CN115850638A - Biodegradable polyurethane elastomer, preparation method thereof and elastomer sponge with porous structure - Google Patents
Biodegradable polyurethane elastomer, preparation method thereof and elastomer sponge with porous structure Download PDFInfo
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- CN115850638A CN115850638A CN202211606693.XA CN202211606693A CN115850638A CN 115850638 A CN115850638 A CN 115850638A CN 202211606693 A CN202211606693 A CN 202211606693A CN 115850638 A CN115850638 A CN 115850638A
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a biodegradable polyurethane elastomer, a preparation method thereof and an elastomer sponge with a porous structure, wherein the polyurethane elastomer preparation raw materials comprise polyesteramide polylol, diisocyanate and a chain extender; the raw materials for preparing the polyesteramide polylol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride. The polyurethane elastomer prepared by adopting the raw materials has good biodegradability and biocompatibility, and also has higher tensile strength and elongation at break. The polyurethane elastomer sponge is prepared by a method of solution freeze drying or supercritical carbon dioxide foaming, and has good elasticity and degradability.
Description
Technical Field
The invention belongs to the technical field of medical materials, and particularly relates to a biodegradable polyurethane elastomer, a preparation method thereof and an elastomer sponge with a porous structure.
Background
The biomedical polyurethane elastomer is widely applied to manufacturing various infusion catheters and disposable medical devices for clinical use due to good physicochemical and mechanical properties. With the development of drug controlled release and tissue engineering technologies, higher requirements are put forward on the performance of medical polymer materials, so that the development of polyurethane elastomers with good biocompatibility and biodegradability becomes an important direction in the field.
CN1771061B provides a method for preparing amphiphilic degradable polyol by ring-opening polymerization of epsilon-caprolactone, glycolide and DL-lactide initiated by polyethylene glycol, and a biodegradable polyurethane elastomer is obtained by further chain extension with tetramethylene diisocyanate and butanediol. The elastomer is formulated into a polymer solution, and the biomedical foam is prepared by freeze-drying and used for sinus or other cavity tamponade. CN112386747B provides a method for preparing polyurethane elastomer from epsilon-caprolactone polyol, and a biodegradable ureteral stent tube is obtained by co-extrusion with polylactic acid and polyglycolic acid copolymer. CN102002142A provides a novel polyalkylene carbonate-polylactide polyurethane material with biodegradability and good elasticity developed by chain extension reaction using polyalkylene carbonate glycol-polylactide block copolymer glycol as raw material.
Currently, although some biodegradable polyurethane elastomers have been developed, these materials all have two major drawbacks: (1) The biodegradable polyurethane polyol is prepared by utilizing the ring-opening reaction of lactide or cyclic ester, the reaction needs to be carried out under strict anhydrous and anaerobic conditions, the reaction conditions are harsh, and higher requirements are also imposed on reaction equipment; (2) The lactide or cyclic ester has a single chemical structure and limited types, so that the structural change of the synthesized polyol is limited, the obtained polyurethane does not have a reactive group which can be further functionalized, and the adjustable range of the degradation and mechanical properties of the polyurethane is narrow.
Disclosure of Invention
In view of the above, the present invention aims to provide a biodegradable polyurethane elastomer having excellent elasticity, a method for preparing the same, and an elastomer sponge having a porous structure.
The invention provides a biodegradable polyurethane elastomer, which is prepared from raw materials including polyesteramide polylol, diisocyanate and a chain extender;
the raw materials for preparing the polyesteramide polyol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride.
In the present invention, the natural α -amino acid and its derivatives are selected from one or more of leucine, alanine, tryptophan, phenylalanine, isoleucine, glycine, arginine, valine, methionine, γ -benzyl-L-glutamate, γ -methyl-L-glutamate, β -benzyl-L-aspartate, β -methyl-L-aspartate, O-benzyl-L-serine, N (e) -benzyloxycarbonyl-lysine and N (e) -t-butoxycarbonyl-lysine;
the amino alcohol is selected from amino alkanol containing 2-20 carbon atoms, amino-terminated polyethylene glycol with molecular weight of 100-20000, amino-terminated polypropylene glycol with molecular weight of 100-20000 or amino-terminated polytetramethylene glycol with molecular weight of 100-20000.
