Thermoplastic polyurethane tracheal tube material, and preparation method and application thereof

Abstract

The application provides a thermoplastic polyurethane tracheal tube material and a preparation method and application thereof. The thermoplastic polyurethane tracheal tube material is prepared by the reaction of polyols, a chain extender with a specific structure and diisocyanate. The prepared pneumatic tube has excellent strength, heat resistance and creep resistance.

Description

Technical Field

[0001] This invention relates to the field of thermoplastic polyurethane technology, specifically to a high-strength, heat-resistant thermoplastic polyurethane tubing material, its preparation method, and its application. Background Technology

[0002] Thermoplastic polyurethane elastomer (TPU) is a polymer composed of flexible soft segments and rigid hard segments. It exhibits rubber elasticity at low temperatures and can be plasticized and molded when heated. TPU possesses excellent mechanical properties, including high mechanical strength, wear resistance, and good toughness, and is widely used in the pipe industry.

[0003] Different types of pipes improve their strength or weather resistance through compounding or covalent bonding. CN118290867A addresses the issue of PVC pipes becoming brittle at low temperatures by compounding EVA and TPU, significantly improving impact strength, longitudinal shrinkage rate, and tensile strength. CN116948385A introduces a heat-resistant reinforced medical TPU compound, where polyamic acid added to thermoplastic polyurethane elastomer improves the pipe's bending performance and heat resistance. However, both of these solutions improve the pipe's strength or heat resistance by leveraging the properties of the incorporated materials through compounding, without fundamentally improving the properties of the polyurethane itself.

[0004] Therefore, it is necessary to develop a new method to improve the strength and heat resistance of polyurethane tubing materials. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a thermoplastic polyurethane tubing material with excellent strength, heat resistance and creep resistance, which can be used to prepare extruded tubing products.

[0006] Another object of the present invention is to provide a method for preparing the thermoplastic polyurethane tubing material, which has simple and easy operation steps.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows:

[0008] This invention provides a thermoplastic polyurethane tubing material, prepared from raw materials comprising the following parts by weight:

[0009] (1) 30-80 parts, preferably 32-75 parts, more preferably 40-65 parts of polyol;

[0010] (2) 20-50 parts, preferably 22-48 parts, more preferably 26-45 parts of diisocyanate;

[0011] (3) A composition of 3-17 parts, preferably 4-15 parts, more preferably 6-13 parts, of chain extender A and chain extender B; wherein, chain extender A is selected from small molecule diols; and chain extender B has the structure described in formula (1):

[0012]

[0013] Wherein, R is selected from linear or branched C1-C10 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, aralkyl, alkylaryl, polyether, preferably C1 alkyl (such as methyl), C6 cycloalkyl (such as cyclohexyl), C6 aryl (such as phenyl).

[0014] In one embodiment, the chain extender A is selected from small molecule diols, preferably aliphatic alkylene diols, having the general formula HO-C n H 2n -OH, where n = a natural number from 1 to 10, such as 1, 3, 5, 7, 9, 10, etc., preferably n = 4;

[0015] Preferably, the chain extender A is selected from one or more of butanediol and hexanediol.

[0016] The chain extender B is a product already disclosed in the prior art, and there are no specific requirements for its source. It can be a commercially available product obtained through commercial channels, or it can be prepared based on existing methods, such as the method disclosed in the Journal of Natural Products (2017), 80(1), 2-11.

[0017] For example, in this invention, one of the chain extenders B having the structure described in formula (1) can be prepared by the following method, with the specific steps as follows:

[0018] Under a nitrogen atmosphere, 3-amino-1,5-pentanediol and a compound with a hydroxyl group at one end and a carboxyl group at the other end are dissolved in an organic solvent (such as dichloromethane, dimethylformamide, etc.) at a molar ratio of 1:1-1.05. The reaction is carried out at room temperature for 4-6 hours with a catalyst (such as EDC, HoBt, triethylamine, etc.). The liquid is separated and collected, and after conventional post-treatment such as concentration and purification, a white solid, namely the chain extender B, is obtained.

[0019] The above method is carried out with reference to the process provided in the aforementioned literature Journal of Natural Products (2017). Specifically, for other related operations and process conditions in the above method of the present invention, as well as the apparatus used, the corresponding conventional selections in the art can be adopted. There are no particular restrictions on this. Those skilled in the art can optimize the process based on existing technology and known processes according to actual needs. It will not be elaborated here.

