CN116178666A - Polysiloxane polyurethane supermolecule elastomer and preparation method and application thereof - Google Patents

Abstract

The invention discloses a polysiloxane polyurethane supermolecule elastomer, which comprises the following raw materials: a polycarbonate diol, an amine-terminated polydimethylsiloxane, a diisocyanate, a first chain extender, a second chain extender, and a first catalyst; the first chain extender is a chain extender containing four hydrogen bonds. The invention also discloses a preparation method and application of the polysiloxane polyurethane supermolecular elastomer. The polysiloxane polyurethane supermolecular elastomer provided by the invention has the advantages that the raw materials are simple and easy to obtain, the introduction of the amino-terminated silicone oil increases the interaction among molecular chains, is beneficial to improving the mechanical strength and the dynamic property of the material, overcomes the defects of oxidation resistance stability and hydrolysis resistance stability existing in modified polyurethane, and can not simultaneously consider the defects of biological stability and mechanical stability and the defects of lower mechanical strength, higher modulus and low tearing strength existing in the existing polysiloxane-polyurethane, so that the polysiloxane polyurethane supermolecular elastomer is suitable for being used as a long-term medical implant material.

Description

Polysiloxane polyurethane supermolecule elastomer and preparation method and application thereof

Technical Field

The invention relates to the technical field of medical polyurethane materials, in particular to a polysiloxane polyurethane supermolecular elastomer, a preparation method and application thereof.

Background

Polyurethane (PU) has good blood compatibility, hemodynamics and mechanical properties, making it successful for biomedical applications. By means of their adjustable soft and hard two-phase sections, their stiffness and elasticity can be adjusted. But the degradable chemical bonds in the polyurethane material present a risk of degradation, for example: polyester-based polyurethanes have good dynamic viscoelasticity, but are susceptible to hydrolysis due to the presence of ester linkages in their backbone; polyether polyurethane has good hydrolysis resistance, but has insufficient oxidation aging resistance; polycarbonate-based polyurethanes, although improving the problems of hydrolysis and oxidation of polyester-based polyurethanes and polyether-based polyurethanes, have insufficient calcification resistance. Thus, there is an urgent need to modify or synthesize new polyurethanes to obtain better biostable materials that are both hydrolysis-resistant and oxidation-resistant.

Polysiloxane (PDMS) is one of the most widely used polymer materials for manufacturing biomedical devices, with high biocompatibility, excellent hydrolytic and oxidative stability, low toxicity, and high resistance to protein and platelet adhesion. In order to combine the good biostability of polysiloxane polymers with the excellent mechanical properties of polyurethanes, there have been many attempts to incorporate silicone segments into the hard segments of polyurethanes to improve the in vivo biomaterial properties of polysiloxane-polyurethanes. Although the current generation of silicone-based polyurethanes (e.g.: elast-Eon ^TM ) Having the required biostability and mechanical properties to fit a range of medical implants, but applications such as heart valves require materials with improved mechanical properties, such as: has high mechanical properties of tensile strength and tearing strength, low modulus and low cycle creep and long-term biostability.

Therefore, a polyurethane material which has improved mechanical strength, particularly tear strength while maintaining low modulus, and which has excellent hydrolytic stability and oxidation stability has been a technical problem to be solved.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is that the biological stability and the mechanical stability in the existing polyurethane research cannot be simultaneously considered, so that the polysiloxane polyurethane supermolecular elastomer material with good mechanical property and biological stability is provided, and the long-term implantation requirement of the polymer heart valve is met.

Therefore, the invention adopts the following technical scheme:

the invention provides a polysiloxane polyurethane supermolecular elastomer (SiPUE), which comprises the following raw materials: a polycarbonate diol, an amine-terminated polydimethylsiloxane, a diisocyanate, a first chain extender, a second chain extender, and a first catalyst;

the molar ratio of the sum of the active groups in the amine-terminated polydimethylsiloxane and the polycarbonate diol to the isocyanate groups of the diisocyanate is 1:1.2 to 2; the molar ratio of the polycarbonate diol to the amine-terminated polydimethylsiloxane is 1:2 to 5; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:3 to 9; the mass of the first catalyst accounts for 0.1-0.8% of the mass of all raw materials;

the first chain extender is a chain extender containing four hydrogen bonds.

