CN116715825B - Hydrothermal soft polyurethane and preparation method and application thereof - Google Patents

Hydrothermal soft polyurethane and preparation method and application thereof Download PDF

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CN116715825B
CN116715825B CN202310743011.8A CN202310743011A CN116715825B CN 116715825 B CN116715825 B CN 116715825B CN 202310743011 A CN202310743011 A CN 202310743011A CN 116715825 B CN116715825 B CN 116715825B
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polyurethane
diisocyanate
soft
molecular weight
hydrothermal
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CN116715825A (en
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叶恒
谭遂丹
杨建�
刘灯旺
漆辉刚
黄仕林
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Meishan Youborui New Material Co ltd
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Meishan Youborui New Material Co ltd
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    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
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    • A61L2400/16—Materials with shape-memory or superelastic properties

Abstract

The invention provides hydrothermal soft polyurethane and a preparation method and application thereof, and belongs to the technical field of polyurethane material preparation. The hydrothermal soft polyurethane provided by the invention is prepared by taking a polymer as a soft segment and taking a hydrophilic chain extender and diisocyanate as a hard segment; wherein the hydrophilic chain extender is low molecular weight nylon, and the polymer of the soft segment comprises any one or more of PCDL, PBA, PCL, PLA, PTMEG. The polyurethane provided by the invention releases the interaction between the hard segment and the soft segment and between the hard segment and the hard segment in the polyurethane through the water absorption of the hydrophilic chain extender, so that the polyurethane can be rapidly softened under the conditions of water absorption and heating, the obvious reduction of modulus after hydrothermal is realized, the reduction range of the elastic modulus is 30-80%, and the softening effect is extremely excellent. In addition, the polyurethane does not substantially soften under anhydrous heating conditions and softens under heating and water absorption conditions.

Description

Hydrothermal soft polyurethane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane preparation, and particularly relates to a hydrothermal soft polyurethane and a preparation method and application thereof.
Background
Polyurethane (PU) is short for polyurethane, its molecular structure contains repeated urethane bond (-NHCOO-) in polyurethane structure, hard segment and soft segment are alternatively distributed in polymer chain, macromolecular polyol (such as polyether polyol, polyester polyol, etc.) forms soft segment, diisocyanate and chain extender (such as diamine, diol, etc.) forms hard segment, soft segment gives polyurethane better elasticity, hard chain gives polyurethane good strength and modulus [1] 。
Polyurethane shows obvious difference in performance among different products due to flexible and various adjustment modes and different raw material component selection and preparation modes. Polyurethane materials have different requirements on the properties of the materials such as elongation at break, elastic modulus and the like in different application processes.
The intelligent high molecular material is a stimulus-response polymer or an environment-sensitive polymer, and is becoming an important branch subject in the new material field. It can make inanimate organic material capable of sensing external stimulus and environmental change and producing response driving, also called stimulus-responsive high-molecular material [2] . When the intelligent high polymer material is subjected to external stimulus such as solvent, heat, light, radiation, electricity, magnetic field, stress, enzyme or pH, the property (such as shape, rigidity, color, flexibility and internal energy) of the intelligent polymer which effectively responds to the stimulus can be changed, so that the functions of deformation, color change, self-repairing, energy storage, feedback and the like are realized [3] 。
Polyurethane (PU) with shape memory function is a kind of polyurethane with special structure, and its structure is composed of hard segment and soft segment PUs molecular chains. The shape memory polyurethane (Shape memorypolyurethanes, SMPU) can be prepared by strictly controlling the ratio of soft segments to hard segments in the polyurethane structure by molecular design or modification [4] 。
In particular, thermotropic shape memory polyurethanes generally comprise a stationary phase that determines the initial deformation and a reversible phase that undergoes a reversible softening, hardening transition with temperature changes [5] . In terms of the thermotropic shape memory polyurethane materials, the materials were successfully developed for the first time in the world by the company of Sanpa in 1988 [6] The shape recovery temperature is-30-70 ℃, and the shape recovery temperature has been widely applied to the biomedical field due to the excellent biocompatibility.