[0020] In one embodiment, the molar ratio of chain extender A to chain extender B is 20-5:1, such as 20:1, 18:1, 15:1, 13:1, 10:1, 8:1, 5:1, etc.

[0021] In one embodiment, the number-average molecular weight of the polyol is 500-3000 g / mol, preferably 1000-2000 g / mol.

[0022] In one embodiment, the polyol is selected from one or more of polyester polyols, polyether polyols, polycaprolactone polyols, and polycarbonate polyols.

[0023] In some specific examples, the number average molecular weight of the polyester polyol is between 500 and 3000, preferably between 1000 and 2000;

[0024] Preferably, the average hydroxyl functionality of the polyester polyol is 2;

[0025] Preferably, the polyester polyol is selected from one or more of the following: poly(1,2-propanediol adipate), poly(ethylene adipate), poly(diethylene adipate), poly(butylene adipate), poly(methyl propylene adipate), poly(1,2-propanediol succinate), poly(ethylene succinate), poly(diethylene succinate), poly(diethylene succinate), poly(dipropylene adipate), and poly(methyl propylene adipate).

[0026] In some specific examples, the number average molecular weight of the polyether polyol is between 500 and 000, preferably between 1000 and 2000;

[0027] Preferably, the polyether polyol has an average hydroxyl functionality of 2.

[0028] Preferably, the polyether polyol is selected from one or more of polypropylene glycol, polypropylene glycol copolyol, polytetrahydrofuran glycol, and polybutadiene glycol.

[0029] In some specific examples, the number average molecular weight of the polycaprolactone polyol is 500-3000, preferably between 1000-2000;

[0030] Preferably, the average hydroxyl functionality of the polycaprolactone polyol is 2;

[0031] Preferably, the polycaprolactone polyol is selected from one or more of the following: ethylene glycol polycaprolactone polyols, 1,4-butanediol polycaprolactone polyols, diethylene glycol polycaprolactone polyols, and neopentyl glycol polycaprolactone polyols.

[0032] In some specific examples, the number average molecular weight of the polycarbonate polyol is 500-3000, preferably between 1000-2000;

[0033] Preferably, the average hydroxyl functionality of the polycarbonate polyol is 2.

[0034] Preferably, the polycarbonate polyol can be synthesized by any one of the following methods: phosgene method, carbon dioxide-regulated copolymerization method, cyclic carbonate ring-opening polymerization method, or transesterification method. It is more preferably synthesized by transesterification reaction of diol and carbonate.

[0035] The above-mentioned synthesis methods are all existing processes in the field, and there are no special requirements for them in this invention, so they will not be described in detail here.

[0036] In one embodiment, the diisocyanate is selected from one or more of aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, preferably one or more of diphenylmethane diisocyanate and 4,4-dicyclohexylmethane diisocyanate.

[0037] The present invention also provides a method for preparing the thermoplastic polyurethane tubing material.

[0038] The thermoplastic polyurethane tubing material can be prepared by the conventional co-extrusion method used in the field of thermoplastic polyurethane, such as by a one-step reaction using a twin-screw extruder.

[0039] Specifically, a method for preparing the aforementioned thermoplastic polyurethane tubing material includes the following steps:

[0040] The thermoplastic polyurethane tubing material is prepared by uniformly mixing polyol with diisocyanate, chain extender A and chain extender B, and then granulating by twin-screw reactive extrusion.

[0041] Preferably, the extrusion temperature of the reactive extrusion is 80–240°C, more preferably 120–220°C.

[0042] For any related operations and process conditions not covered in the preparation method of this invention, as well as the apparatus used, conventional choices in the field can be adopted. Those skilled in the art can optimize the process based on existing technology and known processes according to actual needs, and there are no particular restrictions.

[0043] The thermoplastic polyurethane tubing material of the present invention has excellent strength and heat resistance, as well as creep resistance. Its burst pressure strength can reach more than 6.0 MPa, its heat resistance strength retention rate can reach 92%, and its creep constant pressure dimensional change rate can reach 5.3%.

[0044] The thermoplastic polyurethane tubing material described in this invention can be used to prepare extruded tubing products, and is especially suitable for preparing high-strength and heat-resistant extruded tubing products.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] In this invention, chain extender B is bonded to the polyurethane backbone. The amide bonds in the chain extender can participate in the hydrogen bonding of the hard segments, promoting the orientation of the hard segments. At the same time, the trihydroxy structure can form crosslinks in the hard segments through covalent bonds, effectively promoting strength improvement and heat resistance, while also providing creep resistance. Attached Figure Description

[0047] Figure 1 The 1H NMR spectrum of chain extender B1;

[0048] Figure 2 The 1H NMR spectrum of chain extender B2. Detailed Implementation

[0049] The present application will be further described below with reference to the embodiments. However, the present application is not limited to the listed embodiments, but should also include equivalent improvements and modifications of the technical solutions defined in the appended claims.

