CN105273155A - Preparation method of biological-stabilizing thermoplastic polyurethane elastomer - Google Patents

Abstract

The invention discloses a preparation method of a biological-stabilizing thermoplastic polyurethane elastomer, and belongs to the technical field of calendered products. The preparation method comprises the following steps of firstly, using dimethyl terephthalate and ethylene glycol to produce polyethylene glycol terephthalate under the actions of butyl titanate and titanium dioxide, adding rumen of ruminant to biologically modify the polyethylene glycol terephthalate in the reaction process, and using the polyethylene glycol terephthalate, diglycol, terephthaldehyde diisocyanate and the like to produce thermoplastic polyurethane in a container at the nitrogen-protected high-temperature and pressure-relief atmosphere; in the temperature lowering process, using pig blood to further biologically modify, and putting into an extrusion machine to extrude, so as to obtain the biological-stabilizing thermoplastic polyurethane elastomer. The preparation method has the advantages that after proofing by experiments, the degrading rate of the prepared artificial organ under the actions of hydrolase and cell derivative enzyme is reduced by more than 95%, and the conditions of thrombus, infection and calcification in the transplanted human body are avoided; compared with the artificial organ manufactured by the traditional material, the biological stability is improved by more than 85%.

Description

A kind of Biostatic method for preparing thermoplastic polyurethane elastomer

Technical field

The invention discloses a kind of Biostatic method for preparing thermoplastic polyurethane elastomer, belong to calendered goods technical field.

Background technology

The segmented copolymer that thermoplastic polyurethane (TPU) is made up of two kinds of dissimilar segments of chemical property, it is a kind of thermoplastic's elastomerics, be characterized in that there is high tensile and elongation at break, good wearability, anti-oar song, hydrolytic resistance, resistance to microorganism ability, and easy forming process, and there is the controlled advantage of performance, purposes widely can be had in a lot.At present, TPU has been widely used in the aspects such as health care, electronic apparatus, industry and physical culture, have that the incomparable intensity of other plastic material is high, good toughness, wear-resisting, cold-resistant, oil resistant, the characteristic such as water-fast, ageing-resistant, weather, also there is the function of high waterproof, water vapour permeability, windproof, cold-proof, antibacterial, mildew-resistant, warming, many excellences such as uvioresistant and fault offset simultaneously.External at first by this materials application in aviation and medical field, along with the attention further to environmental protection and safety, in recent years domesticly also progressively occur and be applied to the industry such as medical treatment, daily necessities.The most important thing is, urethane has good histocompatibility and blood compatibility.

Since eighties of last century fifties, urethane is as the mould material of chest prosthesis, urethane chain segment copolymer first time in 1967 has been conceived to as since biomaterial, and the application of urethane has expanded to and comprised schrittmacher, conduit, pliable and tough blood vessel graft, accessory heart valve etc.But, they transplant facility at some, the application of particularly some long-term engraftment is still restricted, mainly because their relative instability in coenocorrelation and and faulty anticoagulant property, and some researchs and display urethane lytic enzyme as papoid and cell-derived enzyme as the effect of cholesteryl esterase, elastoser etc. under easily degrade.

In addition, a lot of research work has been had to set about improving the biologically stable of urethane, the particularly stability of soft section of component, as other bio-medical level polymer materials, but still there is several obvious problem, such as inducing thrombosis, infection and calcification after long-term engraftment in vivo in urethane.Therefore, in order to address these problems, a lot of researchist develops new physiologically acceptable at effort research and probe, is applicable to the polyurethane material of human implantation's facility.

Summary of the invention

The technical problem that the present invention mainly solves: for current thermoplastic polyurethane in the process being applied to medical field, during as the vitals such as schrittmacher, blood vessel graft graft materials, the restriction of still being applied, be mainly and easily degrade under lytic enzyme and cell-derived enzyme effect, and the drawback of easily inducing thrombosis, infection and calcification after transplanting, provide a kind of Biostatic method for preparing thermoplastic polyurethane elastomer.The method is first by dimethyl terephthalate (DMT) and ethylene glycol; at butyl (tetra) titanate; under the effect of titanium dioxide; produce polyethylene terephthalate; in its reaction process; add ruminant tumor gastric and also bio-modification is carried out to it; then by itself and glycol ether, the materials such as terephthaldehyde's group diisocyanate, in container; under the environment of nitrogen protection high-temperature pressure-reduction; Heat of Formation plastic polyurethane, when it is lowered the temperature, uses pig blood to its further bio-modification; then put into forcing machine to extrude, obtain Biostatic Polyurethane Thermoplastic Elastomer.The thermoplastic polyurethane that the present invention makes not only safety and sanitation, not easily degrade under the effect of enzyme, and long service life after transplanting, can not breed bacteria, and cause and infect, biologically stable is remarkable.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

