CN118005885A - Deep eutectic solvent, thermoplastic polyurethane elastomer prepared from deep eutectic solvent and preparation method of thermoplastic polyurethane elastomer - Google Patents
Deep eutectic solvent, thermoplastic polyurethane elastomer prepared from deep eutectic solvent and preparation method of thermoplastic polyurethane elastomer Download PDFInfo
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- CN118005885A CN118005885A CN202410423096.6A CN202410423096A CN118005885A CN 118005885 A CN118005885 A CN 118005885A CN 202410423096 A CN202410423096 A CN 202410423096A CN 118005885 A CN118005885 A CN 118005885A
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- eutectic solvent
- deep eutectic
- thermoplastic polyurethane
- amino acid
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- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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Abstract
The invention provides a deep eutectic solvent, a thermoplastic polyurethane elastomer prepared from the deep eutectic solvent and a preparation method of the thermoplastic polyurethane elastomer, and belongs to the field of biomedical materials. The deep eutectic solvent is composed of the following components in mole fraction: 0.5-3.5 parts of amino acid, 0.5-3.5 parts of dihydric alcohol, 0.5-3.5 parts of alkali and 0-1 part of quaternary ammonium salt chain extender, wherein the molar parts of the amino acid and the alkali are equal, and the melting point of the dihydric alcohol is not higher than-20 ℃. The deep eutectic solvent system can be used for chain extension steps of thermoplastic polyurethane preparation, amino acid is simply, conveniently and efficiently successfully synthesized to a polyurethane main chain under the condition of no water or organic solvent, and the prepared thermoplastic polyurethane has excellent bioactivity and mechanical properties and has good application prospect in biomedical materials.
Description
Technical Field
The invention provides a deep eutectic solvent, a thermoplastic polyurethane elastomer prepared from the deep eutectic solvent and a preparation method of the thermoplastic polyurethane elastomer, and belongs to the field of biomedical materials.
Background
Imparting biological activity to biomedical thermoplastic elastomers by simple means is a difficult challenge. The polymerization of amino acids, which are natural small molecules involved in metabolism in living bodies, as chain extenders onto thermoplastic polyurethane elastomers is one possible approach to solve the above-mentioned problems. However, amino acids have a large number of polar groups (such as amino groups, carboxyl groups and hydroxyl groups), which makes the intermolecular force of the amino acid strong, the melting point close to or even higher than the decomposition temperature, and the refractory characteristic makes the amino groups on the amino acid molecule have low reactivity with isocyanate, so that the amino groups are directly added into a polymerization system as a chain extender to participate in the reaction, and thus, the polymerization to the main chain of thermoplastic polyurethane has great difficulty.
In addition, also because of the strong intermolecular forces of the amino acids, they are only readily soluble in very polar solvents such as methanol or water, but such solvents are highly reactive with isocyanate groups and can lead to side reactions during synthesis, for example water can easily lead to crosslinking during polyurethane preparation. Therefore, the conventional strategy of using amino acid chain-extended thermoplastic polyurethane is to disperse amino acids with organic solvents with higher polarity and high boiling point, such as N, N-dimethylformamide or trichloromethane, and then add a polymerization system to participate in chain extension, but the reaction efficiency of amino acids and isocyanate is still not high enough, the polyurethane molecular weight is difficult to be improved, and the residue of organic solvents can cause inflammation when the material is subsequently implanted into the body due to the fact that the solubility of amino acids in the organic solvents is very low.
In addition, researchers have attempted to take other strategies, such as the use of amino acid based ionic liquids or synthetic amino acid derivatives, to overcome the disadvantages of the amino acids themselves being poorly soluble and having a high melting point. The publication CN114907546a proposes a method for synthesizing a multifunctional polyureaurethane derivative, wherein the amino acid derivative concerned is prepared by complex organic synthesis under severe conditions or under the participation of highly toxic phosgene, which is contrary to the principle of green chemistry and limits the industrialized application. While the amino acid ionic liquid disclosed in the patent application publication No. CN109970584A solves the problem of high melting point of amino acid and is simple and convenient to prepare, the amino acid ionic liquid can damage the mechanical property of materials because of inert components in the ionic liquid, and monohydroxy components (such as choline) can interfere with the normal chain extension reaction of polyurethane in the synthesis process, so that the amino acid ionic liquid cannot be used for synthesizing thermoplastic polyurethane. Thus, it remains a challenge to obtain amino acid chain extended thermoplastic polyurethanes with excellent biocompatibility and mechanical properties using simple and green methods and for application as biomedical materials.