Peng Ping et al [7] A series of degradable shape memory polyurethane materials with Polycaprolactone (PCL) dihydric alcohol as a soft segment and Toluene Diisocyanate (TDI) as a hard segment are synthesized by taking stannous octoate as a catalyst and ethylene glycol as a chain extender. The study shows that the minimum recovery temperature can be controlled within the range of 37-42 ℃ by adjusting the molecular weight and the hard segment content of PCL, so as to meet the requirement of human implantation.
Due to the characteristics of the polyurethane structure, the material is easy to soften after heating, and the elastic modulus of the material is obviously reduced, so that the existing medical polyurethane catheter (such as a retention needle) material needs to be stored at a low temperature before being used, and the softening phenomenon caused by the temperature rise is prevented.
The water-sensitive shape memory polyurethane is another type of stimulus-responsive polyurethane, the hydrophilic soft segment of which is thermodynamically non-identical to the hydrophobic hard segmentCompatibility results in microphase separation, there is a significant difference in hydrophilicity between the two phases, and when water is contacted with the shape-immobilized polyurethane foam, it is desired that the water selectively penetrate into the hydrophilic segments, and the rapid water absorption expansion of the polymer results in an increase in volume and weight of the material; in , the hydrogen bonds between molecular chains are broken after water absorption, and the memory phase is driven and pulls the reversible phase to recover the shape; in the recovery process, the isocyanate chain segment is used as a hydrophobic area and a physical crosslinking area to prevent the polyurethane foam from being dissolved, limit the expansion and finally realize the shape recovery [8] 。
Polyurethane is used as a common polymer material for preparing medical catheters, and has the advantages of good biocompatibility, high specific strength, good stability, good flexibility and the like in the medical field [9-10] . The polyurethane material has good physical property, good processing property and controllable performance, and has biocompatibility matched with human cells, tissues and organs, so that the polyurethane polymer material has wide application in the medical field [11-12] 。
The polyurethane medical catheter is used as a medical appliance inserted into a human body and connected with the inside and the outside of the body, and is mainly applied to the aspects of drug delivery, intravenous transfusion, hemodialysis, interventional therapy and the like. This requires a medical catheter with high mechanical strength, which can be inserted into the body and can be used for the above-mentioned functional applications. Because polyurethane medical catheters need to have better flexibility after being inserted into the body, the polyurethane medical catheters are required to be softened to a certain extent in the body, provide better body feeling and avoid friction with tissues and organs and damage to organs, and therefore the polyurethane medical catheters need to be made into intelligent response polyurethane materials.
However, most of the existing intelligent responsive polyurethane materials are mainly used for restoring shape memory or performing a specific function, and few reports on in-vivo softening can be realized. The softening of polyurethane materials is mainly based on the property of increasing the temperature to soften the material, however it determines that such medical catheter materials need to be stored at low temperatures prior to insertion into the body. Patent document CN113372531B relates to a polyurethane with an increased modulus after water absorption, which is used as a lumen stent, and thus requires a lower modulus when implanted, has a better flexibility, and can absorb water and harden after implanted in vivo, thereby meeting the higher requirement of the stent material on modulus when in use. However, the polyurethane does not meet the requirements of medical catheters that require better compliance after insertion into the body to avoid friction and damage to organs and to provide a better feel.
After the medical catheter is inserted into a human body, a large amount of water environment exists in the human body and is contacted with body fluid in the human body, so that the medical catheter is softened, better flexibility is provided, polyurethane with reduced modulus after water absorption is needed to be provided, and the material is ensured not to be obviously softened in the temperature lifting process, so that the material is stored at normal temperature. The prior art reports do not relate to how to prepare polyurethanes having such thermal response properties while at the same time softening upon absorption of water.
Therefore, how to provide polyurethane which can not bring about obvious softening of polyurethane materials when the temperature is increased in a non-aqueous environment and can be heated after water absorption so as to greatly soften the materials, so that the polyurethane can be stored at a higher temperature, and can be obviously softened after being inserted into a body, the body feeling is improved, and the polyurethane is better applied to the field of medical catheters, so that the polyurethane belongs to the technical problem to be solved urgently.
The cited references are as follows:
[1] liu Bo, university of Anhui construction paper, functional polyurethane elastomer preparation and performance study, 2011.