(1) get 400 ~ 600g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 60 ~ 100mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 1 ~ 3MPa to reactor, rise to 180 ~ 200 DEG C with the heat-up rate of 15 DEG C/h, stir 3 ~ 6h with the rotating speed of 300 ~ 500r/min;

(2) after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 15 ~ 20g titanium dioxide wherein, add 60 ~ 100mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 3 ~ 5h, 80 ~ 100Pa is evacuated to reactor, rise to 270 ~ 280 DEG C with the heat-up rate of 20 DEG C/h, stir 10 ~ 16h with the rotating speed of 300 ~ 500r/min;

(3) discharging after above-mentioned end, use temperature is the soaked in absolute ethyl alcohol discharging thing of 5 ~ 10 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 60 ~ 100 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 50 ~ 90Pa, be warming up to 100 ~ 110 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%;

(4) particulate matter of getting the above-mentioned process of 100 ~ 200g puts into container, respectively to wherein adding 5 ~ 10g calcium stearate, 30 ~ 60mL glycol ether, 60 ~ 90mL1,4 butyleneglycols, stir, then 110 ~ 120 DEG C are warming up to, under nitrogen protection condition, be decompressed to 200 ~ 300Pa, heated and stirred 2 ~ 4h;

(5) after above-mentioned stirring heating, 80 ~ 90mL terephthaldehyde group diisocyanate and 4 ~ 6g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 800 ~ 900r/min, stop nitrogen protection and be decompressed to 800 ~ 900Pa, continue stirring reaction 15 ~ 25min, then in container, 300 ~ 400mL fresh pig blood is added, keep temperature 28 ~ 35 DEG C, filter after leaving standstill slaking 10 ~ 15h;

(6) filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 100 ~ 120 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 150 ~ 250 DEG C, screw speed is 700 ~ 900r/min, obtains Polyurethane Thermoplastic Elastomer.

Application method of the present invention is: with the thermoplastic polyurethane obtained by the present invention for starting material obtain artificial organ, afterwards obtained artificial organ is put into human gastric juice to soak, temperature is kept to be 28 ~ 40 DEG C, add the papoid of 10 ~ 15% of artificial organ quality and the cholesteryl esterase of 5 ~ 10% again, after 4 ~ 5 months, the artificial organ after immersion is taken out, clean, after testing, there is not any change in its internal structure and surface, and under lytic enzyme and cell-derived enzyme effect, be not easy degraded, degradation rate reduces 95 ~ 98%, subsequently by clean after artificial organ implant treat in the patient body that organ is repaired, within 3 ~ 5 months, there is not thrombus, the situation of infection and calcification occurs, the artificial organ biologically stable more obtained than traditional material improves more than 85%.

The invention has the beneficial effects as follows:

(1) the present invention's thermoplastic polyurethane safety and sanitation of making, not easily degrade under the effect of enzyme, and long service life after transplanting, can not breed bacteria, cause and infect;

(2) biologically stable is remarkable, and the artificial organ biologically stable more obtained than traditional material improves more than 85%.

Embodiment

First get 400 ~ 600g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 60 ~ 100mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 1 ~ 3MPa to reactor, rise to 180 ~ 200 DEG C with the heat-up rate of 15 DEG C/h, stir 3 ~ 6h with the rotating speed of 300 ~ 500r/min; Then after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 15 ~ 20g titanium dioxide wherein, add 60 ~ 100mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 3 ~ 5h, 80 ~ 100Pa is evacuated to reactor, rise to 270 ~ 280 DEG C with the heat-up rate of 20 DEG C/h, stir 10 ~ 16h with the rotating speed of 300 ~ 500r/min; Discharging after above-mentioned end afterwards, use temperature is the soaked in absolute ethyl alcohol discharging thing of 5 ~ 10 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 60 ~ 100 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 50 ~ 90Pa, be warming up to 100 ~ 110 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%; The particulate matter of getting the above-mentioned process of 100 ~ 200g subsequently puts into container, respectively to wherein adding 5 ~ 10g calcium stearate, 30 ~ 60mL glycol ether, 60 ~ 90mL1,4 butyleneglycols, stir, then 110 ~ 120 DEG C are warming up to, under nitrogen protection condition, be decompressed to 200 ~ 300Pa, heated and stirred 2 ~ 4h; Next after above-mentioned stirring heating, 80 ~ 90mL terephthaldehyde group diisocyanate and 4 ~ 6g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 800 ~ 900r/min, stop nitrogen protection and be decompressed to 800 ~ 900Pa, continue stirring reaction 15 ~ 25min, then in container, 300 ~ 400mL fresh pig blood is added, keep temperature 28 ~ 35 DEG C, filter after leaving standstill slaking 10 ~ 15h; Finally the filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 100 ~ 120 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 150 ~ 250 DEG C, screw speed is 700 ~ 900r/min, obtains Polyurethane Thermoplastic Elastomer.