Further, the molar ratio of the polycarbonate diol, the amine-terminated polydimethylsiloxane, the diisocyanate, and the reactive groups of the first chain extender and the second chain extender is 1:2 to 5:3.6 to 12:0.15 to 0.6:0.45 to 5.4.

The polycarbonate diol comprises Polytetramethylene Carbonate Diol (PCDL) with molecular weight of 1000-2000; the amine-terminated polydimethylsiloxane includes an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) ₂ ) The molecular weight of the catalyst is 1000-2000g/mol.

The preparation method of the amine butyl end-capped polydimethylsiloxane comprises the steps of mixing octamethyl cyclotetrasiloxane (D4) and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane (AMM), reacting under the action of a second catalyst to obtain a crude product, and distilling under reduced pressure to obtain the amine butyl end-capped polydimethylsiloxane.

The preparation method of the polytetramethylene carbonate glycol comprises the steps of taking diethyl carbonate (DEC) and 1, 4-Butanediol (BDO) as raw materials, reacting under the action of a third catalyst to obtain a crude product, and distilling under reduced pressure to obtain the polytetramethylene carbonate glycol.

The diisocyanate comprises at least one of diphenylmethane-4, 4 '-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4' -diisocyanate and m-phenylene diisocyanate;

the first chain extender comprises at least one of an allopyrimidinone and an imidazolidinyl urea;

the second chain extender comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, ethylenediamine and 1, 6-hexamethylenediamine;

the first catalyst comprises at least one of pentamethyldiethylenetriamine, dibutyltin dilaurate, N-dimethylcyclohexylamine and an organobismuth catalyst.

The second catalyst is tetramethyl ammonium hydroxide pentahydrate, and the molar ratio of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane to octamethyl cyclotetrasiloxane is 1:3-10.

The third catalyst is tetrabutyl titanate, 1, 4-butanediol: the molar ratio of diethyl carbonate is 1:1.1 to 1.4.

The invention also provides a preparation method of the polysiloxane polyurethane supermolecule elastomer, which comprises the following steps:

s1: dehydrating the polycarbonate diol and the diisocyanate;

s2: carrying out a first prepolymerization reaction on polycarbonate diol, diisocyanate and a first catalyst in an organic solvent to obtain a first prepolymer;

s3: adding amine-terminated polydimethylsiloxane into the first prepolymer to perform a second prepolymerization reaction to obtain a second prepolymer;

s4: and adding the first chain extender and the second chain extender into the second prepolymer to perform chain extension reaction to obtain the polysiloxane polyurethane supermolecular elastomer.

Further, the first prepolymerization reaction is carried out for 1-3 hours at 55-65 ℃ under the anhydrous and anaerobic condition;

the second prepolymerization reaction is carried out for 3-5 h at 45-55 ℃ under the anhydrous and anaerobic condition;

the chain extension reaction is carried out for 4-8 hours at 50-80 ℃ under the anhydrous and anaerobic condition;

the organic solvent comprises at least one of N, N-dimethylamide, N-dimethylacetamide and tetrahydrofuran.

The invention also provides application of the polysiloxane polyurethane supermolecular elastomer to preparation of medical materials;

the medical material comprises a medical implant material comprising a prosthetic blood vessel, a dirty stent, or a prosthetic heart valve.

The technical scheme of the invention has the following advantages:

(1) The polysiloxane polyurethane supermolecular elastomer provided by the invention has the advantages that the raw materials are simple and easy to obtain; the introduction of the amino-terminated silicone oil increases the interaction among molecular chains, is beneficial to improving the mechanical strength and the dynamic property of the material, and solves the defects of oxidation resistance stability and hydrolysis resistance stability of the existing modified polyurethane, wherein the defects of biological stability and mechanical stability of the silicon-containing polyurethane cannot be simultaneously considered, and the defects of lower mechanical strength, higher modulus and low tearing strength of the existing polysiloxane-polyurethane are overcome.

