Shape memory composite material for uterus support and preparation method of shape memory composite material

Abstract

The invention relates to the technical field of medical material preparation, and particularly discloses a shape memory composite material for a uterus support and a preparation method thereof.The shape memory composite material is prepared by adding 1, 4-butylene glycol into raw materials for synthesizing polyurethane, introducing a double-bond functional group into the structure of a polyurethane elastomer and meanwhile modifying nano silicon dioxide; a double-bond functional group is introduced to the surface of nano silicon dioxide, and double-bond crosslinking is realized through ultraviolet radiation, so that the shape memory composite material is obtained and has good mechanical properties and deformation recovery rate; allyl alcohol glycidyl ether is used for modifying nano silicon dioxide, the compatibility of nano silicon dioxide and a material matrix is improved, meanwhile, allyl alcohol glycidyl ether serves as a flexible chain segment to be introduced into the shape memory composite material, and after the material is subjected to external force, the flexible chain segment can be used for modifying the nano silicon dioxide. Energy can be effectively absorbed and can be quickly recovered after the external force is relieved, so that the deformation recovery rate of the material is increased.

Description

Technical Field

[0001] The invention relates to the technical field of medical material preparation, and in particular to a shape memory composite material for a pessary and a preparation method thereof. Background Art

[0002] A pessary is a medical device used to treat female uterine prolapse. Its manufacturing materials mainly include polyethylene, silicone rubber and polymer materials. Polyethylene is a widely used plastic material with the characteristics of non-toxicity, corrosion resistance and easy processing. In the production of pessaries, polyethylene is used to make support-type pessaries, such as ring-shaped pessaries; silicone rubber is a material with excellent biocompatibility, which is non-toxic and non-irritating to the human body, and has good elasticity and aging resistance. Therefore, silicone rubber is widely used to make pessaries, especially filled pessaries, such as horn-type and donut-type. These pessaries can better adapt to the needs of different patients and improve the treatment effect; in recent years, with the development of medical technology, some imported polymer materials have also been used to make pessaries. These materials have the advantages of high temperature resistance, corrosion resistance, long service life, etc., and meet relevant medical standards. They not only improve the comfort and durability of pessaries, but also reduce the risk of allergies and infections in patients.

[0003] Shape memory polymer material, as a kind of smart material, refers to a material that can sense the stimulation of environmental changes (such as external force) and respond to such changes, thereby adjusting its mechanical parameters (such as shape, position, strain, etc.) until it returns to its initial state. Currently, most pessaries are made of hard silicone, which does not have shape memory function and cannot adjust itself according to the patient's bladder fullness. Summary of the invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide a shape memory composite material for a pessary and a preparation method thereof. The prepared shape memory composite material has good mechanical properties and also has excellent shape memory properties.

[0005] In order to achieve the above object, the present invention adopts the following technical scheme:

[0006] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0007] S1, adding polyol and diisocyanate into a reactor, heating and stirring to react, then adding chain extender diethanolamine, stirring evenly and putting into a mold, letting it stand and then demoulding, and then placing in an oven for aging to obtain a polyurethane elastomer;

[0008] S2. Evenly mix the polyurethane elastomer, polycaprolactone and photoinitiator, then add modified nano-silica and mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then perform ultraviolet light irradiation treatment to obtain a shape memory composite material.

[0009] In the technical solution disclosed in the present invention, in step S1, the mass ratio of polyol, diisocyanate and diethanolamine is 1:3-4:1-1.5, for example, 1:3:1, 1:3:1.5, 1:3.5:1, 1:3.5:1.5, 1:4:1, 1:4:1.5 can be selected, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0010] In the technical solution disclosed in the present invention, the polyol is selected from polybutylene adipate diol and 1,4-butene diol.

[0011] Specifically, the mass ratio of the polybutylene adipate diol and 1,4-butene diol is 3-5:1-2, for example, 3:1, 3:1.5, 3:2, 4:1, 4:1.5, 4:2, 5:1, 5:1.5, 5:2 can be selected, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0012] In the technical solution disclosed in the present invention, the diisocyanate is selected from 4,4'-methylenebis(phenyl isocyanate), isophorone diisocyanate or toluene-2,4-diisocyanate.