[2] Zhang Lan bionic preparation of shape memory polymers and deformation Property study [ D ] Changchun: university of Jilin institute of biological and agricultural engineering, 2021.
[3] Application of the shape memory polymer matrix composites in aerospace applications [ J ]. Aviation manufacturing technology 2012, (18): 58-59.
[4]Li X,Liu W,Li Y,et al.Mechanically robust enzymatically degradable shape memory polyurethane urea with a rapid recovery response inducedby nir[J].Journal ofMaterials Chemistry B,2020,8(23):5117-5130.
[5] Wang Lin, doctor's paper, southwest university of transportation, application study of multifunctional shape memory polyurethane and polyester in biomaterials, 2014.
[6] Wang Shiren, et al, polymer science and engineering, 2000, 16 (1): 1-4.
[7]Peng Ping，et al.Biomacromolecules，2005，6(2):587-592.
[8]Gu X，MatherP T.Water-triggered shape memory ofmultiblock thermoplastic polyurethanes(TPUs)[J].Rsc Advances,2013,3(36):15783-15791.
[9] Guo Jintang, liu Bing. Synthesis of thermoplastic polyurethane biomaterials and surface modification progress [ J ]. Polymer bulletin. 2005,6:43-50.
[10] Jin Gang, lei Yucai, he Wei, etc. thermoplastic polyurethane processing characteristics study for medical catheters [ J ]. Plastics industry, 2011, 39:59-62.
[11] The application potential and market prospect of polyurethane elastomers in the medical field [ J ] polyurethane industry, 2016, 11:76-82.
[12] Bao Junjie, liu Doubao, li soldier medical polyurethane materials research progress [ J ]. Polyurethane industry, 2007,9:72-79.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a hydrothermal soft polyurethane and a preparation method and application thereof. The invention aims to provide a polyurethane material which is not obviously softened after the temperature is increased in a non-aqueous environment, but can be greatly softened by heating after water absorption, and a preparation method thereof, so that the problems of high cost and difficult transportation caused by low-temperature preservation in the preservation process of the existing polyurethane medical catheter material are solved; on the other hand, the problems that the existing polyurethane medical catheter has higher modulus in vivo, cannot effectively realize softening, is easy to rub tissues and organs and damage the organs and brings poor body feeling are solved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a hydrothermal soft polyurethane, which is prepared by taking a polymer as a soft segment and taking a hydrophilic chain extender and diisocyanate as a hard segment; wherein the hydrophilic chain extender is low molecular weight nylon, and the polymer comprises any one or more of PCDL, PBA, PCL, PLA, PTMEG.
Firstly, the invention relates to the "hydrothermally soft" polyurethane, which means that the polyurethane material can not obviously soften even if the temperature is raised under the anhydrous environment, and can well maintain the elastic modulus, and the modulus loss is not more than 3%; on the other hand, in the environment with water, when the temperature is raised, the material can well show the characteristic of hydrothermal softening, so as to realize the obvious softening of the material, and the reduction range of the elastic modulus can reach 30-80%.
According to the preparation method of the polyurethane, the low-molecular nylon is used as the hydrophilic chain extender, and the interaction between the hard segment and the soft segment and between the hard segment and the hard segment in the polyurethane is relieved through the water absorption of the hydrophilic chain extender, so that the polyurethane cannot be obviously softened after the temperature is increased (without water), but can be quickly softened through the temperature increase under the water condition, the great reduction of the elastic modulus after water absorption is realized, the softening effect is excellent, and the maximum 80% of the reduction of the modulus can be realized within 2 hours. On the one hand, the existing polyurethane medical catheter material cannot be prevented from being obviously softened in the heating process, and on the other hand, the softening effect after water absorption does not reach the degree of the invention.
Further, the number average molecular weight of the low molecular weight nylon is 200-4000Da.
Further, the number average molecular weight of the polymer is in the range of 20000 to 200000Da.
Further, the diisocyanate is at least one of aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate.
Further, the diisocyanate includes at least one of dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine ethyl ester diisocyanate, xylylene diisocyanate, hydrogenated toluene diisocyanate, naphthalene diisocyanate, or p-phenylene diisocyanate.