In the invention, the number of carbon atoms of the dibasic acid is 3 to 20;
the number of carbon atoms of the binary acyl chloride is 3-20;
the number of carbon atoms of the dihydric alcohol is 2 to 20.
In the present invention, the diisocyanate is selected from one or more of hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.
Preferably, the chain extender is selected from one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, and 1, 6-hexanediol.
The invention provides a preparation method of the biodegradable polyurethane elastomer, which comprises the following steps:
reacting dibasic acid or dibasic acyl chloride with a nitro-substituted phenol compound to obtain an electrophilic monomer;
reacting dihydric alcohol, natural alpha-amino acid and derivatives thereof with p-toluenesulfonic acid to obtain a nucleophilic monomer;
carrying out solution polycondensation on the nucleophilic monomer and the electrophilic monomer, and then reacting with amino alcohol to obtain polyesteramide polyol;
and reacting the polyester amide polyol, diisocyanate and a chain extender to obtain the polyurethane elastomer.
Preferably, the molar ratio of electrophilic monomer and nucleophilic monomer is 10 to 1.005.
The invention provides an elastomer sponge with a porous structure, which is prepared by adopting freeze drying or supercritical carbon dioxide foaming of the biodegradable polyurethane elastomer in the technical scheme.
Preferably, the porosity of the elastomer sponge with a porous structure is 90-95%.
The invention provides a biodegradable polyurethane elastomer, which is prepared from raw materials including polyesteramide polylol, diisocyanate and a chain extender; the raw materials for preparing the polyesteramide polylol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride. The polyurethane elastomer prepared by adopting the raw materials has good biodegradability and biocompatibility, and also has higher tensile strength and elongation at break. The polyurethane elastomer sponge is prepared by a method of solution freeze drying or supercritical carbon dioxide foaming, and has good elasticity and degradability. The experimental results show that: the tensile strength of the polyurethane elastomer is 5-20 MPa; the elongation at break is 400-1300%. The compressive strength of the polyurethane elastomer sponge is 2-10 kPa; the porosity is 75-99%; the intrinsic viscosity loss is 10-35%.
Detailed Description
The invention provides a biodegradable polyurethane elastomer, which is prepared from polyester amide polylol, diisocyanate and a chain extender;
the raw materials for preparing the polyesteramide polyol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride.
The raw materials for preparing the biodegradable polyurethane elastomer comprise polyesteramide polylol. In the invention, the raw materials for preparing the polyesteramide polyol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride.
In the present invention, the natural α -amino acid and its derivatives are selected from one or more of leucine, alanine, tryptophan, phenylalanine, isoleucine, glycine, arginine, valine, methionine, γ -benzyl-L-glutamate, γ -methyl-L-glutamate, β -benzyl-L-aspartate, β -methyl-L-aspartate, O-benzyl-L-serine, N (e) -benzyloxycarbonyl-lysine and N (e) -t-butoxycarbonyl-lysine. The invention introduces natural alpha-amino acid into the synthesis of polyurethane, thereby greatly expanding the performance and application range of the synthesized polyurethane elastomer.
In the present invention, the aminoalcohol is selected from the group consisting of aminoalkanols containing 2 to 20 carbon atoms, amino-terminated polyethylene glycols having a molecular weight of 100 to 20000, amino-terminated polypropylene glycols having a molecular weight of 100 to 20000 or amino-terminated polytetramethylene glycols having a molecular weight of 100 to 20000.
In the invention, the number of carbon atoms of the dihydric alcohol is 2 to 20; the dihydric alcohol is specifically 1, 6-hexanediol.
In the invention, the number of carbon atoms of the dibasic acid is 3 to 20; the number of carbon atoms of the binary acyl chloride is 3-20.
The preparation raw materials of the biodegradable polyurethane elastomer provided by the invention comprise diisocyanate; the diisocyanate is selected from one or more of hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate and naphthalene diisocyanate.
The raw materials for preparing the biodegradable polyurethane elastomer comprise a chain extender, wherein the chain extender is one or more selected from ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
In the invention, the biodegradable polyurethane elastomer can be processed into polyurethane products and polyurethane films by injection molding, film coating or film blowing.
