Wear-resistant medical connecting line and preparation method thereof

Abstract

The invention relates to a wear-resistant medical connecting line and a preparation method thereof, and belongs to the technical field of high polymer materials. The wear-resistant medical connecting line is prepared from the following components in parts by weight: 50 to 80 parts of TPU (thermoplastic polyurethane), 1 to 8 parts of flexibilizer, 0.1 to 1 part of antioxidant, 4 to 12 parts of glass fiber and 5 to 18 parts of modified flame retardant, the modified flame retardant generates non-combustible substances in the combustion process, covers the surface of the material and isolates oxygen, acryloyl chloride releases free radicals in the combustion process and promotes carbon formation, so that the flame retardant effect is enhanced, tetraphenyl bisphenol A diphosphate can rapidly form a compact carbonized layer in the combustion process, meanwhile, good compatibility is kept, and the service life of the material is prolonged. The stable performance is maintained at a relatively high temperature, and the flame retardant is synergistically flame-retardant with phosphorus-oxygen double bonds and silicon-oxygen bonds; the wear-resistant medical connecting line prepared by the invention not only has a good wear-resistant effect, but also has excellent heat-resistant and flame-retardant effects.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a wear-resistant medical connecting wire and a preparation method thereof. Background Art

[0002] TPU, namely thermoplastic polyurethane elastomer rubber, is an important material for manufacturing medical connecting wires. Due to its excellent processability, flexibility and wide hardness range, it shows good comprehensive properties in wear resistance, elasticity and mechanical properties, and is widely used in daily necessities, sports goods, toys and decorative materials.

[0003] However, the oxygen index of ordinary TPU is relatively low, it is flammable and accompanied by serious melting drop phenomenon during combustion, which limits its scope of use. To improve the flame retardancy of TPU, the common method is to add halogen-containing flame retardants. However, these flame retardants act through gas-phase flame retardancy and will release a large amount of toxic gases and smoke during combustion, which not only pollutes the environment but also poses a serious threat to human health, and may even cause suffocation and death, bringing major safety hazards to production and life. Therefore, the research and development of wear-resistant medical connecting wires with excellent properties has important practical significance and application value. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a wear-resistant medical connecting wire and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A wear-resistant medical connecting wire and a preparation method thereof, comprising the following raw materials in parts by weight: 50-80 parts of thermoplastic polyurethane elastomer TPU, 1-8 parts of toughening agent, 0.1-1 part of antioxidant, 4-12 parts of glass fiber, 5-18 parts of modified flame retardant;

[0007] The toughening agent is polycaprolactone diol;

[0008] The antioxidant is antioxidant 1010.

[0009] The modified flame retardant is prepared by the following method:

[0010] Step A1: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tetrahydrofuran evenly, then add azobisisobutyronitrile and acryloyl chloride, and react at 65 °C for 24 h under nitrogen protection, followed by distillation under reduced pressure and vacuum drying for 8 h to obtain a compound;

[0011] Furthermore, the dosage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrahydrofuran, azobisisobutyronitrile, and acryloyl chloride is 0.01-0.03 mol: 20-50 mL: 0.16 g: 0.01-0.03 mol;

[0012] First, use the carbon-carbon double bond of acryloyl chloride to react with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to synthesize a compound;

[0013] Step A2: Mix 3-chloropropylmethyldimethoxysilane and an ethanol-water mixed solution at 35 °C for 10 min. Under nitrogen protection, add the compound and triethylamine and mix them. Then, raise the temperature to 60 °C and react for 5 h. After the temperature drops to room temperature, wash, rotary evaporate, and dry under vacuum at 60 °C to obtain an intermediate product;

[0014] Furthermore, the dosage ratio of 3-chloropropylmethyldimethoxysilane, the ethanol-water mixed solution, the compound, and triethylamine is 0.01 - 0.03 mol: 150 mL: 0.02 - 0.06 mol: 14 mL, and the volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 4:1;

[0015] Secondly, use the silicon hydroxyl group formed by the hydrolysis of 3-chloropropylmethyldimethoxysilane to react with the chlorine atom of the compound to obtain an intermediate product;

[0016] Step A3: Mix the intermediate product and tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add anhydrous aluminum trichloride, raise the temperature to 105 - 110 °C, react for 4 h, distill, wash, and dry to obtain a modified flame retardant;

[0017] Furthermore, the dosage ratio of the intermediate product, tetraphenylbisphenol A diphosphate, and anhydrous aluminum trichloride is 0.04 - 0.08 mol: 0.01 - 0.02 mol: 0.15 g;

[0018] Finally, use the acyl chloride of the intermediate product to react with the hydroxyl group of tetraphenylbisphenol A diphosphate to synthesize a modified flame retardant.

