurethane in the prior art is solved, the obtained material has high content of phosphorylcholine, good hydrophilicity and good mechanical modulus response characteristic, is stable for a long time after water absorption balance, and does not change the water absorption rate and the swelling property; and the mechanical property is stable, and the degradation does not occur in the environment of water or simulated body fluid.
Drawings
FIG. 1 is a stress-strain curve diagram of a swelling-resistant phosphorylcholine-modified polyurethane material in an embodiment of the invention;
FIG. 2 is a graph showing the change of water absorption of the swelling-resistant phosphorylcholine-modified polyurethane material in the example of the present invention;
FIG. 3 is a graph comparing the change of tensile strength and elongation at break of swelling-resistant phosphorylcholine-modified polyurethane material in the examples of the present invention.
Detailed Description
In a first aspect, the invention provides a swelling-resistant phosphorylcholine modified polyurethane material, which comprises the following components in parts by mass: 24-72 parts of micromolecular diol and 90-235 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 20-41 parts of diisocyanate; wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol. The invention comprises a component A and a component B, wherein the component A does not use oligomer polyol, and the component A is directly polymerized by adopting a micromolecular chain extender and polyisocyanate to form a prepolymer; then, the prepolymer is combined with the component B to polymerize the swelling-resistant phosphorylcholine modified polyurethane material, the content of functional group phosphorylcholine of the material can be greatly improved, the expression of the functional group is obvious, and compared with the prior art, the swelling-resistant phosphorylcholine modified polyurethane material can effectively ensure the key performances such as mechanical strength, swelling resistance and the like, and has very strong application value and significance; and the components can effectively balance the steric hindrance and the water absorption of the phosphorylcholine, so that strong hydrogen bonds are formed among the polyurethane materials, the polyurethane material with high content of the phosphorylcholine is obtained, and the hydrophilicity, the mechanical modulus response characteristic and the swelling resistance of the polyurethane material are effectively improved.
The swelling-resistant phosphorylcholine modified polyurethane material disclosed by the invention is preferably prepared from the following components in parts by mass: 48-72 parts of micromolecular diol and 235 parts of diisocyanate 176-; and (B) component: 100 parts of glycerophosphorylcholine and 20-26 parts of diisocyanate; wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol.
In a second aspect, the invention also provides a preparation method of the swelling-resistant phosphorylcholine modified polyurethane material, which comprises the following steps:
s01, mixing the component A with the expected amount of drying into the solvent, and reacting for a period of time under the condition of the preset temperature;
s02, adding a pre-measured amount of dried component B for reaction overnight;
s03, precipitating or evaporating the reacted product to dryness, and vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Further, in the step S01, the solvent is a mixed solvent including one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide, and the reaction is carried out at a temperature of 30 ℃ to 80 ℃ for 0.5h to 8 h; in the step S02, the reaction time after adding the component B is 8h-10 h.
And in the step S03, precipitating the reacted product in ether, washing for many times, and drying in vacuum at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material. Preferably, the volume of the ether is 3-10 times of the volume of the product, and the precipitated product is washed with one or a mixed solvent of water and ethanol.
The present invention will now be described in detail with reference to specific examples, which are intended to be illustrative of the preferred embodiments of the present invention and are not to be construed as limiting the invention.