The invention provides a preparation method of the biodegradable polyurethane elastomer, which comprises the following steps:
reacting dibasic acid or dibasic acyl chloride with a nitro-substituted phenol compound to obtain an electrophilic monomer;
reacting dihydric alcohol, natural alpha-amino acid and derivatives thereof with p-toluenesulfonic acid to obtain a nucleophilic monomer;
carrying out solution polycondensation on the nucleophilic monomer and the electrophilic monomer, and then reacting with amino alcohol to obtain polyesteramide polyol;
and reacting the polyester amide polyol, diisocyanate and a chain extender to obtain the biodegradable polyurethane elastomer.
The preparation method adopts a solution polycondensation method of nucleophilic and electrophilic solid monomers, has the advantages of short polymerization time, low reaction temperature and the like, can effectively control the molecular weight by adjusting the molar ratio of the nucleophilic monomer to the electrophilic monomer, and is simpler and easier than the ring-opening polymerization of lactide and cyclic ester. Another advantage of the synthesis method is that by selecting raw materials with different chemical structures, polyesteramide polyols with various physicochemical and mechanical properties are obtained, and then polyurethane elastomers with different properties are obtained, for example, by introducing a polyethylene glycol chain segment with hydrophilicity, polyurethane elastomers with amphipathy are obtained.
The invention makes dibasic acid or dibasic acyl chloride react with nitro-substituted phenol compound to obtain electrophilic monomer. The electrophilic monomer is diacid nitrophenol ester; the specific reaction route is as follows:
the R is 1 An alkyl group having 1 to 18 carbon atoms.
The nitro-substituted phenol compound is nitrophenol, dinitrophenol or trinitrophenol. In the invention, the temperature adopted in the preparation process of the electrophilic monomer is 70-150 ℃ and the time is 12-48 hours.
The invention makes dihydric alcohol, natural alpha-amino acid and its derivative react with p-toluenesulfonic acid to obtain nucleophilic monomer. The nucleophilic monomer is diol diamino acid ester p-toluenesulfonate. The specific reaction route is as follows:
in the invention, the temperature adopted in the preparation process of the nucleophilic monomer is 70-150 ℃ and the time is 12-48 hours.
The preparation method comprises the steps of carrying out solution polycondensation on the nucleophilic monomer and the electrophilic monomer, and then reacting with amino alcohol to obtain the polyesteramide polyol. Carrying out solution polycondensation on a nucleophilic monomer and an excessive electrophilic monomer; the molar ratio of the electrophilic monomer to the nucleophilic monomer is preferably 10 to 1.005. The molecular weight of the polyesteramide polyol is controlled by the molar ratio of nucleophilic monomer to electrophilic monomer. The reaction route for synthesizing polyesteramide polyol is as follows:
said H 2 N-R 3 OH is an aminoalkanol containing 2 to 20 carbon atoms and having a molecular weight of 100 to 20000Amino-terminated polyethylene glycol, amino-terminated polypropylene glycol with molecular weight of 100-20000 or amino-terminated polytetramethylene glycol with molecular weight of 100-20000.
In the invention, the solvent for solution polycondensation is dimethyl acetamide; the temperature of the polycondensation reaction is 75-85 ℃, and the time is 110-130 min. The temperature for the reaction with the amino alcohol is 75-85 ℃ and the time is 110-130 min.
The polyurethane elastomer is obtained by reacting the polyester amide polyol, the diisocyanate and the chain extender. The polymerization reaction route is as follows:
wherein HO-PEA-OH is polyesteramide polyalcohol; OCN-R 4 -NCO is diisocyanate; HO-R 5 -OH is a chain extender.
In the present invention, the molar ratio of the polyesteramide polyol, diisocyanate and chain extender is 1: 1.
the invention provides an elastomer sponge with a porous structure, which is prepared by adopting freeze drying or supercritical carbon dioxide foaming of the biodegradable polyurethane elastomer in the technical scheme.
In the present invention, the porosity of the elastomer sponge having a porous structure is 90 to 95%.
In the invention, the temperature of the freeze drying is-30 ℃, the pressure of the freeze drying is 0.1-10 Pa, and the time of the freeze drying is 24-72 hours; the pressure of the supercritical carbon dioxide is 15-18 MPa.