(2) In the invention, diisocyanate, a chain extender containing multiple hydrogen bonds and a chain extender are used as hard segment structures of polyurethane, polycarbonate diol and amino-terminated polydimethylsiloxane are used as soft segment structures of polyurethane, and the polyurethane elastomer has good hydrophobicity and good dynamic property due to the introduced amino-terminated silicone oil and multiple hydrogen bonds, so that the dynamic bond can play a role in blood, and a certain self-healing property is realized. Amino-terminated silicone oil and ureido pyrimidinone (UPy) containing quadruple hydrogen bonds are introduced into a polyurethane structure, so that the technical problem of the invention is well solved, the hydrolytic property and the oxidative stability of the polyurethane are improved, the tensile strength is high, the tearing strength is high, and the mechanical stability is good. Meanwhile, the problem that the existing silicon-containing polyurethane cannot simultaneously achieve biological stability and mechanical stability is solved, so that the silicon-containing polyurethane is suitable for being used as a long-term medical implant material.

(3) The invention defines a molar ratio of the sum of the amine-terminated polydimethylsiloxane and the reactive groups in the polycarbonate diol in the starting materials to the isocyanate groups of the diisocyanate of 1:1.2 to 2, if the diisocyanate content is too high, the proportion of hard segments of the polymer is too high, which is detrimental to the tensile properties of the polymer, and if the diisocyanate content is too low, the mechanical properties of the polymer are poor. Therefore, the content of the polyurethane elastomer is in the range, and the obtained polyurethane elastomer has good comprehensive mechanical properties.

(4) The polysiloxane polyurethane supermolecular elastomer provided by the invention has a simple preparation method and is convenient for large-scale production and use.

(5) Compared with the existing silicon-containing polyurethane, the polyurethane provided by the invention can be better applied to the field of long-term implantation medical materials, such as artificial blood vessels, artificial heart valves, artificial valve stents, various interventional catheters and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

FIG. 1 is a synthetic flow chart of a polysiloxane polyurethane supermolecular elastomer prepared in an embodiment of the present invention;

FIG. 2 is an infrared spectrum of polysiloxane polyurethane supermolecular elastomer obtained in examples 1 to 4 of the present invention;

FIG. 3 is a GPC chart of polysiloxane polyurethane supermolecular elastomers obtained in examples 1 to 4 of the present invention;

FIG. 4 is a graph showing the rheological temperature profile of polysiloxane polyurethane supermolecular elastomers obtained in examples 1-4 of the present invention;

FIG. 5 is a stress relaxation curve (strain 10%) of the polysiloxane polyurethane supermolecular elastomer obtained in examples 1 to 4 of the present invention.

Detailed Description

The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.

The specific experimental procedure or conditions are not noted and may be followed by the operation or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.

In the specific embodiment of the invention, the preparation method of the aminobutyl end-capped polydimethylsiloxane comprises the following steps:

octamethyl cyclotetrasiloxane, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane and tetramethyl ammonium hydroxide pentahydrate are added into a 500mL three-neck flask, mechanically stirred, nitrogen is filled for protection, condensation reflux is carried out, reaction is carried out for 10 hours at 80 ℃, the temperature is raised to 150 ℃ and kept for 1 hour after the reaction is finished to decompose the catalyst, then low boiling substances are removed by rotary evaporation, and the amine butyl terminated polydimethyl siloxane (PDMS-NH) is obtained ₂ ) Wherein the molar ratio of the 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane to the octamethyl cyclotetrasiloxane is 1:3-10.