Disclosure of Invention
The invention provides a deep eutectic solvent which comprises the following components in parts by mole: 0.5-3.5 parts of amino acid, 0.5-3.5 parts of dihydric alcohol, 0.5-3.5 parts of alkali and 0-1 part of quaternary ammonium salt chain extender; the molar parts of the amino acid and the alkali are equal, and the melting point of the dihydric alcohol is not higher than-20 ℃.
Further, the deep eutectic solvent consists of the following components in parts by mole: 1 part of amino acid, 1 part of dihydric alcohol and 1 part of alkali; or 1 part of amino acid, 1 part of dihydric alcohol, 1 part of alkali and 1 part of quaternary ammonium salt chain extender.
Further, the amino acid is any one or more of lysine, arginine, serine, threonine, proline, histidine, tryptophan, aspartic acid, tyrosine, glutamic acid, glycine, leucine, phenylalanine, and alanine;
The dihydric alcohol is one or more of 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol and 1, 3-butanediol;
The alkali is one or more of sodium hydroxide, triethylamine, N-methyl morpholine, N-ethyl morpholine, potassium hydroxide, triethylenediamine, dimethylcyclohexylamine, tetramethyl ethylenediamine and dimethylethanolamine;
The quaternary ammonium salt chain extender comprises the following components: wherein R is hydroxyl or amino, X is halogen; p and q are independently selected from integers of 1 to 5, and n is selected from integers of 2 to 17.
Further, the amino acid is arginine, the dihydric alcohol is 1, 2-propylene glycol, the alkali is sodium hydroxide, and the quaternary ammonium salt chain extender is:
Or (b)
。
The invention also provides application of the deep eutectic solvent in preparation of thermoplastic polyurethane elastomer.
The invention also provides thermoplastic polyurethane which is prepared from the raw materials comprising the deep eutectic solvent.
Further, the thermoplastic polyurethane is prepared from the following raw materials in parts by mole: 100 parts of macromolecular diol, 200-450 parts of diisocyanate and 100-350 parts of deep eutectic solvent, preferably 100 parts of macromolecular diol, 380-420 parts of diisocyanate and 280-320 parts of deep eutectic solvent.
Further, the thermoplastic polyurethane is prepared from the following raw materials in parts by mole: 100 parts of macromolecular diol, 400 parts of diisocyanate and 300 parts of deep eutectic solvent.
Further, in the thermoplastic polyurethane raw material, the macromolecular diol is polycaprolactone diol or a mixture of the macromolecular diol and other macromolecular diols, wherein the mole fraction of the polycaprolactone diol in the mixture is not less than 50%; the other macromolecular diols are any one or a mixture of more than one of polycarbonate diol, polylactic acid diol and polyethylene glycol; preferably, the macrodiol is a polycaprolactone diol;
the diisocyanate is any one or a mixture of a plurality of isophorone diisocyanate, dicyclohexylmethane diisocyanate, lysine ethyl ester diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate and cyclohexane dimethylene diisocyanate; preferably isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate; more preferably isophorone diisocyanate.
The invention also provides a preparation method of the thermoplastic polyurethane, which comprises the following steps:
(1) The dried and dehydrated macromolecular diol and diisocyanate react for at least 2 hours at the temperature of 82-88 ℃;
(2) And (3) reducing the temperature to 67-73 ℃, adding a deep eutectic solvent, and reacting for at least 6 hours at 110-130 ℃.