[0050] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0051] Unless otherwise specified, certain specific steps involved in the experimental methods used in the following examples are routine operations.

[0052] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0053] The main raw material sources used in the embodiments of this invention are as follows:

[0054] BDO (1,4-butanediol), MDI (diphenylmethane diisocyanate), HMDI (4,4-dicyclohexylmethane diisocyanate), and PBA (polybutylene adipate) are all products sold by Wanhua Chemical Group Co., Ltd.

[0055] PTMG (polytetramethylene ether glycol) was purchased from BASF;

[0056] 3-Amino-1,5-pentanediol, 3-hydroxypropionic acid, and 3-hydroxymethylbenzoic acid were all purchased from Aladdin;

[0057] Chain extender B was prepared according to the method disclosed in the Journal of Natural Products (2017), 80(1), 2-11. The specific steps are as follows:

[0058] Chain extender B1: 1 mole of 3-amino-1,5-pentanediol and 1 mole of 3-hydroxypropionic acid were dissolved in dimethylformamide. The reaction was catalyzed by EDC, HoBt, and triethylamine, and carried out at room temperature under a nitrogen atmosphere for 4 hours. The liquid was separated, collected, concentrated, and purified to obtain a white solid, which is chain extender B1. Its structural formula is shown below, and its 1H NMR spectrum is attached. Figure 1 :

[0059]

[0060] Chain extender B2: 1 mole of 3-amino-1,5-pentanediol and 1 mole of 3-hydroxymethylbenzoic acid were dissolved in dimethylformamide. The reaction was catalyzed by EDC, HoBt, and triethylamine, and carried out at room temperature under a nitrogen atmosphere for 4 hours. The liquid was separated, collected, concentrated, and purified to obtain a white solid, which is chain extender B2. Its structural formula is shown below, and its NMR spectrum is attached. Figure 2 :

[0061]

[0062] The thermoplastic polyurethane tubing material provided by the present invention will be described in detail below through specific embodiments.

[0063] Example 1:

[0064] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0065] (1) 50.0 parts of PBA (polybutylene adipate, molecular weight 2000 g / mol),

[0066] (2) 38.3 parts of MDI (diphenylmethane diisocyanate),

[0067] (3) 12.5 parts of BDO (1,4-butanediol) and chain extender B1, with a molar ratio of 5:1.

[0068] The above raw materials are mixed evenly, and then subjected to twin-screw reactive extrusion (extruder temperature 120-210℃, die temperature 220℃), followed by underwater pelletizing to obtain thermoplastic polyurethane tubing material.

[0069] Example 2:

[0070] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0071] (1) PTMG (polytetramethylene ether glycol, molecular weight 1000 g / mol) 50.0 parts,

[0072] (2) 40.0 parts of MDI (diphenylmethane diisocyanate),

[0073] (3) 10.2 parts of BDO (1,4-butanediol) and chain extender B1, with a molar ratio of 20:1.

[0074] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0075] Example 3:

[0076] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0077] (1) 60.0 parts of PBA (polybutylene adipate, molecular weight 2000 g / mol),

[0078] (2) 29.5 parts of MDI (diphenylmethane diisocyanate),

[0079] (3) 10.9 parts of HDO (1,6-hexanediol) and chain extender B2, with a molar ratio of 10:1.

[0080] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0081] Example 4:

[0082] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0083] (1) 60.0 parts of PTMG (polytetramethylene ether glycol, molecular weight 2000 g / mol),

[0084] (2) 33.7 parts of HMDI (4,4-dicyclohexylmethane diisocyanate),

[0085] (3) 7.19 parts of BDO (1,4-butanediol) and chain extender B2, with a molar ratio of 5:1.

[0086] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0087] Example 5:

[0088] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0089] (1) 65.0 parts of PBA (polybutylene adipate, molecular weight 2000 g / mol),

[0090] (2) 28.2 parts of HMDI (4,4-dicyclohexylmethane diisocyanate),

[0091] (3) 7.1 parts of BDO (1,4-butanediol) and chain extender B2, with a molar ratio of 20:1.