In the specific embodiment of the invention, the polytetramethylene carbonate diol is prepared by the following steps:

adding 1, 4-butanediol and tetrabutyl titanate into a 500mL three-neck flask, mechanically stirring, charging nitrogen for protection, condensing and refluxing, heating to 150 ℃, adding diethyl carbonate into a constant pressure burette, and dropwise adding into a round bottom flask; after 4h, the temperature was then raised to 170℃and reacted for 2h. Then removing low-boiling substances by rotary evaporation to obtain Polytetramethylene Carbonate Diol (PCDL), wherein 1, 4-butanediol: the molar ratio of diethyl carbonate is 1:1.1 to 1.4.

Preparation of the first chain extender in a specific embodiment of the present invention:

10.00g of acetyl butyrolactone, 14.10g of guanidine carbonate, 100mL of absolute ethanol and 26mL of triethylamine are added into a 250mL three-neck flask, the mixture is mechanically stirred, nitrogen is filled for protection, condensation reflux is carried out, the temperature is increased to 80 ℃, and the reflux reaction is carried out for 12 hours. Cooled to room temperature, the solid was filtered and then washed with ethanol. And (3) drying the mixture in a vacuum oven to obtain the first chain extender ureido pyrimidinone (UPy) containing quadruple hydrogen bonds.

Example 1

The embodiment provides a polysiloxane polyurethane supermolecule elastomer, the preparation flow of which is shown in figure 1, and the specific preparation method is as follows:

filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50℃and an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) was added ₂ ) The method comprises the steps of carrying out a first treatment on the surface of the Finally, the temperature is increased to 65 ℃ and the first chain extender ureido pyrimidinone (UPy) and the second chain extender 1, 4-Butanediol (BDO) dissolved in the N, N-dimethylacetamide are added to volatilize the solvent; and (3) obtaining the polysiloxane polyurethane supermolecular elastomer, leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 2000g/mol, and the molecular weight of the amine butyl terminated polydimethylsiloxane is 2000g/mol; the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.5; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:4, a step of; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the polysiloxane polyurethane supermolecular elastomer obtained is denoted SiPUE1.

Example 2

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.3, the polysiloxane polyurethane supermolecular elastomer obtained is denoted SiPUE2.

Example 3

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:6, the polysiloxane polyurethane supermolecular elastomer is obtained and is marked as SiPUE3.

Example 4

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:8, the polysiloxane polyurethane supermolecular elastomer is obtained and is marked as SiPUE4.

Example 5

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.8, the polysiloxane polyurethane supermolecular elastomer obtained is denoted SiPUE5.

Example 6

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.3; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:6, the polysiloxane polyurethane supermolecular elastomer is obtained and is marked as SiPUE6.

Example 7

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.8; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:6, the polysiloxane polyurethane supermolecular elastomer is obtained and is marked as SiPUE7.

Example 8

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.3; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:8, the polysiloxane polyurethane supermolecular elastomer is marked as SiPUE8.

Example 9

This example provides a polysiloxane polyurethane supermolecular elastomer, the preparation flow of which is shown in fig. 1, and the preparation method is the same as that of example 1, except that: the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:4, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.8; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:8, the polysiloxane polyurethane supermolecular elastomer is obtained and is marked as SiPUE9.

Example 10

The embodiment provides a polysiloxane polyurethane supermolecule elastomer, the preparation flow of which is shown in figure 1, and the specific preparation method is as follows:

filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50℃and an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) was added ₂ ) The method comprises the steps of carrying out a first treatment on the surface of the Finally, the temperature is increased to 65 ℃ and the first chain extender ureido pyrimidinone (UPy) and the second chain extender 1, 4-Butanediol (BDO) dissolved in the N, N-dimethylacetamide are added to volatilize the solvent; and (3) obtaining the polysiloxane polyurethane supermolecular elastomer, leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 1000g/mol, and the molecular weight of the amine butyl terminated polydimethylsiloxane is 1000g/mol; the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:2; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:4, a step of; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the polysiloxane polyurethane supermolecular elastomer obtained is designated SiPUE10.