The invention has the beneficial effects that: the invention provides an amino acid deep eutectic solvent system with excellent stability, which is composed of specific types and proportions of raw materials, can be used for chain extension steps of thermoplastic polyurethane preparation, can simply and efficiently successfully synthesize amino acid to a polyurethane main chain, and can prepare the thermoplastic polyurethane with excellent bioactivity and mechanical properties by amino acid chain extension, thereby having good application prospects in biomedical materials.
The macromolecular dihydric alcohol disclosed by the invention is dihydric alcohol with the index average molecular weight not lower than 400.
The quaternary ammonium salt chain extender disclosed by the invention is a quaternary ammonium salt compound with a structure comprising 2 hydroxyl groups or 2 amino groups and at least one quaternary ammonium group, wherein the carbon chain length of the quaternary ammonium group is not less than 4 carbons.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a DSC test of a deep eutectic solvent of the present invention.
FIG. 2 is the results of stability testing of the deep eutectic solvent of the present invention and the comparative example.
Figure 3 is the FTIR test results of the deep eutectic solvent chain extended TPU of the present invention.
FIG. 4 is the degradation performance test results of the deep eutectic solvent extended TPU of the present invention and a comparative example TPU.
FIG. 5 is an ultraviolet absorption spectrum of a degradation solution of the deep eutectic solvent chain extended TPU of the present invention.
Detailed Description
EXAMPLE 1 preparation of deep eutectic solvent A
1, 2-Propanediol, L-lysine, sodium hydroxide according to 1:1:1, dissolving in water, and completely evaporating the water in the system by using a rotary evaporator to obtain transparent homogeneous yellowish liquid, thus obtaining the deep eutectic solvent A.
EXAMPLE 2 preparation of deep eutectic solvent B
The preparation method is the same as in example 1, except that L-lysine is replaced with L-arginine to obtain deep eutectic solvent B.
Example 3 preparation of deep eutectic solvent C
The preparation was identical to example 2, except that half of the L-lysine was replaced with L-serine to give deep eutectic solvent C.
Example 4 preparation of deep eutectic solvent D
1, 2-Propylene glycol, L-lysine, sodium hydroxide and a quaternary ammonium salt chain extender Q6 are dissolved in water according to the molar ratio of 1:1:1:1, and the water in the system is completely evaporated by using a rotary evaporator to obtain transparent homogeneous light yellow liquid, so as to obtain a deep eutectic solvent D. The structure of the quaternary ammonium salt chain extender Q6 is as follows:
。
Example 5 preparation of deep eutectic solvent E
The preparation process is the same as in example 4 except that the quaternary ammonium salt chain extender Q6 is replaced with a quaternary ammonium salt chain extender Q12 to the deep eutectic solvent E. The structure of the quaternary ammonium salt chain extender Q12 is as follows:
。
Comparative example 1
The sodium hydroxide used in example 1 was 0 part, and the deep eutectic solvent could not be obtained under the same conditions.
Comparative example 2
The deep eutectic solvent cannot be obtained by substituting L-lysine for L-serine in example 1 under the same conditions.
Comparative example 3
The 1, 2-propanediol in example 1 was changed to ethylene glycol, and the conditions were not changed, so that the prepared deep eutectic solvent was unstable, and after 18 hours, amino acid was crystallized and precipitated in the deep eutectic solvent.
TABLE 1 relation of molar amounts of starting materials for examples and comparative examples of deep eutectic solvents
EXAMPLE 6 Synthesis of Thermoplastic Polyurethane (TPU)
100 Parts of dried and dehydrated polycaprolactone diol (number average molecular weight 1000) and 400 parts of isophorone diisocyanate are subjected to heat preservation and prepolymerization reaction for 2 hours at 85+/-3 ℃ under the action of a catalyst, the temperature is reduced to about 70 ℃, 300 parts of deep eutectic solvent in the example 1 is added, and the uniformly mixed prepolymer is poured into a blowing oven for reaction for 6 hours at 120 ℃ in a tetrafluoroethylene mold, so that the thermoplastic polyurethane Lys-TPU is obtained.