[0019] A preparation method of a wear-resistant medical connecting wire specifically includes the following steps:

[0020] S1. Mix thermoplastic polyurethane elastomer TPU, a toughening agent, an antioxidant, and glass fiber and stir for 10 - 15 min to obtain a mixed material;

[0021] S2. Put the mixed material and the modified flame retardant into a twin-screw extruder, extrude, and pelletize to obtain a wear-resistant medical connecting wire. The temperature of the conveying and melting section of the twin-screw extruder is 160 - 190 °C, the temperature of the mixing section is 170 - 195 °C, the temperature of the exhaust and homogenization section is 175 - 200 °C, and the temperature of the head of the extruder is 205 - 215 °C.

[0022] The beneficial effects of the present invention:

[0023] The wear-resistant medical connecting wire of the present invention has good wear resistance, and at the same time has excellent heat resistance and flame retardant effects, prolonging the service life of the material.

[0024] The modified flame retardant prepared by the present invention can generate non-flammable substances during combustion, covering the surface of the material and isolating oxygen to achieve the flame retardant effect; among them, acryloyl chloride releases free radicals during combustion, quenching the combustion chain reaction and promoting carbonization, thereby enhancing the flame retardant effect; at the same time, tetraphenyl bisphenol A diphosphate can rapidly form a dense carbonized layer during combustion, effectively isolating oxygen and heat, while maintaining good compatibility and high thermal stability, and can maintain stable performance at a relatively high temperature; in addition, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a phosphaphenanthrene compound with high thermal stability, promotes the formation of a dense and continuous carbon layer during combustion, further isolating oxygen and heat exchange, and synergistically retarding fire with phosphorus-oxygen double bonds and silicon-oxygen bonds, prolonging its service life; in addition, the modified flame retardant prepared by the present invention is halogen-free, which helps to reduce environmental pollution and damage to the ecosystem, is harmless to human health, and realizes sustainable development. Specific embodiments

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] Example 1: A preparation method of a wear-resistant medical connecting wire specifically includes the following steps:

[0027] S1. Weigh the raw materials by weight: 50 parts of thermoplastic polyurethane elastomer TPU, 1 part of toughening agent, 0.1 part of antioxidant, 4 parts of glass fiber, and 5 parts of modified flame retardant (prepared in this example); mix and stir the thermoplastic polyurethane elastomer TPU, polycaprolactone diol, antioxidant 1010 and glass fiber for 10 minutes to obtain a mixture.

[0028] S2. Put the mixture and the modified flame retardant into a twin-screw extruder, extrude and pelletize to obtain a wear-resistant medical connecting wire. The temperature of the conveying and melting section of the twin-screw extruder is 160 °C, the temperature of the mixing section is 170 °C, the temperature of the exhaust and homogenization section is 175 °C, and the temperature of the head of the extruder is 205 °C.

[0029] The modified flame retardant is prepared by the following method:

[0030] Step A1: Mix 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 20 mL of tetrahydrofuran evenly, then add 0.16 g of azobisisobutyronitrile and 0.01 mol of acryloyl chloride. Under nitrogen protection, react at 65 °C for 24 h, carry out vacuum distillation, and dry in vacuum for 8 h to obtain a compound;

[0031] Step A2: Mix 0.01 mol of 3-chloropropylmethyldimethoxysilane and 150 mL of ethanol-water mixed solution at 35 °C for 10 min. Under nitrogen protection, add 0.02 mol of the compound and 14 mL of triethylamine and mix. Heat up to 60 °C and react for 5 h. Wait for the temperature to drop to room temperature, wash, rotary evaporate, and dry at 60 °C in vacuum to obtain an intermediate product. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 4:1;

[0032] Step A3: Mix 0.04 mol of the intermediate product and 0.01 mol of tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add 0.15 g of anhydrous aluminum trichloride, heat up to 105 °C, and react for 4 h. Distill, wash, and dry to obtain a modified flame retardant.

[0033] Example 2: A preparation method of a wear-resistant medical connecting wire, specifically including the following steps:

[0034] S1. Weigh raw materials by weight parts: 60 parts of thermoplastic polyurethane elastomer TPU, 3.3 parts of toughening agent, 0.4 part of antioxidant, 6.7 parts of glass fiber, 9.3 parts of modified flame retardant (prepared by this example); Mix thermoplastic polyurethane elastomer TPU, polycaprolactone diol, antioxidant 1010 and glass fiber and stir for 11.7 min to obtain a mixed material;

[0035] S2. Put the mixed material and the modified flame retardant into a twin-screw extruder, extrude, and pelletize to obtain a wear-resistant medical connecting wire. The temperature of the conveying and melting section of the twin-screw extruder is 170 °C, the temperature of the mixing section is 178 °C, the temperature of the exhaust and homogenization section is 183 °C, and the temperature of the head of the extruder is 208 °C;

[0036] The modified flame retardant is prepared by the following method:

[0037] Step A1: Mix 0.017 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 30 mL of tetrahydrofuran evenly, then add 0.16 g of azobisisobutyronitrile and 0.017 mol of acryloyl chloride. Under nitrogen protection, react at 65 °C for 24 h, carry out vacuum distillation, and dry in vacuum for 8 h to obtain a compound;

[0038] Step A2: Mix 0.017 mol of 3-chloropropylmethyldimethoxysilane with 150 mL of ethanol-water mixed solution at 35 °C for 10 min. Under nitrogen protection, add 0.033 mol of the compound and 14 mL of triethylamine and mix. Heat up to 60 °C and react for 5 h. Wait for the temperature to drop to room temperature, wash, rotary evaporate, and dry in vacuum at 60 °C to obtain the intermediate product. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 4:1;

[0039] Step A3: Mix 0.053 mol of the intermediate product and 0.013 mol of tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add 0.15 g of anhydrous aluminum trichloride, heat up to 106.7 °C, react for 4 h, distill, wash, and dry to obtain the modified flame retardant.

[0040] Example 3: A preparation method of a wear-resistant medical connecting wire, specifically including the following steps:

[0041] S1. Weigh the raw materials by weight: 70 parts of thermoplastic polyurethane elastomer TPU, 5.6 parts of toughening agent, 0.7 part of antioxidant, 9.3 parts of glass fiber, 13.7 parts of modified flame retardant (prepared by this example); Mix the thermoplastic polyurethane elastomer TPU, polycaprolactone diol, antioxidant 1010 and glass fiber and stir for 13.3 min to obtain a mixed material;

[0042] S2. Put the mixed material and the modified flame retardant into a twin-screw extruder, extrude and pelletize to obtain a wear-resistant medical connecting wire. The temperature of the conveying and melting section of the twin-screw extruder is 180 °C, the temperature of the mixing section is 187 °C, the temperature of the exhaust and homogenization section is 192 °C, and the temperature of the head of the extruder is 212 °C;

[0043] The modified flame retardant is prepared by the following method:

[0044] Step A1: Mix 0.023 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with 40 mL of tetrahydrofuran evenly, then add 0.16 g of azobisisobutyronitrile and 0.023 mol of acryloyl chloride. Under nitrogen protection, react at 65 °C for 24 h, carry out vacuum distillation, and dry in vacuum for 8 h to obtain the compound;

[0045] Step A2: Mix 0.023 mol of 3-chloropropylmethyldimethoxysilane with 150 mL of ethanol-water mixed solution at 35 °C for 10 min. Under nitrogen protection, add 0.047 mol of the compound and 14 mL of triethylamine and mix. Heat up to 60 °C and react for 5 h. Wait for the temperature to drop to room temperature, wash, rotary evaporate, and dry in vacuum at 60 °C to obtain the intermediate product. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 4:1;

[0046] Step A3: Mix 0.067 mol of the intermediate product and 0.017 mol of tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add 0.15 g of anhydrous aluminum trichloride, heat up to 108.3 °C, react for 4 h, then distill, wash, and dry to obtain the modified flame retardant.

[0047] Example 4: A preparation method of a wear-resistant medical connecting wire, specifically including the following steps:

[0048] S1. Weigh the raw materials by weight parts: 80 parts of thermoplastic polyurethane elastomer TPU, 8 parts of toughening agent, 1 part of antioxidant, 12 parts of glass fiber, and 18 parts of modified flame retardant (prepared by this example); Mix the thermoplastic polyurethane elastomer TPU, polycaprolactone diol, antioxidant 1010, and glass fiber and stir for 15 min to obtain a mixture.

[0049] S2. Put the mixture and the modified flame retardant into a twin-screw extruder, extrude, and pelletize to obtain the wear-resistant medical connecting wire. The temperature of the conveying and melting section of the twin-screw extruder is 190 °C, the temperature of the mixing section is 195 °C, the temperature of the exhaust and homogenization section is 200 °C, and the temperature of the head of the extruder is 215 °C.

[0050] The modified flame retardant is prepared by the following method:

[0051] Step A1: Mix 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 50 mL of tetrahydrofuran evenly, then add 0.16 g of azobisisobutyronitrile and 0.03 mol of acryloyl chloride. Under nitrogen protection, react at 65 °C for 24 h, carry out reduced pressure distillation, and vacuum dry for 8 h to obtain the compound.

[0052] Step A2: Mix 0.03 mol of 3-chloropropylmethyldimethoxysilane and 150 mL of ethanol-water mixed solution at 35 °C for 10 min. Under nitrogen protection, add 0.06 mol of the compound and 14 mL of triethylamine and mix. Heat up to 60 °C and react for 5 h. Wait for the temperature to drop to room temperature, wash, rotary evaporate, and dry at 60 °C under vacuum to obtain the intermediate product. The volume ratio of ethanol to deionized water in the ethanol-water mixed solution is 4:1.