Example 11

The embodiment provides a polysiloxane polyurethane supermolecule elastomer, the preparation flow of which is shown in figure 1, and the specific preparation method is as follows:

filled with 99.999% N ₂ In a glove box, polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate are mixed in tetrahydrofuran as an organic solvent and reacted at 60 ℃ for 2hThe method comprises the steps of carrying out a first treatment on the surface of the The temperature was then reduced to 50℃and an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) was added ₂ ) The method comprises the steps of carrying out a first treatment on the surface of the Finally, the temperature is increased to 65 ℃ and the first chain extender ureido pyrimidinone (UPy) and the second chain extender 1, 4-Butanediol (BDO) dissolved in the N, N-dimethylacetamide are added to volatilize the solvent; and (3) obtaining the polysiloxane polyurethane supermolecular elastomer, leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 2000g/mol, and the molecular weight of the amine butyl terminated polydimethylsiloxane is 2000g/mol; the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.5; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:4, a step of; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the polysiloxane polyurethane supermolecular elastomer obtained is designated SiPUE11.

Example 12

The embodiment provides a polysiloxane polyurethane supermolecule elastomer, the preparation flow of which is shown in figure 1, and the specific preparation method is as follows:

filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50℃and an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) was added ₂ ) Finally, the temperature is raised to 65 ℃ and the first chain extender ureido pyrimidinone (UPy) and the second chain extender 1, 4-Butanediol (BDO) dissolved in the N, N-dimethylacetamide are added to volatilize the solvent; and (3) obtaining the polysiloxane polyurethane supermolecular elastomer, leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 1000g/mol, and the molecular weight of the amine butyl terminated polydimethylsiloxane is 1000g/mol; the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:2; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:4, a step of; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the polysiloxane polyurethane supermolecular elastomer obtained is designated SiPUE12.

Comparative example 1

This comparative example provides an elastomer differing from example 1 in that hydroxy-terminated polydimethylsiloxane (PDMS-OH) was used in place of aminobutyl-terminated polydimethylsiloxane (PDMS-NH) ₂ ) The method is characterized by comprising the following steps: filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50 ℃ and hydroxyl-terminated polydimethylsiloxane (PDMS-OH) was added; finally, the temperature is increased to 65 ℃ and the first chain extender ureido pyrimidinone (UPy) and the second chain extender 1, 4-Butanediol (BDO) dissolved in the N, N-dimethylacetamide are added to volatilize the solvent; and leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 2000g/mol, and the molecular weight of the hydroxyl-terminated polydimethylsiloxane is 2000g/mol; the molar ratio of polytetramethylene carbonate glycol to hydroxyl-terminated polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the hydroxyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.5; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the elastomer obtained is designated as comparative example 1.

Comparative example 2

This comparative example provides an elastomer, differing from example 1 in that the first chain extender ureidopyrimidinone (UPy) is not added, as follows: filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50℃and an aminobutyl-terminated polydimethylsiloxane (PDMS-NH) was added ₂ ) The method comprises the steps of carrying out a first treatment on the surface of the Finally, the temperature is increased to 60 ℃ and 1, 4-Butanediol (BDO) dissolved in tetrahydrofuran is added, and the solvent is volatilized; and leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 2000g/mol, and the molecular weight of the amine butyl terminated polydimethylsiloxane is 2000g/mol; the molar ratio of polytetramethylene carbonate glycol to aminobutyl end-capped polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the aminobutyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.5; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the elastomer obtained is designated as comparative example 2.

Comparative example 3

This comparative example provides an elastomer differing from example 1 in that hydroxy-terminated polydimethylsiloxane (PDMS-OH) was used in place of aminobutyl-terminated polydimethylsiloxane (PDMS-NH) ₂ ) And without the addition of the first chain extender ureido pyrimidinone (UPy), the following are specific: filled with 99.999% N ₂ In a glove box of (2), firstly mixing polytetramethylene carbonate glycol (PCDL), isophorone diisocyanate and dibutyltin dilaurate in an organic solvent tetrahydrofuran, and reacting for 2 hours at 60 ℃; the temperature was then reduced to 50 ℃ and hydroxyl-terminated polydimethylsiloxane (PDMS-OH) was added; finally, the temperature is increased to 60 ℃ and 1, 4-Butanediol (BDO) dissolved in tetrahydrofuran is added, and the solvent is volatilized; and leveling in a mould to form a film, and drying to obtain the polyurethane elastomer film.