Example 1

First get 400g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 60mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 1MPa to reactor, rise to 180 DEG C with the heat-up rate of 15 DEG C/h, stir 3h with the rotating speed of 300 ~ 500r/min; Then after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 15g titanium dioxide wherein, add 60mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 3h, 80Pa is evacuated to reactor, rise to 270 DEG C with the heat-up rate of 20 DEG C/h, stir 10h with the rotating speed of 300r/min; Discharging after above-mentioned end afterwards, use temperature is the soaked in absolute ethyl alcohol discharging thing of 5 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 60 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 50Pa, be warming up to 100 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%; The particulate matter of getting the above-mentioned process of 100g subsequently puts into container, respectively to wherein adding 5g calcium stearate, and 30mL glycol ether, 60mL1,4 butyleneglycols, stir, and are then warming up to 110 DEG C, under nitrogen protection condition, are decompressed to 200Pa, heated and stirred 2h; Next after above-mentioned stirring heating, 80mL terephthaldehyde group diisocyanate and 4g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 800r/min, stop nitrogen protection and be decompressed to 800Pa, continue stirring reaction 15min, then in container, 300mL fresh pig blood is added, keep temperature 28 DEG C, filter after leaving standstill slaking 10h; Finally the filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 100 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 150 DEG C, screw speed is 700r/min, obtains Polyurethane Thermoplastic Elastomer.

This example is unique novel, with the thermoplastic polyurethane obtained by the present invention for starting material obtain artificial organ, afterwards obtained artificial organ is put into human gastric juice to soak, temperature is kept to be 28 DEG C, add the papoid of 10% of artificial organ quality and the cholesteryl esterase of 5% again, after 4 months, the artificial organ after immersion is taken out, clean, after testing, there is not any change in its internal structure and surface, and under lytic enzyme and cell-derived enzyme effect, be not easy degraded, degradation rate reduces 95%, subsequently by clean after artificial organ implant treat in the patient body that organ is repaired, within 3 months, there is not thrombus, the situation of infection and calcification occurs, the artificial organ biologically stable more obtained than traditional material improves 85%.

Example 2

First get 500g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 80mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 2MPa to reactor, rise to 190 DEG C with the heat-up rate of 15 DEG C/h, stir 5h with the rotating speed of 400r/min; Then after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 18g titanium dioxide wherein, add 80mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 4h, 90Pa is evacuated to reactor, rise to 275 DEG C with the heat-up rate of 20 DEG C/h, stir 13h with the rotating speed of 400r/min; Discharging after above-mentioned end afterwards, use temperature is the soaked in absolute ethyl alcohol discharging thing of 8 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 85 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 75Pa, be warming up to 105 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%; The particulate matter of getting the above-mentioned process of 150g subsequently puts into container, respectively to wherein adding 8g calcium stearate, and 45mL glycol ether, 80mL1,4 butyleneglycols, stir, and are then warming up to 115 DEG C, under nitrogen protection condition, are decompressed to 250Pa, heated and stirred 3h; Next after above-mentioned stirring heating, 85mL terephthaldehyde group diisocyanate and 5g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 850r/min, stop nitrogen protection and be decompressed to 850Pa, continue stirring reaction 20min, then in container, 350mL fresh pig blood is added, keep temperature 32 DEG C, filter after leaving standstill slaking 13h; Finally the filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 110 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 200 DEG C, screw speed is 800r/min, obtains Polyurethane Thermoplastic Elastomer.

This example is unique novel, with the thermoplastic polyurethane obtained by the present invention for starting material obtain artificial organ, afterwards obtained artificial organ is put into human gastric juice to soak, temperature is kept to be 32 DEG C, add the papoid of 13% of artificial organ quality and the cholesteryl esterase of 8% again, after 4.5 months, the artificial organ after immersion is taken out, clean, after testing, there is not any change in its internal structure and surface, and under lytic enzyme and cell-derived enzyme effect, be not easy degraded, degradation rate reduces 97%, subsequently by clean after artificial organ implant treat in the patient body that organ is repaired, within 4 months, there is not thrombus, the situation of infection and calcification occurs, the artificial organ biologically stable more obtained than traditional material improves 88%.