It is a further object of the present invention to provide a hydrothermally soft polyurethane prepared by the process described above.
Further, the elastic modulus of the polyurethane material is reduced by 30-80% before and after water absorption and heating.
Further, the elastic modulus of the polyurethane material does not decrease by more than 3% under heating only (anhydrous).
It is a further object of the present invention to provide a polyurethane prepared by the process as described above or the use of a polyurethane as described above as a medical catheter material.
Specifically, the medical catheter comprises an indwelling needle catheter, a PCI catheter, a catheter, an endotracheal tube catheter, a central venous catheter and the like.
The beneficial effects of the invention are as follows:
(1) The invention provides a hydrothermal soft polyurethane material, which can not generate obvious softening of the material when in anhydrous heating, the loss rate of elastic modulus is not more than 3 percent, the material can be quickly and obviously softened by heating after water absorption in water environment, the reduction of the elastic modulus can reach 30-80 percent, and the softening effect is obvious;
(2) The polyurethane material provided by the invention is used as a medical catheter material, can realize softening due to moisture in an absorber and temperature rise after body temperature contact after being inserted into a human body, can well avoid friction and damage of the medical catheter material to organs in the human body, has the characteristic of good body feel, is stored at normal temperature or higher temperature before being used, does not need to be stored at low temperature, and reduces the use cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be specifically described with reference to the following examples, which are provided for explaining and illustrating the present invention only and are not intended to limit the present invention. Some non-essential modifications and adaptations of the invention according to the foregoing summary will still fall within the scope of the invention.
The relevant terms mentioned in the present invention and their meanings are as follows:
IPDI: isophorone diisocyanate, LDI: lysine diisocyanate, MDI: diphenylmethane diisocyanate, HMDI: dicyclohexylmethane diisocyanate, HDI: hexamethylene diisocyanate, XDI: xylylene diisocyanate;
PCDL: a polycarbonate diol; PBA: polyadipic acid-1, 4-butanediol ester diol; PCL: polycaprolactone; PLA: polylactic acid; PTMG: polytetrahydrofuran ether glycol.
Example 1
A kind of hydrothermally soft polyurethane, it is to regard polymer as the soft segment, regard hydrophilic chain extender and diisocyanate (MDI, diphenylmethane diisocyanate) as the hard segment to prepare; wherein the hydrophilic chain extender is low molecular weight nylon, the number average molecular weight of the hydrophilic chain extender is 2000Da, the polymer is PTMG, and the number average molecular weight of the hydrophilic chain extender is 1000Da.
The preparation method of the polyurethane comprises the following steps:
(1) Stirring and mixing PTMG, BDO and low molecular weight nylon uniformly at 80 ℃;
(2) Melting MDI at 50 ℃;
(3) Mixing the heated materials, wherein the mass ratio of the materials is PTMG: BDO: nylon: mdi=55: 10:8:27, then injecting into a double-screw reactor for reaction plasticization, extruding, granulating, and drying to obtain the thermoplastic polyurethane elastomer.
Example 2
Polyurethane was prepared according to the method of example 1, wherein the soft segment was PCL, the number average molecular weight thereof was 100000Da, the number average molecular weight of the hydrophilic chain extender low molecular weight nylon was 4000Da, the diisocyanate was isophorone diisocyanate (IPDI), and the mass ratio of each material was PCL: BDO: nylon: ipdi=60: 5:10:25.
example 3
Polyurethane was prepared according to the method of example 1, wherein the soft segment was PBA with a number average molecular weight of 50000Da, the hydrophilic chain extender low molecular weight nylon with a number average molecular weight of 500Da, the diisocyanate was Hexamethylene Diisocyanate (HDI), the mass ratio of the materials was PBA: BDO: nylon: hdi=62: 8:15:15.
example 4
Polyurethane was prepared according to the method of example 1, wherein the soft segment was PLA, its number average molecular weight was 200000Da, the number average molecular weight of the hydrophilic chain extender low molecular weight nylon was 200Da, the diisocyanate was diphenylmethane diisocyanate (MDI), the mass ratio of the respective materials was PBA: BDO: nylon: mdi=55: 18:5:22.
example 5
Polyurethane was prepared according to the method of example 1, wherein the soft segment was PCDL, the number average molecular weight thereof was 100000Da, the number average molecular weight of the hydrophilic chain extender low molecular weight nylon was 3000Da, the diisocyanate was diphenylmethane diisocyanate (MDI), and the mass ratio of the respective materials was PCDL: BDO: nylon: mdi=58: 18:5:19.
comparative example 1
According to the method of example 1, no nylon was added, but BDO alone was used as a chain extender.