[0013] In the technical scheme disclosed in the present invention, the temperature of the heating and stirring reaction is 70-80°C, for example, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, and 80°C can be selected; the time of the heating and stirring reaction is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, and 4h can be selected, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0014] In the technical solution disclosed in the present invention, the aging temperature in the oven is 100-120°C, for example, 100°C, 105°C, 110°C, 115°C, 120°C can be selected; the aging time in the oven is 12-24h, for example, 12h, 15h, 18h, 21h, 24h can be selected, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0015] In the technical solution disclosed in the present invention, in step S2, the mass ratio of polyurethane elastomer, polycaprolactone, photoinitiator and modified nano-silica is 40-60:30-40:2-3:5-10.

[0016] Specifically, the photoinitiator is selected from 4-propyleneoxy-2-hydroxybenzophenone.

[0017] Specifically, the preparation method of the modified nano-silica is as follows: disperse nano-silica in deionized water, then add allyl alcohol glycidyl ether and catalyst stannous chloride thereto, heat and stir to react, then filter, wash and dry to obtain the modified nano-silica.

[0018] More specifically, the mass ratio of the nano-silicon dioxide, allyl alcohol glycidyl ether and stannous chloride is 10-15:4-8:1-2. In some embodiments of the present invention, for example, 10:4:1, 10:6:1.5, 10:8:2, 12:6:1, 12:8:2, 15:8:2 can be selected, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0019] More specifically, the temperature of the heating and stirring reaction is 75-90°C, for example, 75°C, 80°C, 85°C, and 90°C can be selected; the time of the heating and stirring reaction is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, and 4h can be selected, but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0020] In the technical solution disclosed in the present invention, in step S2, the wavelength of the ultraviolet light is 200-400nm, and the intensity of the ultraviolet light is 100-200W / cm 2 , irradiation time is 1-5h.

[0021] The present invention also provides a shape memory composite material for a pessary prepared by the above preparation method.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The present invention introduces double bond functional groups into the structure of polyurethane elastomer by adding 1,4-butenediol into the raw materials for synthesizing polyurethane, and introduces double bond functional groups on the surface of nano-silicon dioxide by modifying the nano-silicon dioxide, and then realizes double bond cross-linking by ultraviolet irradiation, thereby obtaining a shape memory composite material having good mechanical properties and deformation recovery rate.

[0024] (2) The present invention utilizes allyl alcohol glycidyl ether to modify nano-silica, thereby improving the compatibility of nano-silica and the material matrix, making it difficult for nano-silica to agglomerate in the material matrix. At the same time, allyl alcohol glycidyl ether is introduced into the shape memory composite material as a flexible chain segment. After the material is subjected to an external force, the flexible chain segment can effectively absorb energy and quickly recover after the external force is released, thereby improving the deformation recovery rate of the material. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below through specific preferred embodiments, but the present invention is not limited to the following embodiments.

[0026] It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention were purchased through commercial channels.

[0027] The polybutylene adipate diol used in the embodiments of the present invention was purchased from Hubei Xinyuhong Biopharmaceutical Technology Co., Ltd., CAS No.: 150923-12-9, product model: hk-1044, molecular weight: 1000; polycaprolactone CAS No.: 36890-68-3, product model: kq-051; the particle size of nano-silica is 40-60nm.

[0028] Example 1

[0029] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0030] S1, add 6 parts of polybutylene adipate diol, 4 parts of 1,4-butene diol and 30 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heat and stir at 70°C for 4 hours, then add 10 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1 hour and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18 hours, to obtain a polyurethane elastomer;

[0031] S2, add 40 parts of polyurethane elastomer, 30 parts of polycaprolactone and 2 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 5 parts of modified nano-silica, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 2h, the irradiation intensity is 100W / cm 2 , that is, a shape memory composite material is obtained;

[0032] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0033] 10 g of nano-silica was dispersed in 150 mL of deionized water, and then 4 g of allyl alcohol glycidyl ether and 1 g of catalyst stannous chloride were added thereto, and the mixture was heated and stirred at 75° C. for 4 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0034] Example 2

[0035] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0036] S1, adding 8 parts of polybutylene adipate diol, 2 parts of 1,4-butene diol and 30 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heating and stirring at 80°C for 2h, then adding 12 parts of chain extender diethanolamine, stirring evenly and putting into a mold, standing for 1h and then demoulding, and then placing in an oven for aging at a aging temperature of 100°C and a aging time of 18h to obtain a polyurethane elastomer;

[0037] S2, add 50 parts of polyurethane elastomer, 35 parts of polycaprolactone and 2 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 8 parts of modified nano-silica, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 1h, the irradiation intensity is 200W / cm 2 , that is, a shape memory composite material is obtained;