The elastomer sponge has good elasticity and degradability, can be used as hemostatic sponge for nasal cavities and auditory canals, performs compression hemostasis on wounds in the nasal cavities and the auditory canals, and gradually degrades into colloid after absorbing blood and interstitial fluid to flow out of the body.
In order to further illustrate the present invention, the biodegradable polyurethane elastomer, the preparation method thereof and the elastomer sponge having a porous structure according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Preparatory example 1
43.0g of p-nitrophenol and 43.1mL of triethylamine were dissolved in 500mL of acetone, and the solution was cooled in an ice-water bath at 0 ℃. Dissolving 28.5mL of sebacoyl chloride in 100mL of acetone, gradually dripping into a p-nitrophenol solution, heating the reaction to room temperature, carrying out stirring for 2 hours, carrying out suction filtration after the reaction is finished, and carrying out vacuum drying at 40 ℃ to constant weight.
Preparatory example 2
25.0g of phenylalanine, 31.7g of p-toluenesulfonic acid monohydrate and 8.8g of 1, 6-hexanediol were placed in a round-bottomed flask containing 300mL of toluene and equipped with a water separator. The reaction is refluxed for 2 hours under the condition of stirring, cooled to room temperature, filtered, and dried in vacuum at 40 ℃ to constant weight.
Example 1
Taking 8.9g of the electrophilic monomer synthesized in the preparative example 1 and 7.6g of the nucleophilic monomer synthesized in the preparative example 2 (mole ratio of electrophilic monomer to nucleophilic monomer is 2.
Example 2
Taking 8.9g of the electrophilic monomer synthesized in the preparative example 1 and 7.6g of the nucleophilic monomer synthesized in the preparative example 2 (mole ratio of electrophilic monomer to nucleophilic monomer is 2).
Example 3
9.0g of the polyesteramide polyol synthesized in example 1 was charged into a 50mL reaction flask, heated to 90 ℃ and added with 10 times excess Hexamethylene Diisocyanate (HDI) under mechanical stirring, after 2 hours of reaction, excess HDI was removed by distillation under reduced pressure, and 0.9g of butanediol was added to the reaction flask and the reaction was continued for 2 hours to obtain a polyurethane elastomer. The tensile strength of the polyurethane elastomer was determined to be 16MPa and the elongation at break was 740% according to ASTM D412.
Example 4
9.5g of the amphiphilic polyesteramide polyol synthesized in example 2 was taken and added into a 50mL reaction flask, after heating to 90 ℃, 10-fold excess HDI was added under mechanical stirring, after 2 hours of reaction, excess HDI was removed by reduced pressure distillation, and 0.45g of butanediol was added into the reaction flask to continue the reaction for 2 hours to obtain an amphiphilic polyurethane elastomer. The tensile strength of the amphiphilic polyurethane elastomer was determined to be 14MPa and the elongation at break was 910% according to ASTM D412.
Example 5:
1.0g of polyurethane elastomer strip sample synthesized in the example 3 is placed in a sealed high-pressure kettle, the high-pressure kettle is heated to 170-190 ℃, high-pressure carbon dioxide is introduced into the high-pressure kettle by using a high-pressure metering pump, the pressure of the high-pressure kettle is controlled to be 15.0-18.0 MPa, after the saturation time is 1-2 hours, a pressure relief valve is opened to carry out rapid pressure relief, the pressure relief rate is 6-8 MPa/s, and after the pressure relief is finished, the high-pressure kettle is opened to take out the foamed polyurethane sponge.
The compressive strength of the polyurethane sponge was determined to be 5.5kPa according to GB/T8813-2008.
The porosity of the polyurethane sponge was determined according to the formula "porosity = [ 1-sponge mass/(sponge volume × polyurethane density) ] × 100%", and was 94.3%;
the polyurethane sponge was immersed in a phosphate buffer solution with pH =7.4 ± 0.2 for 7 days, and the intrinsic viscosity loss of the polyurethane sponge was determined to be 21% according to the formula "intrinsic viscosity loss = [ (intrinsic viscosity before degradation-intrinsic viscosity after degradation)/intrinsic viscosity before degradation ] × 100%".
Example 6
1.0g of the amphiphilic polyurethane elastomer synthesized in example 4 was dissolved in 1, 4-dioxane to prepare a 1.5wt% polymer solution, the solution was filtered and poured into a mold, the polymer solution was frozen at-18 ℃ for 2 hours and then freeze-dried, and after 24 hours, a porous amphiphilic polyurethane sponge was taken out.