Comparative example 2
According to the method of example 1, nylon was not added, but only HDO was used as a chain extender.
Comparative example 3
According to the method of example 1, nylon was not added, but only pentanediol was used as a chain extender.
Comparative example 4
According to the method of example 1, no nylon was added, but only ethylenediamine was used as a chain extender.
Comparative example 5
According to the method of example 1, nylon was not added, but only dimethylolpropionic acid was used as a chain extender.
Experimental example 1
The polyurethanes obtained in examples and comparative examples were subjected to temperature-rising thermal softening property test and characterization, young's modulus in a dry state at 23℃and Young's modulus after transferring the product to a dry state at 37℃for 2 hours, and Young's modulus retention was calculated, and the results are shown in Table 1 below.
Table 1 comparison of results of thermal Soft energy tests of materials in 23 ℃ Dry state and 37 ℃ Dry state
As can be seen from the results in Table 1, the polyurethane prepared in the examples of the present invention has a high modulus retention rate when heated in an anhydrous environment, and substantially no softening occurs, and the softening degree is lower than 3%. The polyurethane prepared by the comparative example scheme has a larger softening range with the rise of temperature.
Experimental example 2
The polyurethanes obtained in examples and comparative examples were subjected to the hydrothermal softening energy test and characterization, the Young's modulus was tested in a dry state at 23℃and the Young's modulus after the product was transferred to a wet state at 37℃for 2 hours, and the Young's modulus retention was calculated, and the results are shown in Table 2 below.
Table 2 comparison of results of thermal Soft energy tests of materials in Dry state at 23℃and in Wet state at 37 ℃
From the results shown in table 2, the polyurethane material prepared by the embodiment of the invention has good hydrothermal softening energy, can realize the softening degree of the material after water absorption of 30-80% through water absorption and temperature rise in a water environment, and shows excellent temperature rise water absorption softening property. When the nylon with small molecular weight is not added as a chain extender, but is replaced by other chain extenders, the softening effect of the material is limited, and the softening degree of the material cannot be achieved.

Claims (9)

1. The preparation method of the hydrothermal soft polyurethane is characterized in that the hydrothermal soft polyurethane is prepared by taking a polymer as a soft segment and taking a hydrophilic chain extender and diisocyanate as a hard segment; wherein the hydrophilic chain extender is low molecular weight nylon, and the number average molecular weight of the low molecular weight nylon is 200-4000Da; the polymer includes any one or more of PCDL, PBA, PCL, PLA, PTMEG.
2. The method of claim 1, wherein the polymer has a number average molecular weight in the range of 20000 to 200000Da.
3. The method according to claim 1, wherein the diisocyanate comprises at least one of aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
4. The method according to claim 3, wherein the diisocyanate comprises at least one of dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine ethyl ester diisocyanate, xylylene diisocyanate, hydrogenated toluene diisocyanate, naphthalene diisocyanate, and p-phenylene diisocyanate.
5. A hydrothermally soft polyurethane prepared by the process of any one of claims 1-4.
6. The polyurethane of claim 5, wherein the polyurethane has a decrease in elastic modulus after heating and water absorption of 30 to 80%.
7. The polyurethane of claim 5 wherein the polyurethane exhibits a material elastic modulus reduction of no more than 3% under heating only anhydrous conditions.
8. Use of a polyurethane obtainable by the process according to any one of claims 1 to 4 or a polyurethane according to any one of claims 5 to 7 as a medical catheter material.
9. The use according to claim 8, wherein the medical catheter comprises an indwelling needle catheter, a PCI catheter, a urinary catheter, an endotracheal tube or a central venous catheter.
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