[0053] Step A3: Mix 0.08 mol of the intermediate product and 0.02 mol of tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add 0.15 g of anhydrous aluminum trichloride, heat up to 110 °C, react for 4 h, then distill, wash, and dry to obtain the modified flame retardant.

[0054] Comparative example: This comparative example is a wear-resistant medical connecting wire. The difference from Example 3 is that magnesium hydroxide in equal amount is used instead of the modified flame retardant prepared in Example 3, and the rest are the same.

[0055] Performance test: The wear-resistant medical connecting wires prepared in Examples 1-3 and Comparative Examples were used to determine the flame retardancy performance according to the standard GB / T 2408-2008; the tensile strength at 25 °C and 50 °C was determined according to the standard GB / T 528-2009; the friction and wear test was determined according to the standard GB / T 3960-2016 (the smaller the value of the wear index, the better the wear resistance); the test results are shown in Table 1 below:

[0056] Table 1

[0057]

[0058] It can be seen from the data tested in Table 1 that the wear-resistant medical connecting wire prepared by the present invention has good wear resistance. It can also be seen from the above table that the wear-resistant medical connecting wire prepared by the present invention has heat resistance and flame retardancy effects, extending the service life of the material.

[0059] The above content is only an example and explanation of the concept of the present invention. Those skilled in the art of the present technology make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

Claims

1. A preparation method of a wear-resistant medical connection line, characterized in that, Specifically, it includes the following steps: S1. Weigh the raw materials by weight parts: 50 - 80 parts of thermoplastic polyurethane elastomer (TPU), 1 - 8 parts of toughening agent, 0.1 - 1 part of antioxidant, 4 - 12 parts of glass fiber, and 5 - 18 parts of modified flame retardant; Mix the thermoplastic polyurethane elastomer (TPU), toughening agent, antioxidant, and glass fiber and stir for 10 - 15 min to obtain a mixture. S2. Put the mixture and the modified flame retardant into a twin - screw extruder, extrude and pelletize to obtain a wear - resistant medical connecting wire. The temperature of the conveying and melting section of the twin - screw extruder is 160 - 190 °C, the temperature of the mixing section is 170 - 195 °C, the temperature of the exhaust and homogenization section is 175 - 200 °C, and the temperature of the head of the extruder is 205 - 215 °C.

2. The preparation method of a wear-resistant medical connecting wire according to claim 1, characterized in that, The modified flame retardant is prepared by the following method: Step A1: Mix 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide and tetrahydrofuran evenly, then add azobisisobutyronitrile and acryloyl chloride, and react at 65 °C for 24 h under nitrogen protection. Carry out vacuum distillation and vacuum drying for 8 h to obtain a compound. Step A2: Mix 3 - chloropropylmethyldimethoxysilane and an ethanol - water mixed solution at 35 °C for 10 min. Under nitrogen protection, add the compound and triethylamine and mix, then raise the temperature to 60 °C and react for 5 h. Wait until the temperature drops to room temperature, wash, rotary evaporate, and dry at 60 °C in vacuum to obtain an intermediate product. Step A3: Mix the intermediate product and tetraphenylbisphenol A diphosphate evenly. Under nitrogen protection, add anhydrous aluminum trichloride, raise the temperature to 105 - 110 °C, and react for 4 h. Distill, wash, and dry to obtain the modified flame retardant.

3. The preparation method of an abrasion-resistant medical connecting wire according to claim 2, characterized in that, In step A1, the dosage ratio of 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, tetrahydrofuran, azobisisobutyronitrile, and acryloyl chloride is 0.01 - 0.03 mol: 20 - 50 mL: 0.16 g: 0.01 - 0.03 mol.

4. The preparation method of a wear-resistant medical connection line according to claim 2, characterized in that, In step A2, the dosage ratio of 3 - chloropropylmethyldimethoxysilane, ethanol - water mixed solution, compound, and triethylamine is 0.01 - 0.03 mol: 150 mL: 0.02 - 0.06 mol: 14 mL, and the volume ratio of ethanol to deionized water in the ethanol - water mixed solution is 4:

1.

5. The preparation method of a wear-resistant medical connecting wire according to claim 2, characterized in that, In step A3, the dosage ratio of the intermediate product, tetraphenylbisphenol A diphosphate, and anhydrous aluminum trichloride is 0.04 - 0.08 mol: 0.01 - 0.02 mol: 0.15 g.

6. The preparation method of a wear-resistant medical connection line according to claim 1, characterized in that, The toughening agent is polycaprolactone diol, and the antioxidant is antioxidant 1010.

7. A wear-resistant medical connecting wire, characterized in that, Prepared according to the preparation method described in any one of claims 1 - 6.

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