The compressive strength of the polyurethane sponge was determined to be 4.3kPa according to GB/T8813-2008.
The porosity of the polyurethane sponge was determined to be 93.0% according to the formula "porosity = [ 1-sponge mass/(sponge volume × polyurethane density) ] × 100%";
the polyurethane sponge was immersed in a phosphate buffer solution with pH =7.4 ± 0.2 for 7 days, and the intrinsic viscosity loss of the polyurethane sponge was determined to be 34% according to the formula "intrinsic viscosity loss = [ (intrinsic viscosity before degradation-intrinsic viscosity after degradation)/intrinsic viscosity before degradation ] × 100%".
From the above embodiments, the invention provides a biodegradable polyurethane elastomer, and the preparation raw materials include polyesteramide polyol, diisocyanate and chain extender; the raw materials for preparing the polyesteramide polyol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride. The polyurethane elastomer prepared by adopting the raw materials has good biodegradability and biocompatibility, and also has higher tensile strength and elongation at break. The polyurethane elastomer sponge is prepared by a method of solution freeze drying or supercritical carbon dioxide foaming, and has good elasticity and degradability. The experimental results show that: the tensile strength of the polyurethane elastomer is 5-20 MPa; the elongation at break is 400-1300%. The compressive strength of the polyurethane elastomer sponge is 2-10 kPa; the porosity is 75-99%; the intrinsic viscosity loss is 10-35%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A biodegradable polyurethane elastomer is prepared from polyester amide polylol, diisocyanate and a chain extender;
the raw materials for preparing the polyesteramide polyol comprise natural alpha-amino acid and derivatives thereof, amino alcohol, dihydric alcohol, dibasic acid or dibasic acyl chloride.
2. The biodegradable polyurethane elastomer according to claim 1, wherein the natural α -amino acid and its derivatives are selected from one or more of leucine, alanine, tryptophan, phenylalanine, isoleucine, glycine, arginine, valine, methionine, γ -benzyl-L-glutamate, γ -methyl-L-glutamate, β -benzyl-L-aspartate, β -methyl-L-aspartate, O-benzyl-L-serine, N (e) -benzyloxycarbonyl-lysine and N (e) -t-butoxycarbonyl-lysine;
the amino alcohol is selected from amino alkanol containing 2-20 carbon atoms, amino-terminated polyethylene glycol with molecular weight of 100-20000, amino-terminated polypropylene glycol with molecular weight of 100-20000 or amino-terminated polytetramethylene glycol with molecular weight of 100-20000.
3. The biodegradable polyurethane elastomer according to claim 1, wherein the number of carbon atoms of the dibasic acid is 3 to 20;
the number of carbon atoms of the binary acyl chloride is 3-20;
the number of carbon atoms of the dihydric alcohol is 2 to 20.
4. The biodegradable polyurethane elastomer according to claim 1, wherein the diisocyanate is selected from one or more of hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.
5. The biodegradable polyurethane elastomer according to claim 1, wherein the chain extender is selected from one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, and 1, 6-hexylene glycol.
6. A method for preparing the biodegradable polyurethane elastomer of claim 1, comprising the steps of:
reacting dibasic acid or dibasic acyl chloride with a nitro-substituted phenol compound to obtain an electrophilic monomer;
reacting dihydric alcohol, natural alpha-amino acid and derivatives thereof with p-toluenesulfonic acid to obtain a nucleophilic monomer;
carrying out solution polycondensation on the nucleophilic monomer and the electrophilic monomer, and then reacting with amino alcohol to obtain polyesteramide polyol;
and reacting the polyester amide polyol, diisocyanate and a chain extender to obtain the polyurethane elastomer.
7. The method according to claim 6, wherein the molar ratio of the electrophilic monomer to the nucleophilic monomer is 10 to 1.005.
8. An elastomer sponge with a porous structure, which is prepared from the biodegradable polyurethane elastomer as claimed in any one of claims 1 to 5 by freeze drying or supercritical carbon dioxide foaming.
9. The cellular structure elastomer sponge according to claim 8, wherein the cellular structure elastomer sponge has a porosity of 90 to 95%.
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