Example 1:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 72 parts of micromolecular diol and 235 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 26 parts of diisocyanate; wherein the small molecular diol is ethylene glycol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 72 parts of dried ethylene glycol and 235 parts of diisocyanate (HDI) in dimethyl sulfoxide (DMSO), and reacting at 50 ℃ for 2 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 26 parts by mass of diisocyanate (HDI) to react for 8 hours;
s03, precipitating the reacted product in 5 times volume of ether, and washing with ethanol solution for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 2:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 48 parts of small molecular diol and 176 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 20 parts of diisocyanate; wherein the small molecular diol is ethylene glycol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 48 parts of dried ethylene glycol and 176 parts of diisocyanate (HDI) in dimethyl sulfoxide (DMSO), and reacting at 50 ℃ for 2 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 20 parts by mass of diisocyanate (HDI) to react for 8 hours;
s03, precipitating the reacted product in 5 times volume of ether, and washing with ethanol solution for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 3:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 24 parts of small molecular diol and 90 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 41 parts of diisocyanate; wherein the small molecular diol is ethylene glycol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 24 parts of dried ethylene glycol and 90 parts of diisocyanate (HDI) in dimethyl sulfoxide (DMSO), and reacting at 50 ℃ for 2 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 41 parts by mass of diisocyanate (HDI) to react for 8 hours;
s03, precipitating the reacted product in 5 times volume of ether, and washing with ethanol solution for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 4:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 72 parts of micromolecular diol and 176 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 23 parts of diisocyanate; wherein the small molecular diol is 1, 3 butanediol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 72 parts of dried 1, 3-butanediol and 176 parts of diisocyanate (HDI) in a tetrahydrofuran solvent, and reacting at 30 ℃ for 1 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 23 parts by mass of diisocyanate (HDI) to react for 10 hours;
s03, precipitating the reacted product in 3 times volume of ether, and washing with a mixed solvent of water and ethanol for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 5:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 68 parts of small molecular diol and 227 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 23 parts of diisocyanate; wherein the small molecular diol is 1, 4 butanediol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 68 parts of dried 1, 4-butanediol and 227 parts of diisocyanate (HDI) in a tetrahydrofuran solvent, and reacting at 80 ℃ for 8 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 23 parts by mass of diisocyanate (HDI) to react for 10 hours;
s03, precipitating the reacted product in 10 times volume of ether, and washing with a mixed solvent of water and ethanol for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 6:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 68 parts of small molecular diol and 227 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 23 parts of diisocyanate; wherein the small molecular diol is 1, 4 butanediol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 68 parts of dried 1, 4-butanediol and 227 parts of diisocyanate (HDI) in N, N-dimethylformamide and reacting at 80 ℃ for 8 h;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 23 parts by mass of diisocyanate (HDI) to react for 10 hours;
s03, precipitating the reacted product in 10 times volume of ether, and washing with a mixed solvent of water and ethanol for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 7:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 72 parts of micromolecular diol and 176 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 23 parts of diisocyanate; wherein the small molecular diol is 1, 3 butanediol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 72 parts of dried 1, 3-butanediol and 176 parts of diisocyanate (HDI) in a mixed solvent of N, N-dimethylformamide and N, N-dimethylacetamide, and reacting for 6h at 80 ℃;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 23 parts by mass of diisocyanate (HDI) to react for 10 hours;
s03, precipitating the reacted product in 3 times volume of ether, and washing three times with mixed solvent of water and ethanol to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Example 8:
a swelling-resistant phosphorylcholine modified polyurethane material comprises the following components in parts by mass: 72 parts of micromolecular diol and 235 parts of diisocyanate; and (B) component: 100 parts of glycerophosphorylcholine and 26 parts of diisocyanate; wherein the small molecular diol is ethylene glycol.
The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material comprises the following steps:
s01, mixing 72 parts of dried ethylene glycol and 235 parts of diisocyanate (HDI) in a mixed solvent of dimethyl sulfoxide (DMSO) and tetrahydrofuran, and reacting at 65 ℃ for 6 hours;
s02, adding 100 parts by mass of dried glycerophosphorylcholine and 26 parts by mass of diisocyanate (HDI) to react for 8 hours;
s03, precipitating the reacted product in 5 times volume of ether, and washing with ethanol solution for three times to remove small molecular raw materials or low molecular weight polymers possibly existing in the reactant; vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
Comparative example 1:
based on example 1, the difference is only that: in this comparative example 1, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 2:
based on example 2, the difference is only that: in this comparative example 2, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 3:
based on example 3, the difference is only that: in this comparative example 3, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 4:
based on example 4, the difference is only that: in this comparative example 4, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 5:
based on example 5, the difference is only that: in this comparative example 5, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 6:
based on example 6, the only difference is that: in this comparative example 6, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 7:
based on example 7, the only difference is that: in this comparative example 7, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Comparative example 8:
based on example 8, the difference is only that: in this comparative example 8, an equimolar amount of oligomer diol having a molecular weight of 1000 was used instead of the small molecule diol.