Example 7 Synthesis of thermoplastic polyurethane
The preparation is identical to example 6, except that 100 parts of polycaprolactone diol (number average molecular weight 1000) are replaced by a mixture of 50 parts of polycaprolactone diol (number average molecular weight 1000) and 50 parts of polycarbonate diol (number average molecular weight 1000).
Example 8 Synthesis of thermoplastic polyurethane
The preparation process is identical to example 6, except that isophorone diisocyanate is replaced by dicyclohexylmethane diisocyanate.
Example 9 Synthesis of thermoplastic polyurethane
The preparation process is identical to example 6, except that the deep eutectic solvent of example 1 is replaced with the deep eutectic solvent of example 2.
Example 10 Synthesis of thermoplastic polyurethane
The preparation process is identical to example 6, except that the deep eutectic solvent of example 1 is replaced with the deep eutectic solvent of example 3.
Comparative example 4
The preparation process is identical to example 5, except that the polycaprolactone diol is completely replaced by a polycarbonate diol.
Comparative example 5
The preparation process is identical to example 5, except that isophorone diisocyanate is replaced by hexamethylene diisocyanate.
Comparative example 6
The preparation process was identical to example 5, except that isophorone diisocyanate was replaced with lysine ethyl ester diisocyanate.
Comparative example 7
The preparation method is the same as in example 5, except that the PG-PU is prepared by replacing the deep eutectic solvent with 1, 2-propanediol.
Comparative example 8
100 Parts of dried and dehydrated polycaprolactone diol (number average molecular weight 1000) and 400 parts of isophorone diisocyanate are subjected to a heat preservation prepolymerization reaction for 2 hours at 85+/-3 ℃ under the action of a catalyst, the temperature is reduced to about 70 ℃, 100mL of DMF is added into the prepolymer, then 150 parts of lysine and 150 parts of 1, 2-propanediol are added into the mixture (namely 300 parts of comparative example 1 are added), and the mixture is reacted for 10 hours at 80 ℃ to obtain the thermoplastic polyurethane CTPU of the control sample.
TABLE 2 relation of molar amounts of raw materials for thermoplastic polyurethane examples and comparative examples
Experimental example 1 characterization of the deep eutectic solvent of the invention
DSC test: taking 5-8mg of the deep eutectic solvent in examples 1,2 and 3, 4 and 5, testing a sample of the deep eutectic solvent by using a differential scanning calorimeter with the model DSC250 manufactured by TA company of America, wherein the test mode is set to be LN2P mode, the temperature program is to firstly cool to-90 ℃, then keep the temperature for 5min, then adopt the heating rate of 10 ℃/min to heat to 0 ℃, and the whole test process is protected by adopting high-purity N 2.
As a result, as shown in FIG. 1, all the deep eutectic solvents showed a distinct step at low temperature, which is much smaller than the melting point of the amino acid, indicating that the amino acid was present in amorphous form in the deep eutectic solvent, which was successfully synthesized.
Deep eutectic solvent stability test: the deep eutectic solvents of example 1, example 2, example 3, example 4, example 5, and the systems of comparative examples 1,2, and 3 were taken and observed after being left to stand at room temperature for 1 month in a dark and dry condition at 25 ℃ to see if a clear and transparent liquid state was maintained.
The results are shown in FIG. 2, and after 1 month of standing, the deep eutectic solvent of the example is still clear and transparent, and the system is stable. The system of the comparative example shows different degrees of precipitation and stability failure.
Experimental example 2 characterization of thermoplastic polyurethane of the invention
FTIR test: the TPU synthesized in examples 6-10 and comparative examples 4-8 was used for infrared spectroscopy test using an infrared spectrometer model NICOLET iS manufactured by Thermo FISHER SCIENTIFIC company, the test mode was total reflection (ATR), the number of scans was set to 32, the resolution was set to 4cm -1, and the collection range of the spectra was set to 4000-600cm -1.
