CN105085857A - Waterproof breathable antibacterial thermoplastic polyurethane elastomer and preparation method thereof - Google Patents

Abstract

The present invention provides a waterproof, breathable and antibacterial thermoplastic polyurethane elastomer and a preparation method thereof. The thermoplastic polyurethane elastomer is mainly prepared from the following components by weight: 40 to 50 parts of polymerized polyol, 30 to 40 parts of isophorone diisocyanate, 10 to 15 parts of 1,4-butanediol, 10 to 15 parts of dihydroxy polydiphenylsiloxane modified by nano ZnO and 5 to 10 parts of hydroxyethyl acrylate. The present invention uses a mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol as the polymerized polyol, and the two act synergistically to improve the waterproof and oil-proof properties of the target product. At the same time, the antibacterial properties of the thermoplastic polyurethane elastomer are improved by adding nano ZnO-modified dihydroxy polydiphenylsiloxane and hydroxyethyl acrylate, and the thermoplastic polyurethane elastomer has good mechanical properties.

Description

Waterproof, breathable and antibacterial thermoplastic polyurethane elastomer and preparation method thereof

technical field

The invention belongs to the technical field of macromolecules, and relates to a thermoplastic polyurethane elastomer and a preparation method thereof, in particular to a waterproof, breathable and antibacterial thermoplastic polyurethane elastomer and a preparation method thereof.

Background technique

Thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) is a polymer material that can be melted by heating and can be dissolved by solvent. TPU molecules are linear, there is little crosslinking between molecules, and the glass transition temperature is low, so it has high strength, high elasticity and excellent wear resistance, oil resistance and low temperature resistance.

There are two types of thermoplastic polyurethane elastomers: polyester type and polyether type. The white irregular spherical or columnar particles have a relative density of 1.10 to 1.25. The relative density of the polyether type is smaller than that of the polyester type. The outstanding features of polyurethane thermoplastic elastomers are excellent wear resistance, excellent ozone resistance, high hardness, high strength, good elasticity, low temperature resistance, good oil resistance, chemical resistance and environmental resistance. The hydrolytic stability of type ester is much higher than that of polyester type.

Water-resistant thermoplastic polyurethane resin has excellent hydrolysis resistance and is widely used in waterproof coating process. Water has two effects on TPU. One is plasticization, that is, water molecules drill into the macromolecular chain and form hydrogen bonds with the polar groups in the polymer molecules, which weakens the force between the polymer molecules and stretches them. The strength, tear strength and wear performance decrease. This process is reversible. After drying and dehydration, the original performance can be restored; the second is the degradation of water, that is, the chemical degradation of TPU. This process is irreversible and the most harmful. of. TPU can be divided into polyester type and polyether type, and the hydrolysis process of the two is different. Since the ester group is easy to hydrolyze, the hydrolysis of the polyester TPU shows that the main chain is broken, the molecular weight is reduced, and the tensile strength and elongation are dropped sharply; while the polyether TPU is resistant to hydrolysis due to the ether group and the carbamate group. The hydrolysis shows that the crosslinks are broken slowly, the tensile strength decreases slowly, and the elongation increases first and then decreases. Therefore, polyether TPU has better water resistance.

Patent CN104448788A discloses a waterproof and moisture-permeable thermoplastic polyurethane film and its preparation method. The waterproof and moisture-permeable thermoplastic polyurethane film includes the following components in mass percentage: 80-85% thermoplastic polyurethane, 8-10% polyurethane slippery agent and 7-10% fogging agent; wherein, the raw materials for the preparation of the thermoplastic polyurethane include: 58-63 parts of polytetramethylene ether glycol, 30-35 parts of toluene diisocyanate, ethylene glycol ether acetate 5-8 parts and 1-3 parts of dibutyltin diacetate. Although the thermoplastic polyurethane film prepared by the invention has waterproof and moisture-permeable properties, it is very easy to grow and reproduce bacteria under suitable temperature and humidity conditions during actual application and storage, which affects its use.