[0092] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0093] Example 6:

[0094] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0095] (1) 65.0 parts of PTMG (polytetramethylene ether glycol, molecular weight 2000 g / mol),

[0096] (2) 29.4 parts of HMDI (4,4-dicyclohexylmethane diisocyanate),

[0097] (3) 5.7 parts of HDO (1,6-hexanediol) and chain extender B1, with a molar ratio of 10:1.

[0098] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0099] Comparative Example 1:

[0100] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0101] (1) 60.0 parts of PBA (polybutylene adipate, molecular weight 2000 g / mol),

[0102] (2) 31.5 parts of MDI (diphenylmethane diisocyanate),

[0103] (3) 8.5 parts of BDO (1,4-butanediol).

[0104] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0105] Comparative Example 2:

[0106] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0107] (1) 65.0 parts of PTMG (polytetramethylene ether glycol, molecular weight 1000 g / mol),

[0108] (2) 28.2 parts of HMDI (4,4-dicyclohexylmethane diisocyanate),

[0109] (3) BDO (1,4-butanediol) 6.8 parts.

[0110] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0111] Comparative Example 3:

[0112] Thermoplastic polyurethane tubing material was prepared using the following raw material composition by weight:

[0113] (1) 65.0 parts of PTMG (polytetramethylene ether glycol, molecular weight 2000 g / mol),

[0114] (2) 29.6 parts of HMDI (4,4-dicyclohexylmethane diisocyanate),

[0115] (3) 5.5 parts of HDO (1,6-hexanediol) and trimethylolethane, with a molar ratio of 10:1.

[0116] Thermoplastic polyurethane tubing material was prepared using the same method as in Example 1.

[0117] The thermoplastic polyurethane tubing materials prepared in Examples 1-6 and Comparative Examples 1-3 were extruded to prepare tubing samples, and their performance was tested using the following methods. The results are shown in Table 1.

[0118] Bursting pressure test: On the bursting pressure testing machine, three 30cm long pipes were used to test the bursting pressure under the conditions of water flow, 23℃, and pressurization rate of 0.07Mpa / s, and the average value was taken.

[0119] Heat resistance test: Three specimens were placed at 113°C for 8 weeks, and the tensile strength retention rate of the samples before and after the placement was tested. Hardness was tested according to ASTM D2240, and tensile strength was tested according to ASTM D412.

[0120] Creep Expansion Rate Test: Using a pipe static pressure testing machine, three 30cm long pipes were used to test the outer diameter. After maintaining the pressure at 60℃ and 0.9MPa for 72 hours, the outer diameter was tested again. The expansion rate of the outer diameter was calculated.

[0121] Table 1. Performance test results of thermoplastic polyurethane tubing materials in the examples and comparative examples.

[0122]

[0123] As can be seen from Table 1, the thermoplastic polyurethane pipe of the present invention has excellent comprehensive performance. It not only has higher strength, but also higher burst pressure and higher heat resistance strength retention rate in Examples 1-6, and the creep expansion resistance is also improved.

[0124] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is impossible to exhaustively list all embodiments here. All obvious variations or modifications derived from the technical solutions of the present invention are within the spirit and scope of the present invention.

Claims

1. A thermoplastic polyurethane tubing material, characterized in that, It is prepared from raw materials comprising the following parts by weight: (1) 30-80 parts of polyol; (2) 20-50 parts of diisocyanate; (3) A composition of 3-17 parts of chain extender A and chain extender B; wherein, chain extender A is selected from small molecule diols; and chain extender B has the structure described in formula (1): （1） R is selected from linear or branched C1-C10 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, aralkyl, alkylaryl, and polyether.

2. The thermoplastic polyurethane gas tubing material according to claim 1, characterized in that, It is prepared from raw materials comprising the following parts by weight: (1) 32-75 parts of polyols; (2) 22-48 parts of diisocyanate; (3) A combination of 4-15 parts of chain extender A and chain extender B.

3. The thermoplastic polyurethane gas tubing material according to claim 2, characterized in that, It is prepared from raw materials comprising the following parts by weight: (1) 40-65 parts of polyols; (2) 26-45 parts of diisocyanate; (3) A combination of 6-13 parts of chain extender A and chain extender B.

4. The thermoplastic polyurethane gas tube material according to claim 1, characterized in that, R is selected from C1 alkyl, C6 cycloalkyl, and C6 aryl.

5. The thermoplastic polyurethane tubing material according to claim 1, characterized in that, The chain extender A is selected from aliphatic alkylene glycols, which have the general formula HO-CnH2n-OH, where n is a natural number from 1 to 10.