As a result, as shown in FIG. 3, the complete disappearance of the isocyanate peak near 2250 cm -1 indicates successful synthesis of the urethane structure. The broad peak at 3335cm -1 is the-N-H stretching vibration of the polymer. Further, the infrared absorption peak in the range of 1600 cm -1 to 1800 cm -1 corresponds to urethane carbonyl groups and urea carbonyl groups in the polymer matrix, and the peak appearing at 1712cm -1 is attributed to the stretching vibration of the urethane carbonyl groups. Another peak of 1630cm -1 is attributed to the stretching vibration of the urea carbonyl group; the peak at 1460 cm -1 is the bending vibration of the-N-H bond. Whereas there are two small peaks at 961cm -1 and 1232cm -1 corresponding to-O-c=o and-C-N bond formation. The presence of all these bonds confirms the presence of urethane groups and urea groups in the polymer, a successful synthesis of thermoplastic polyurethane.
Experimental example 3 molecular weight test of thermoplastic polyurethane of the invention
The TPU synthesized in examples 6-10 and comparative examples 4-8 was dissolved in chromatographically pure N, N-dimethylformamide to prepare a solution of 2-3 mg/mL. Characterization was performed using Waters-1515 gel permeation chromatography. The mobile phase of the instrument is DMF solution with LiBr concentration of 2 g/L, the flow rate of the mobile phase is 1 mL/min, and the test temperature is 40 ℃. The relative molecular weight of the TPU, calibrated with monodisperse polymethyl methacrylate (PMMA), was detected using a differential detector.
The results are shown in Table 3:
TABLE 3 Table 3
Although the IR spectrum results showed successful polymerization and 2250 cm -1 did not show the appearance of a peak for-NCO, the molecular weight of the synthesized polyurethane differed from the deep eutectic solvent for the different monomers. As can be seen from the results of this experimental example, the molecular weight of the polyurethane of the example is not much different or even slightly higher than that of the polyurethane of comparative example 7 obtained by chain extension with an equivalent amount of chain extender containing no amino acid, which indicates that the polyurethane backbone can be successfully synthesized by using a specific deep eutectic solvent as the chain extender in the example of the present invention. The molecular weights of comparative examples 4-6 and comparative example 8 are significantly lower than those of examples, wherein the comparative result of comparative example 4 proves that the mole fraction of polycaprolactone diol in the macrodiol cannot be lower than 50%; the comparison results of comparative examples 5 and 6 prove that the reactivity of isocyanate cannot be too strong, otherwise, the prepolymer and amino acid can undergo side reaction, one part of the prepolymer is solidified into gel, the other part of the prepolymer does not react at all, the reaction is uneven, the molecular weight distribution is wide, the processability is poor, the mobile phase is dissolved in the GPC test process and is the part with low molecular weight, a large amount of insoluble gel exists in the matrix, and the data of the molecular weight test are low. In addition, the comparison of comparative example 8 demonstrates that the use of DMF as a solvent, without the deep eutectic solvent of the present invention, does not successfully polymerize amino acids onto the TPU backbone, and therefore the TPU molecular weight is lower.
The present invention focuses on the polymerization of amino acids on the TPU backbone, and the following experimental examples will focus on the characterization of properties of polyurethanes with different amino acids in the backbone.
Experimental example 4 characterization of the thermoplastic polyurethane Properties of the backbone of the invention containing amino acids
Hemolysis test: the TPU of example 6, example 9, example 10, and the PG-PU of comparative example 7 were taken. Taking fresh venous blood of a person into a blood collection tube containing an anticoagulant, centrifugally washing for 3 times, collecting only red blood cells, and adding physiological saline into the blood collection tube to form 10% red blood cell suspension. And (3) carrying out gradient half-half dilution on the sample to obtain a sample diluent with the concentration range of 500 mu g/mL-7.8125 mu g/mL. The sample dilutions were added to equal volumes of red blood cell suspension and incubated for 1h in a 37℃incubator. Centrifugation, taking 200. Mu.L of the supernatant into a 96-well plate, measuring absorbance at 570nm using a microplate reader, and calculating the hemolysis rate using the following formula: hemolysis ratio (%) = (a_sample-a_negative)/(a_positive-a_negative) ×100%
Physiological saline containing 1% triton x 100 was used as a positive control and pure physiological saline was used as a negative control.