Antibacterial polyurethane materials refer to a new class of functional materials that modify polyurethane materials by introducing antibacterial agents with antibacterial groups, so that polyurethane materials have the ability to inhibit or kill bacteria on their surfaces. At present, the commonly used antibacterial agents mainly include three categories: natural, inorganic and organic. Organic antibacterial agents can effectively inhibit the generation and reproduction of harmful bacteria and molds, with quick results. However, this type of antibacterial agent has poor thermal stability (can only be used below 300 ° C), is easy to decompose, has poor persistence, and is usually more toxic, and is harmful to the human body if used for a long time; the advantage of inorganic antibacterial agents is that it has low toxicity, Heat resistance, durability, persistence, broad antibacterial spectrum, etc., are the most suitable antibacterial agents for daily products such as fibers, plastics, and building materials.

Patent CN104109332A discloses an antibacterial thermoplastic elastomer and its preparation method and application. The antibacterial thermoplastic elastomer includes the following components in weight percentage: SEBS15-30%, rubber filler oil 10-30%, polyurethane 10-25%, antibacterial 15-30% of the masterbatch, 5-25% of the first inorganic filler, 5-15% of the first compatibilizer and 0-2% of other additives; the preparation method includes the steps of weighing each component and adopting side feeding The steps of processing each component by means of melt mixing and extruding. Although the antibacterial thermoplastic elastomer prepared in this patent has excellent antibacterial effect, its waterproof and breathable performance is not ideal, the antibacterial performance is not durable, and its mechanical properties need to be improved.

Therefore, it is an urgent problem to be solved to prepare a thermoplastic polyurethane elastomer with excellent waterproof and breathable properties, antibacterial properties and good mechanical properties.

Contents of the invention

Aiming at the problem that thermoplastic elastomers in the prior art cannot have both waterproof, breathable and antibacterial properties, and improve their mechanical properties at the same time, the present invention provides a waterproof, breathable and antibacterial thermoplastic polyurethane elastomer and a preparation method thereof. In the present invention, a mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol acts synergistically to improve the water and oil repellency of the target product; at the same time, nano-ZnO is added to modify Non-toxic dihydroxypolydiphenylsiloxane improves the antibacterial properties of thermoplastic polyurethane elastomers and makes them have good mechanical properties.

For reaching this purpose, the present invention adopts following technical scheme:

In a first aspect, the present invention provides a thermoplastic polyurethane elastomer, which is mainly prepared by the following components in parts by weight:

Wherein, the polymer polyol is a mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol.

The parts by weight of polymer polyol can be 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts or 50 parts etc.; The parts by weight of isophorone diisocyanate can be 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts or 40 parts etc.; the weight part of 1,4-butanediol can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.; The parts by weight of hydroxypolydiphenylsiloxane can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.; the parts by weight of hydroxyethyl acrylate can be 5 parts, 6 parts, 7 parts, 8, 9 or 10 etc.

Preferably:

Further preferred are:

In the present invention, the mass ratio of fluorine-containing polyether diol to 1,4-butanediol adipate diol in the polymer polyol is (3～5):1, for example 3:1, 3.5: 1, 4:1, 4.5:1 or 5:1, etc., preferably 4:1.

The mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol is used as a polymer polyol to participate in the reaction, and the characteristics of high surface energy and non-lipophilic and non-hydrophilic characteristics of fluorine-containing compounds are used to improve The water and oil repellency of the target product. At the same time, the hydrolysis of polyester type and polyether type thermoplastic polyurethane is different. The present invention utilizes the synergistic effect of the two by adjusting the mixing ratio of fluorine-containing polyether diol and 1,4-butanediol adipate diol. Function, improve its mechanical properties while improving waterproof and breathable properties. If the mass ratio of fluorine-containing polyether diol and 1,4-butanediol adipate diol is less than 3:1, it will reduce the waterproof and air permeability of thermoplastic polyurethane elastomer; if fluorine-containing polyether diol and The mass ratio of 1,4-butanediol adipate diol is greater than 5:1, which will reduce the mechanical properties of thermoplastic polyurethane elastomers, such as tensile strength and elongation at break.