Example 3

First get 600g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 100mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 3MPa to reactor, rise to 200 DEG C with the heat-up rate of 15 DEG C/h, stir 6h with the rotating speed of 500r/min; Then after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 20g titanium dioxide wherein, add 100mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 5h, 100Pa is evacuated to reactor, rise to 280 DEG C with the heat-up rate of 20 DEG C/h, stir 16h with the rotating speed of 500r/min; Discharging after above-mentioned end afterwards, use temperature is the soaked in absolute ethyl alcohol discharging thing of 10 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 100 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 90Pa, be warming up to 110 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%; The particulate matter of getting the above-mentioned process of 200g subsequently puts into container, respectively to wherein adding 10g calcium stearate, and 60mL glycol ether, 90mL1,4 butyleneglycols, stir, and are then warming up to 120 DEG C, under nitrogen protection condition, are decompressed to 300Pa, heated and stirred 4h; Next after above-mentioned stirring heating, 90mL terephthaldehyde group diisocyanate and 6g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 900r/min, stop nitrogen protection and be decompressed to 900Pa, continue stirring reaction 25min, then in container, 400mL fresh pig blood is added, keep temperature 35 DEG C, filter after leaving standstill slaking 15h; Finally the filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 120 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 250 DEG C, screw speed is 900r/min, obtains Polyurethane Thermoplastic Elastomer.

This example is unique novel, with the thermoplastic polyurethane obtained by the present invention for starting material obtain artificial organ, afterwards obtained artificial organ is put into human gastric juice to soak, temperature is kept to be 40 DEG C, add the papoid of 15% of artificial organ quality and the cholesteryl esterase of 10% again, after 5 months, the artificial organ after immersion is taken out, clean, after testing, there is not any change in its internal structure and surface, and under lytic enzyme and cell-derived enzyme effect, be not easy degraded, degradation rate reduces 98%, subsequently by clean after artificial organ implant treat in the patient body that organ is repaired, within 5 months, there is not thrombus, the situation of infection and calcification occurs, the artificial organ biologically stable more obtained than traditional material improves 92%.

Claims (1)

1. a Biostatic method for preparing thermoplastic polyurethane elastomer, is characterized in that concrete preparation process is:

(1) get 400 ~ 600g dimethyl terephthalate (DMT) and put into reactor, ethylene glycol is added wherein by solid-to-liquid ratio 1:3, stir, add 60 ~ 100mL butyl (tetra) titanate wherein again, then nitrogen is used to be forced into 1 ~ 3MPa to reactor, rise to 180 ~ 200 DEG C with the heat-up rate of 15 DEG C/h, stir 3 ~ 6h with the rotating speed of 300 ~ 500r/min;

(2) after above-mentioned stirring terminates, be cooled to normal temperature, pressure release is to standard atmospheric pressure, add 15 ~ 20g titanium dioxide wherein, add 60 ~ 100mL ruminant tumor gastric juice with the speed of 5mL/min, after stirring 3 ~ 5h, 80 ~ 100Pa is evacuated to reactor, rise to 270 ~ 280 DEG C with the heat-up rate of 20 DEG C/h, stir 10 ~ 16h with the rotating speed of 300 ~ 500r/min;

(3) discharging after above-mentioned end, use temperature is the soaked in absolute ethyl alcohol discharging thing of 5 ~ 10 DEG C, is cooled to after room temperature and filters, the filtrate of gained is put into pulverizer and pulverizes until discharging thing, sieve to obtain 60 ~ 100 order powder, the powder of gained is put into container, sealed vessel, be filled with nitrogen and the air in container is discharged, then to container decompression to 50 ~ 90Pa, be warming up to 100 ~ 110 DEG C, stir in temperature-rise period simultaneously, make the water content of particulate matter lower than 0.5%;

(4) particulate matter of getting the above-mentioned process of 100 ~ 200g puts into container, respectively to wherein adding 5 ~ 10g calcium stearate, 30 ~ 60mL glycol ether, 60 ~ 90mL1,4 butyleneglycols, stir, then 110 ~ 120 DEG C are warming up to, under nitrogen protection condition, be decompressed to 200 ~ 300Pa, heated and stirred 2 ~ 4h;

(5) after above-mentioned stirring heating, 80 ~ 90mL terephthaldehyde group diisocyanate and 4 ~ 6g manganese acetate is added wherein, stir until the mixed solution in container becomes thick with the rotating speed of 800 ~ 900r/min, stop nitrogen protection and be decompressed to 800 ~ 900Pa, continue stirring reaction 15 ~ 25min, then in container, 300 ~ 400mL fresh pig blood is added, keep temperature 28 ~ 35 DEG C, filter after leaving standstill slaking 10 ~ 15h;

(6) filtrate of above-mentioned mistake is put into baking oven to dry, the filtrate of gained is put into pulverizer pulverize, sieve to obtain 100 ~ 120 order particles, the particulate matter of gained is put into twin screw extruder, adjustment twin screw extruder temperature is 150 ~ 250 DEG C, screw speed is 700 ~ 900r/min, obtains Polyurethane Thermoplastic Elastomer.