Wherein the molecular weight of the tetramethylene carbonate glycol is 2000g/mol, and the molecular weight of the hydroxyl-terminated polydimethylsiloxane is 2000g/mol; the molar ratio of polytetramethylene carbonate glycol to hydroxyl-terminated polydimethylsiloxane was 1:3, a step of; the molar ratio of the sum of the reactive groups in the hydroxyl-terminated polydimethylsiloxane and polytetramethylene carbonate diol to the isocyanate groups of isophorone diisocyanate was 1:1.5; the mass of dibutyltin dilaurate accounts for 0.5wt% of the mass of all reactants; the elastomer obtained is designated as comparative example 3.

Test example 1

The elastomers obtained in examples 1 to 4 were tested.

(1) Infrared testing: an infrared spectrometer with Attenuated Total Reflectance (ATR) accessory was chosen, the infrared light transmitting material being ZnSe (refractive index 2.4). During testing, the ATR accessory is firstly placed in a light path of an infrared spectrometer, an air background is scanned, then the surface to be tested of the sample is tightly attached to the infrared light-transmitting crystal surface of the ATR accessory, and the infrared spectrum of the surface to be tested of the sample is obtained through scanning, and the result is shown in figure 2;

(2) GPC test: measuring the molecular weight and the distribution of the supermolecular elastomer by taking tetrahydrofuran as a mobile phase, the flow rate is 1.0mL/min, the temperature of a test column incubator is 40 ℃, the temperature of a detector is 35 ℃, and monodisperse polystyrene as a standard sample, wherein the molecular weight and the distribution of the supermolecular elastomer are shown in figure 3;

(3) Rheology analysis: cutting the iron ion crosslinking polysiloxane supermolecular elastomer into round sample strips with the diameter of 25mm, putting the round sample strips into a 60 ℃ oven for drying, preparing for testing the rheological property of the round sample strips, and recording the change curves of storage modulus and loss modulus with temperature at the temperature of 20-180 ℃ under the normal force of 1N, the strain of 1% and the strain frequency of 1Hz, wherein the results are shown in figure 4;

(4) Stress relaxation performance test: an elastomeric film having a thickness of 1mm was obtained, cut into a bar of 30mm by 5mm, stretched at a rate of 100mm/min on a stretcher, and tested for stress relaxation curve (strain 10%) and the results are shown in FIG. 5.

Test example 2

The mechanical properties of the elastomers obtained in examples 1 to 4 and comparative examples 1 to 3 were tested by the test method of GB/T528-2009, and the test results are shown in Table 1:

table 1 mechanical properties results for examples and comparative examples

It can be seen that the tensile strength and elongation at break of comparative examples 1-3 are much smaller than those of example 1, and the Young's modulus is both greater than that of example 1, which demonstrates that the present application introduces amino-terminated silicone oil and ureido pyrimidinone containing four hydrogen bonds into polyurethane structure, while maintaining low modulus, high tensile strength, good elongation at break, and excellent mechanical properties.

It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (10)

1. A polysiloxane polyurethane supermolecular elastomer, characterized in that the raw materials comprise: a polycarbonate diol, an amine-terminated polydimethylsiloxane, a diisocyanate, a first chain extender, a second chain extender, and a first catalyst;

the molar ratio of the sum of the active groups in the amine-terminated polydimethylsiloxane and the polycarbonate diol to the isocyanate groups of the diisocyanate is 1:1.2 to 2; the molar ratio of the polycarbonate diol to the amine-terminated polydimethylsiloxane is 1:2 to 5; the molar ratio of the active groups of the first chain extender to the active groups of the second chain extender is 1:3 to 9; the mass of the first catalyst accounts for 0.1-0.8% of the mass of all raw materials;

the first chain extender is a chain extender containing four hydrogen bonds.