[0038] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0039] 15 g of nano-silica was dispersed in 150 mL of deionized water, and then 8 g of allyl alcohol glycidyl ether and 2 g of catalyst stannous chloride were added thereto, and the mixture was heated and stirred at 90° C. for 2 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0040] Example 3

[0041] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0042] S1, add 6 parts of polybutylene adipate diol, 4 parts of 1,4-butene diol and 40 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heat and stir at 80°C for 2h, then add 15 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1h and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18h, to obtain a polyurethane elastomer;

[0043] S2, add 60 parts of polyurethane elastomer, 40 parts of polycaprolactone and 3 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 10 parts of modified nano-silica, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 2h, the irradiation intensity is 200W / cm 2 , that is, a shape memory composite material is obtained;

[0044] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0045] 12 g of nano-silica was dispersed in 150 mL of deionized water, and then 6 g of allyl alcohol glycidyl ether and 1.5 g of catalyst stannous chloride were added thereto, and the mixture was heated and stirred at 80° C. for 3 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0046] Example 4

[0047] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0048] S1, add 6 parts of polybutylene adipate diol, 4 parts of 1,4-butene diol and 35 parts of isophorone diisocyanate into a reactor, heat and stir at 75°C for 3 hours, then add 10 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1 hour and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18 hours, to obtain a polyurethane elastomer;

[0049] S2, 55 parts of polyurethane elastomer, 35 parts of polycaprolactone and 3 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone were added to the torque rheometer and mixed evenly, and then 8 parts of modified nano-silica were added and mixed evenly to obtain a mixture, and the mixture was placed in a flat vulcanizer for molding, and then irradiated with a 365nm ultraviolet lamp for 2h, and the irradiation intensity was 200W / cm 2 , that is, a shape memory composite material is obtained;

[0050] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0051] 10 g of nano-silica was dispersed in 150 mL of deionized water, and then 4 g of allyl alcohol glycidyl ether and 1 g of catalyst stannous chloride were added thereto, and the mixture was heated and stirred at 80° C. for 3 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0052] Comparative Example 1

[0053] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0054] S1. Add 10 parts of polybutylene adipate diol and 30 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heat and stir at 70°C for 4 hours, then add 10 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1 hour and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18 hours to obtain a polyurethane elastomer;

[0055] S2, add 40 parts of polyurethane elastomer, 30 parts of polycaprolactone and 2 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 5 parts of modified nano-silica, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 2h, the irradiation intensity is 100W / cm 2 , that is, a shape memory composite material is obtained;

[0056] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0057] 10 g of nano-silica was dispersed in 150 mL of deionized water, and then 4 g of allyl alcohol glycidyl ether and 1 g of catalyst stannous chloride were added thereto, and the mixture was heated and stirred at 75° C. for 4 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0058] Compared with Example 1, Comparative Example 1 replaces 1,4-butene diol in the raw material with polybutylene adipate diol.

[0059] Comparative Example 2

[0060] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0061] S1, add 6 parts of polybutylene adipate diol, 4 parts of 1,4-butene diol and 30 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heat and stir at 70°C for 4 hours, then add 10 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1 hour and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18 hours, to obtain a polyurethane elastomer;

[0062] S2, add 40 parts of polyurethane elastomer, 30 parts of polycaprolactone and 2 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 5 parts of nano-silicon dioxide, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 2h, the irradiation intensity is 100W / cm 2 , that is, a shape memory composite material is obtained.

[0063] Compared with Example 1, Comparative Example 2 did not perform modification treatment on the nano-silicon dioxide.

[0064] Comparative Example 3

[0065] A method for preparing a shape memory composite material for a pessary comprises the following steps:

[0066] S1, add 6 parts of polybutylene adipate diol, 4 parts of 1,4-butene diol and 30 parts of 4,4'-methylenebis(phenyl isocyanate) into a reactor, heat and stir at 70°C for 4 hours, then add 10 parts of chain extender diethanolamine, stir evenly and put into a mold, let stand for 1 hour and then demould, then put in an oven for aging, the aging temperature is 100°C, and the aging time is 18 hours, to obtain a polyurethane elastomer;

[0067] S2, add 40 parts of polyurethane elastomer, 30 parts of polycaprolactone and 2 parts of photoinitiator 4-propyleneoxy-2-hydroxybenzophenone into the torque rheometer, mix evenly, then add 5 parts of modified nano-silica, mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then irradiate with a 365nm ultraviolet lamp for 2h, the irradiation intensity is 100W / cm 2 , that is, a shape memory composite material is obtained;

[0068] Wherein, the preparation method of modified nano silicon dioxide is as follows:

[0069] 10 g of nano-silica was dispersed in 150 mL of 60 wt% ethanol aqueous solution, and then 4 g of vinyltriethoxysilane was added thereto. The mixture was heated and stirred at 75° C. for 4 h, and then filtered, washed, and dried to obtain modified nano-silica.