Test example 1: mechanical modulus response characteristic verification
Cutting the swelling-resistant phosphorylcholine modified polyurethane material obtained in the examples 1-8 into dumbbell-shaped sample strips by using national standard 4 x 75 dumbbell cutters respectively for testing, and performing tensile test on the dumbbell-shaped sample strips in a dry state and in a state of completely realizing equilibrium after soaking for 8 hours respectively to obtain stress-strain curves of the dumbbell-shaped sample strips as shown in the attached drawing 1; wherein E in the attached figure 1 represents the elastic modulus, and the elastic modulus is measured according to the calculation method of the elastic modulus in the national standard.
As can be seen from the stress-strain curve diagram of figure 1, the elastic modulus of the dumbbell-shaped sample strip is 764Mpa in a dry environment, and 30 Mpa in a water environment; therefore, the swelling-resistant phosphorylcholine modified polyurethane materials in the embodiments 1 to 8 show different mechanical properties in different environments, and have good mechanical response properties.
Test example 2: verification of hydrophilicity and swelling resistance
The swelling-resistant phosphorylcholine-modified polyurethane materials obtained in examples 1 to 8 were cut into long samples of 100mm × 10mm × 1mm, the long samples were weighed by mass in a dry state and in a state of being immersed in water for different times, and the change curve of the water absorption rate of the swelling-resistant phosphorylcholine-modified polyurethane material long samples of examples 1 to 8 was calculated from the change in mass as shown in fig. 2.
As can be seen from the small graph of the water absorption change curve of FIG. 2, the long sample reaches water absorption equilibrium within about 10 minutes; from the large graph of the water absorption change curve of fig. 2, it can be seen that the water absorption of the long sample is not changed in the subsequent 20 hours of soaking time; from this, it is understood that the swelling-resistant phosphorylcholine-modified polyurethane materials of examples 1 to 8 can reach a swelling equilibrium in a short time after being soaked, and the swelling resistance thereof does not change even when being soaked for a long time.
Test example 3: mechanical strength verification
The swelling-resistant phosphorylcholine-modified polyurethane materials obtained in examples 1 to 8 were respectively cut out into dumbbell-shaped sample strips by a national standard 4 x 75 dumbbell cutter for testing, and the tensile strength and elongation at break of the swelling-resistant phosphorylcholine-modified polyurethane material sample strips were compared with those of fig. 3 by testing the stress-strain curves of the swelling-resistant phosphorylcholine-modified polyurethane material sample strips in an initial equilibrium state and after being soaked in a PBS solution for 30 days by a tensile machine.
As can be seen from the comparison of the changes in tensile strength and elongation at break in FIG. 3, the tensile strength of the specimen at initial equilibrium is about 13 MPa and the elongation at break is about 275%; after the sample strips are soaked in the PBS solution for 30 strips, the tensile strength is about 10 Mpa, and the breaking elongation is about 290%; it can be seen that, after the swelling-resistant phosphorylcholine modified polyurethane material in examples 1 to 8 is soaked in the simulated liquid for 30 days, the tensile strength and the elongation at break of the swelling-resistant phosphorylcholine modified polyurethane material are not significantly changed, and it can be proved that the mechanical strength of the swelling-resistant phosphorylcholine modified polyurethane material is basically maintained unchanged after the swelling-resistant phosphorylcholine modified polyurethane material is soaked in the simulated liquid for 30 days.
Test example 4: improvement of surface hydrophilicity brought by increase of phosphorylcholine content
The swelling-resistant phosphorylcholine modified polyurethane materials obtained in examples 1 to 4 and comparative examples 1 to 4 were selected, and water static contact angles were used for testing, that is, a water drop was dropped on the surface of the material, a camera was used to rapidly capture the static shape of the water drop on the surface of the material, and the static water contact angle of the material was calculated by calculation software, and the results were as follows:
| phosphorylcholine content | Contact angle | |
| Example 1 | 23% | 28° |
| Example 2 | 29% | 21° |
| Example 3 | 46% | 15° |
| Example 4 | 23% | 29° |
| Comparative example 1 | 6.6% | 68° |
| Comparative example 2 | 9.3% | 56° |
| Comparative example 3 | 17.7% | 39° |
| Comparative example 4 | 9.1% | 59° |
Therefore, the phosphorylcholine content in the examples 1 to 4 is high, the static water contact angle is small, and the hydrophilicity of the material is strong; in comparative examples 1-4, phosphorylcholine content is low, static water contact angle is large, and material hydrophilicity is weak.