2. The polysiloxane polyurethane supermolecular elastomer according to claim 1, wherein the molar ratio of polycarbonate diol, amine-terminated polydimethylsiloxane, diisocyanate and reactive groups of the first and second chain extenders is 1:2 to 5:3.6 to 12:0.15 to 0.6:0.45 to 5.4.

3. The polysiloxane polyurethane supermolecular elastomer according to claim 2, wherein,

the polycarbonate diol comprises polytetramethylene carbonate diol, and the molecular weight of the polytetramethylene carbonate diol ranges from 1000g/mol to 2000g/mol; the amine-terminated polydimethylsiloxane comprises an aminobutyl-terminated polydimethylsiloxane having a molecular weight in the range of 1000-2000g/mol.

4. A polysiloxane polyurethane supermolecular elastomer according to claim 3, characterized in that the preparation method of the aminobutyl end-capped polydimethylsiloxane comprises the steps of mixing octamethyl cyclotetrasiloxane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, reacting under the action of a second catalyst to obtain a crude product, and distilling under reduced pressure to obtain the aminobutyl end-capped polydimethylsiloxane;

the preparation method of the polytetramethylene carbonate glycol comprises the steps of taking diethyl carbonate and 1, 4-butanediol as raw materials, reacting under the action of a third catalyst to obtain a crude product, and distilling under reduced pressure to obtain the polytetramethylene carbonate glycol.

5. The polysiloxane polyurethane supermolecular elastomer according to claim 4, wherein,

the diisocyanate comprises at least one of diphenylmethane-4, 4 '-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4' -diisocyanate and m-phenylene diisocyanate;

the first chain extender comprises at least one of an allopyrimidinone and an imidazolidinyl urea;

the second chain extender comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, ethylenediamine and 1, 6-hexamethylenediamine;

the first catalyst comprises at least one of pentamethyldiethylenetriamine, dibutyltin dilaurate, N-dimethylcyclohexylamine and an organobismuth catalyst.

6. The polysiloxane polyurethane supermolecular elastomer according to claim 5, wherein the second catalyst is tetramethylammonium hydroxide pentahydrate, and the molar ratio of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane to octamethyl cyclotetrasiloxane is 1:3-10.

7. The polysiloxane polyurethane supermolecular elastomer according to claim 6, wherein the third catalyst is tetrabutyl titanate, 1, 4-butanediol: the molar ratio of diethyl carbonate is 1:1.1 to 1.4.

8. A process for the preparation of a polysiloxane polyurethane supermolecular elastomer according to any one of claims 1 to 7, characterized in that it comprises the following steps:

s1: dehydrating the polycarbonate diol and the diisocyanate;

s2: carrying out a first prepolymerization reaction on polycarbonate diol, diisocyanate and a first catalyst in an organic solvent to obtain a first prepolymer;

s3: adding amine-terminated polydimethylsiloxane into the first prepolymer to perform a second prepolymerization reaction to obtain a second prepolymer;

s4: and adding the first chain extender and the second chain extender into the second prepolymer to perform chain extension reaction to obtain the polysiloxane polyurethane supermolecular elastomer.

9. The method according to claim 8, wherein the first prepolymerization is carried out at 55-65 ℃ for 1-3 hours under anhydrous and anaerobic conditions;

the second prepolymerization reaction is carried out for 3-5 h at 45-55 ℃ under the anhydrous and anaerobic condition;

the chain extension reaction is carried out for 4-8 hours at 50-80 ℃ under the anhydrous and anaerobic condition;

the organic solvent comprises at least one of N, N-dimethylamide, N-dimethylacetamide and tetrahydrofuran.

10. Use of a polysiloxane polyurethane supermolecular elastomer according to any one of claims 1 to 8 for the preparation of a medical material;

the medical material comprises a medical implant material comprising a prosthetic blood vessel, a dirty stent, or a prosthetic heart valve.

Images