[0070] Compared with Example 1, Comparative Example 3 uses vinyltriethoxysilane to modify the nano-silicon dioxide.

[0071] The shape memory composite materials prepared in Examples 1-4 and Comparative Examples 1-3 were subjected to performance tests, and the test results are shown in Table 1.

[0072] The test steps of deformation recovery rate are as follows: take the initial length as L 0 The spline is loaded onto the fixture and then stretched to a length L. 1 Keep it for five minutes, take out the sample and keep it at room temperature for 5 minutes, and record its length L 2 , calculate the deformation recovery rate, where deformation recovery rate (%) = (L 1 -L 2 ) / (L 1 -L 0 )×100%, test 5 times and take the average value of the results.

[0073] Table 1 Performance of samples obtained from Examples 1-4 and Comparative Examples 1-3

[0074] Tensile strength(MPa) Elastic modulus (MPa) Deformation recovery rate (%) Example 1 51.2 264 99.3 Example 2 49.6 253 99.1 Example 3 52.1 272 99.4 Example 4 50.5 260 98.8 Comparative Example 1 42.7 208 92.5 Comparative Example 2 38.3 161 89.6 Comparative Example 3 50.4 256 88.2

[0075] It can be seen from Table 1 that the shape memory composite material provided by the present invention has a tensile strength of more than 50 MPa and an elastic modulus of more than 250 MPa, and has excellent mechanical properties; the deformation recovery rate is more than 99%, and has excellent shape memory properties.

[0076] Finally, it should be noted that the above embodiments do not limit the present invention in any form. For those skilled in the art, some modifications and improvements can be made to the present invention. Therefore, any modification or improvement made without departing from the spirit of the present invention belongs to the scope of protection claimed in the present invention.

Claims

1. A method for preparing a shape memory composite material for a pessary, characterized in that: The following steps are involved: S1, adding polyol and diisocyanate into a reactor, heating and stirring to react, then adding chain extender diethanolamine, stirring evenly and putting into a mold, letting it stand and then demoulding, and then placing in an oven for aging to obtain a polyurethane elastomer; S2. Evenly mix the polyurethane elastomer, polycaprolactone and photoinitiator, then add modified nano-silica and mix evenly to obtain a mixture, put the mixture into a flat vulcanizer for molding, and then perform ultraviolet light irradiation treatment to obtain a shape memory composite material.

2. The preparation method according to claim 1, characterized in that: In step S1, the mass ratio of polyol, diisocyanate and diethanolamine is 1:3-4:1-1.

5.

3. The preparation method according to claim 1, characterized in that: In step S1, the polyol is selected from polybutylene adipate diol and 1,4-butene diol, wherein the mass ratio of polybutylene adipate diol to 1,4-butene diol is 3-5:1-2.

4. The preparation method according to claim 1, characterized in that: In step S1, the diisocyanate is selected from 4,4'-methylenebis(phenyl isocyanate), isophorone diisocyanate or toluene-2,4-diisocyanate.

5. The preparation method according to claim 1, characterized in that: In step S1, the temperature of the heating and stirring reaction is 70-80°C, and the time of the heating and stirring reaction is 2-4h.

6. The preparation method according to claim 1, characterized in that: In step S2, the mass ratio of polyurethane elastomer, polycaprolactone, photoinitiator and modified nano-silica is 40-60:30-40:2-3:5-10, wherein the photoinitiator is selected from 4-propyleneoxy-2-hydroxybenzophenone.

7. The preparation method according to claim 1, characterized in that: In step S2, the preparation method of the modified nano-silica is as follows: disperse the nano-silica in deionized water, then add allyl alcohol glycidyl ether and catalyst stannous chloride thereto, heat and stir to react, then filter, wash and dry to obtain the modified nano-silica.

8. The preparation method according to claim 7, characterized in that: The mass ratio of nano silicon dioxide, allyl alcohol glycidyl ether and stannous chloride is 10-15:4-8:1-2.

9. The preparation method according to claim 7, characterized in that: The temperature of the heating and stirring reaction is 75-90°C, and the time of the heating and stirring reaction is 2-4h.

10. A shape memory composite material for a pessary prepared by the preparation method according to any one of claims 1 to 9.