According to the technical scheme of the embodiment, the swelling-resistant phosphorylcholine modified polyurethane material provided by the invention can effectively ensure the key properties such as mechanical strength, swelling resistance and the like, and has strong application value and significance; and the components do not use oligomer polyol, so that the content of functional group phosphorylcholine of the material can be greatly improved, and the expression of the functional group is obvious. In addition, the steric hindrance and the water absorption of phosphorylcholine can be effectively balanced, so that strong hydrogen bonds are formed among polyurethane materials, the polyurethane material with high phosphorylcholine content is obtained, and the hydrophilicity, the mechanical modulus response characteristic and the swelling resistance of the polyurethane material are effectively improved. The invention also provides a preparation method of the swelling-resistant phosphorylcholine modified polyurethane material, which is characterized in that a polyurethane material is synthesized by directly adopting a method of polymerizing a micromolecule chain extender and polyisocyanate under the condition of not depending on oligomer polyol; the swelling problem of phosphorylcholine modified polyurethane in the prior art is solved, the obtained material has high content of phosphorylcholine, good hydrophilicity and good mechanical modulus response characteristic, is stable for a long time after water absorption balance, and does not change the water absorption rate and the swelling property; and the mechanical property is stable, and the degradation does not occur in the environment of water or simulated body fluid.
While the invention has been described in conjunction with the specific embodiments set forth above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and scope of the appended claims.
Claims (9)
1. The swelling-resistant phosphorylcholine modified polyurethane material is characterized by comprising the following components in parts by mass:
and (2) component A:
24-72 parts of micromolecular diol
90-235 parts of diisocyanate;
and (B) component:
100 portions of glycerophosphorylcholine
20-41 parts of diisocyanate;
wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol.
2. The phosphorylcholine-modified polyurethane material according to claim 1, characterized by consisting of the following components in parts by mass:
and (2) component A:
48-72 parts of micromolecular diol
176-235 parts of diisocyanate;
and (B) component:
100 portions of glycerophosphorylcholine
20-26 parts of diisocyanate;
wherein the small molecular diol is ethylene glycol, 1, 4 butanediol or 1, 3 butanediol.
3. A method for preparing the swelling-resistant phosphorylcholine modified polyurethane material according to claim 1 or 2, characterized by comprising the following steps:
s01, mixing the component A with the expected amount of drying into the solvent, and reacting for a period of time under the condition of the preset temperature;
s02, adding a pre-measured amount of dried component B for reaction overnight;
s03, precipitating or evaporating the reacted product to dryness, and vacuum drying at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
4. The method for preparing the swelling-resistant phosphorylcholine-modified polyurethane material according to claim 3, wherein in the step S01, the solvent is a mixed solvent including one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for preparing swelling-resistant phosphorylcholine modified polyurethane material according to claim 3, characterized in that, in step S01, the component A with a pre-determined amount of drying is mixed in a solvent and reacted for 0.5h-8h at the temperature of 30-80 ℃.
6. The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material according to claim 3, characterized in that in the step S02, the reaction time after adding the component B is 8h-10 h.
7. The preparation method of the swelling-resistant phosphorylcholine modified polyurethane material according to claim 3, characterized in that in the step S03, the product after reaction is precipitated in ether, washed for many times, and dried under vacuum at room temperature to obtain the swelling-resistant phosphorylcholine modified polyurethane material.
8. The method for preparing the swelling-resistant phosphorylcholine modified polyurethane material according to claim 7, wherein in the step S03, the volume of the diethyl ether is 3-10 times of that of the product.
9. The method for preparing a swelling-resistant phosphorylcholine-modified polyurethane material according to claim 7, wherein in step S03, the precipitated product is washed with one or two of water and ethanol.
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