The results are shown in table 4, the TPU film using amino acids as chain extenders has significantly lower hemolysis and better biocompatibility.
TABLE 4 Table 4
Degradation test: after taking the TPU of example 6, example 9, example 10 and the PG-PU spline of comparative example 7, the spline was put into an EP tube, immersed in 3 mol/L sodium hydroxide solution, put into an oven at 80 ℃ for degradation, after 72 hours, the morphology of the sample in the EP tube was observed, and the degradation liquid was subjected to ultraviolet absorption spectrum test.
The traditional polycaprolactone soft segment TPU can be completely degraded only in two years, the degradation rate is not matched with the tissue repair rate, and the application scene is limited. The degradation test result of the TPU is shown in figure 4, and it can be seen that the TPU using the amino acid chain extension is degraded faster, namely the degradation rate can be greatly improved after the TPU main chain successfully introduces the amino acid, and the TPU main chain is more beneficial to matching the tissue repair rate. Meanwhile, according to the ultraviolet absorption spectrum (figure 5), the absorption peak of the TPU with the lysine chain extension appears near 202nm, the ultraviolet absorption of the TPU with the arginine chain extension appears near 205nm, and the ultraviolet absorption peak of the TPU with the lysine and serine chain extension appears at 230nm, which indicates that the thermoplastic polyurethane with the amino acid added as the chain extender can release the amino acid in the degradation process. It is known in the art that basic amino acids (e.g., arginine and lysine) can prevent the enrichment of carboxylic acids produced by polycaprolactone degradation at tissues to cause inflammation, the degraded arginine can be used as an NO donor to facilitate hemostasis, and serine can be used as a neurotransmitter; thus, the TPU of the present invention can also produce more beneficial bioactivity during degradation through the release of amino acids.
Mechanical property test: the TPU of example 6, example 9, example 10, and the PG-PU of comparative example 7 were cut into dumbbell-shaped standard bars, the stretching rate was set to 300mm/min, and the tensile properties of the polyurethane in the dry state were tested using a universal tester model HZ-1004 manufactured by Dongguan force display instruments and technologies Co. The test for each spline included five parallel samples.
The results are shown in Table 5, where polyurethane chain extended with deep eutectic solvent exhibits more excellent mechanical properties.
TABLE 5
In summary, the invention provides an amino acid deep eutectic solvent system with excellent stability, which can be used in a chain extension step (without dissolving amino acid with water or an organic solvent) for preparing thermoplastic polyurethane, can simply and efficiently and successfully synthesize amino acid on a polyurethane main chain, provides excellent bioactivity and mechanical properties, and has good application prospect in biomedical materials.
Claims (10)
1. The deep eutectic solvent is characterized by comprising the following components in parts by mole: 0.5-3.5 parts of amino acid, 0.5-3.5 parts of dihydric alcohol, 0.5-3.5 parts of alkali and 0-1 part of quaternary ammonium salt chain extender; the molar parts of the amino acid and the alkali are equal, and the melting point of the dihydric alcohol is not higher than-20 ℃.
2. The deep eutectic solvent of claim 1, consisting of the following components in parts by mole: 1 part of amino acid, 1 part of dihydric alcohol and 1 part of alkali; or 1 part of amino acid, 1 part of dihydric alcohol, 1 part of alkali and 1 part of quaternary ammonium salt chain extender.
3. The deep eutectic solvent of claim 1 or 2, wherein the amino acid is any one or more of lysine, arginine, serine, threonine, proline, histidine, tryptophan, aspartic acid, tyrosine, glutamic acid, glycine, leucine, phenylalanine, alanine;
the dihydric alcohol is any one or more of 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol and 1, 3-butanediol;
The alkali is any one or more of sodium hydroxide, triethylamine, N-methyl morpholine, N-ethyl morpholine, potassium hydroxide, triethylenediamine, dimethylcyclohexylamine, tetramethyl ethylenediamine and dimethylethanolamine;
The quaternary ammonium salt chain extender is as follows: wherein R is hydroxyl or amino, X is halogen; p and q are independently selected from integers of 1 to 5, and n is selected from integers of 2 to 17.