6. The thermoplastic polyurethane gas tubing material according to claim 1, characterized in that, The chain extender A is selected from one or more of butanediol and hexanediol.

7. The thermoplastic polyurethane tubing material according to claim 1, characterized in that, The molar ratio of chain extender A to chain extender B is 20-5:

1.

8. The thermoplastic polyurethane gas tubing material according to claim 1, characterized in that, The number-average molecular weight of the polyol is 500-3000 g / mol.

9. The thermoplastic polyurethane gas tubing material according to claim 1, characterized in that, The number average molecular weight of the polyol is 1000-2000 g / mol.

10. The thermoplastic polyurethane tubing material according to claim 1, characterized in that, The polyol is selected from one or more of polyester polyols, polyether polyols, polycaprolactone polyols, and polycarbonate polyols.

11. The thermoplastic polyurethane tubing material according to claim 10, characterized in that, The number average molecular weight of the polyester polyol is between 500 and 3000; and / or The number average molecular weight of the polyether polyol is between 500 and 3000; and / or The number-average molecular weight of the polycaprolactone polyol is 500-3000; and / or The number average molecular weight of the polycarbonate polyol is 500-3000.

12. The thermoplastic polyurethane tubing material according to claim 11, characterized in that, The number average molecular weight of the polyester polyol is between 1000 and 2000.

13. The thermoplastic polyurethane tubing material according to claim 11, characterized in that, The number average molecular weight of the polyether polyol is between 1000 and 2000.

14. The thermoplastic polyurethane tubing material according to claim 11, characterized in that, The number average molecular weight of the polycaprolactone polyol is between 1000 and 2000.

15. The thermoplastic polyurethane tubing material according to claim 11, characterized in that, The number average molecular weight of the polycarbonate polyol is between 1000 and 2000.

16. The thermoplastic polyurethane tubing material according to claim 10, characterized in that, The average hydroxyl functionality of the polyester polyol is 2; and / or, The polyether polyol has an average hydroxyl functionality of 2; and / or, The average hydroxyl functionality of the polycaprolactone polyol is 2; and / or, The average hydroxyl functionality of the polycarbonate polyol is 2.

17. The thermoplastic polyurethane tubing material according to claim 10, characterized in that, The polyester polyol is selected from one or more of the following: poly(1,2-propanediol adipate), poly(ethylene adipate), poly(diethylene adipate), poly(butylene adipate), poly(methyl propylene adipate), poly(1,2-propanediol succinate), poly(ethylene succinate), poly(diethylene succinate), poly(dipropylene adipate), and poly(methyl propylene adipate); and / or, The polyether polyol is selected from one or more of polypropylene glycol, polypropylene oxide and ethylene oxide copolymer glycol, polytetrahydrofuran glycol, and polybutadiene glycol; and / or The polycaprolactone polyol is selected from one or more of the following: ethylene glycol polycaprolactone polyols, 1,4-butanediol polycaprolactone polyols, diethylene glycol polycaprolactone polyols, and neopentyl glycol polycaprolactone polyols; and / or The polycarbonate polyol is synthesized using any one of the following methods: phosgene method, carbon dioxide-regulated copolymerization method, cyclic carbonate ring-opening polymerization method, or transesterification method.

18. The thermoplastic polyurethane tubing material according to claim 17, characterized in that, The polycarbonate polyol is synthesized through an ester exchange reaction between a diol and a carbonate.

19. The thermoplastic polyurethane tubing material according to claim 10, characterized in that, The diisocyanate is selected from one or more of aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.

20. The thermoplastic polyurethane tubing material according to claim 19, characterized in that, The diisocyanate is selected from one or more of diphenylmethane diisocyanate and 4,4-dicyclohexylmethane diisocyanate.

21. A method for preparing the thermoplastic polyurethane tubing material according to any one of claims 1-20, characterized in that, The steps are as follows: The thermoplastic polyurethane tubing material is prepared by uniformly mixing polyol with diisocyanate, chain extender A and chain extender B, and then granulating by twin-screw reactive extrusion.

22. The preparation method according to claim 21, characterized in that, The extrusion temperature of the reaction extrusion is 80–240°C.

23. The preparation method according to claim 22, characterized in that, The extrusion temperature of the reaction extrusion is 120–220°C.

24. The thermoplastic polyurethane tubing material according to any one of claims 1-20 or the thermoplastic polyurethane tubing material prepared by the method according to any one of claims 21-23, is used to prepare extruded tubing products.

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