4. The deep eutectic solvent of claim 3, wherein the amino acid is arginine, the glycol is 1, 2-propanediol, the base is sodium hydroxide, and the quaternary ammonium salt chain extender is:
Or (b)
。
5. Use of the deep eutectic solvent according to any one of claims 1 to 4 for the preparation of thermoplastic polyurethane elastomers.
6. A thermoplastic polyurethane prepared from a raw material comprising the deep eutectic solvent according to any one of claims 1 to 4.
7. The thermoplastic polyurethane of claim 6, prepared from the following raw materials in parts by mole: 100 parts of macromolecular diol, 200-450 parts of diisocyanate and 100-350 parts of deep eutectic solvent.
8. The thermoplastic polyurethane of claim 7, prepared from the following raw materials in parts by mole: 100 parts of macromolecular diol, 400 parts of diisocyanate and 300 parts of deep eutectic solvent.
9. The thermoplastic polyurethane according to claim 7 or 8, wherein the macrodiol is a polycaprolactone diol or a mixture thereof with other macrodiols, the mole fraction of polycaprolactone diol in the mixture being not less than 50%; the other macromolecular diols are any one or a mixture of more than one of polycarbonate diol, polylactic acid diol and polyethylene glycol;
The diisocyanate is any one or a mixture of a plurality of isophorone diisocyanate, dicyclohexylmethane diisocyanate, lysine ethyl ester diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate and cyclohexane dimethylene diisocyanate.
10. The method for preparing the thermoplastic polyurethane according to any one of claims 6 to 9, characterized by comprising the steps of:
(1) The dried and dehydrated macromolecular diol and diisocyanate react for at least 2 hours at the temperature of 82-88 ℃;
(2) And (3) reducing the temperature to 67-73 ℃, adding a deep eutectic solvent, and reacting for at least 6 hours at 110-130 ℃.
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Citations (5)
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US20050209428A1 (en) * | 2002-06-19 | 2005-09-22 | Krishnan Tamareselvy | Breathable polyurethanes, blends, and articles |
CN102161743A (en) * | 2009-12-14 | 2011-08-24 | 气体产品与化学公司 | Solvent free aqueous polyurethane dispersions and methods of making and using the same |
CN108840991A (en) * | 2018-03-28 | 2018-11-20 | 四川大学 | The hydrophobic water-base polyurethane material and its preparation method and application of outer layer hydrophilic inner layer |
CN113382753A (en) * | 2018-10-24 | 2021-09-10 | 瑟拉诺沃有限公司 | Deep eutectic solvent platform for oral pharmaceutical formulations |
US20220305401A1 (en) * | 2019-06-20 | 2022-09-29 | Givaudan Sa | Eutectic extraction of solids |
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Patent Citations (5)
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US20050209428A1 (en) * | 2002-06-19 | 2005-09-22 | Krishnan Tamareselvy | Breathable polyurethanes, blends, and articles |
CN102161743A (en) * | 2009-12-14 | 2011-08-24 | 气体产品与化学公司 | Solvent free aqueous polyurethane dispersions and methods of making and using the same |
CN108840991A (en) * | 2018-03-28 | 2018-11-20 | 四川大学 | The hydrophobic water-base polyurethane material and its preparation method and application of outer layer hydrophilic inner layer |
CN113382753A (en) * | 2018-10-24 | 2021-09-10 | 瑟拉诺沃有限公司 | Deep eutectic solvent platform for oral pharmaceutical formulations |
US20220305401A1 (en) * | 2019-06-20 | 2022-09-29 | Givaudan Sa | Eutectic extraction of solids |
Non-Patent Citations (1)
Title |
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WEI DING,等: ""Amino acids assisted to improve the voltage window of deep eutectic electrolyte formed by ethylene glycol and tetra methyl ammonium chloride "", 《CHEMICAL ENGINEERING JOURNAL》, vol. 457, 28 February 2023 (2023-02-28), pages 141143 * |
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