In the present invention, nano-ZnO modified dihydroxy polydiphenylsiloxane is added, which can replace a part of hydrophilic TPU, and the functional group therein can also react with the hydroxyl group at the TPU end, reducing the hydrophilicity of TPU. , Improve the antibacterial properties of TPU. However, if the content of nano-ZnO modified dihydroxy polydiphenylsiloxane is too high, it will cause phase separation with TPU and reduce the physical properties.

In the prior art, in order to improve the antibacterial performance of materials, there is a method of dispersing silver nanoparticles in a solvent to obtain a dispersion, and then contacting the dispersion with the surface of the substrate that will impart antibacterial properties to obtain antibacterial properties. Nano-inorganic antibacterial materials can be divided into two categories: one is metal oxides such as _{TiO 2} and ZnO which have antibacterial activity _; Antibacterial zeolite.

However, the particle size of nanoparticles is very small, and its high surface energy makes it easy to agglomerate, poor dispersion, and the formation of secondary particles, which cannot show its favored surface area effect, volume effect and quantum size effect, making it impossible to maintain Long-lasting antimicrobial properties. The invention makes nano ZnO grow and graft on the surface of dihydroxy polydiphenyl siloxane, improves the wettability of the surface of nano ZnO, increases its affinity with other materials, increases the antibacterial effect, and simultaneously dihydroxy poly diphenyl The adhesive properties of siloxane can improve the antimicrobial durability of the material.

In the present invention, adding hydroxyethyl acrylate as a crosslinking agent can provide crosslinking points for polyurethane, so that polyurethane forms a network structure, and it is difficult for water and solvent molecules to enter the macromolecular structure, thereby improving its waterproof performance and air permeability and mechanical properties.

In the present invention, the molecular structure of the fluorine-containing polyether diol is HO-(CH ₂ CH ₂ O)n ₁ -CH ₂ -CF ₂ O-(CF ₂ CF ₂ O) _m -(CF ₂ O) n ₂ -CF ₂ -CH ₂ -(OCH ₂ CH ₂ )n ₃ -OH;

Wherein, m=3～6, such as 3, 4, 5 or 6 etc.; n ₁ =3～6, such as 3, 4, 5 or 6 etc.; n ₂ =3～6, such as 3, 4, 5 or 6 etc.; n ₃ =3-6, such as 3, 4, 5 or 6, etc.

That is, the two ends of the fluorine-containing polyether diol are hydroxyl-terminated polyethoxy groups, and the middle is a block perfluoropolyethoxy polymethoxy group.

Preferably, the molecular weight of the fluorine-containing polyether diol is 1500-2000, such as 1500, 1600, 1700, 1800, 1900 or 2000;

In the present invention, the preparation method of the dihydroxy polydiphenylsiloxane modified by the nanometer ZnO is:

(a) dispersing nano-ZnO in dihydroxy polydiphenylsiloxane emulsion, and ultrasonically dispersing for 1-2 hours to obtain a dispersion;

(b) Add the dispersion liquid into a closed container with a reflux condenser and a stirrer, then raise the temperature to 40-50° C., stir and reflux for 5-8 hours to obtain nano ZnO-modified dihydroxy polydiphenylsiloxane.

Among them, the ultrasonic dispersion time in step (a) can be 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, etc.; °C, 45 °C, 46 °C, 48 °C or 50 °C, etc.; the stirring and reflux time can be 5h, 6h, 7h or 8h, etc.

Preferably, the mass ratio of the nano-ZnO and dihydroxypolydiphenylsiloxane emulsion is 1:(6-10), such as 1:6, 1:7, 1:8, 1:9 or 1:10 etc., preferably 1:8.

In a second aspect, the present invention provides a method for preparing the above-mentioned thermoplastic polyurethane elastomer, the method comprising the following steps:

(1) Put the polymerized polyol, 1,4-butanediol and hydroxyethyl acrylate in the formula into the container in sequence, and vacuumize at 60-80°C under stirring conditions to obtain the mixture A;

(2) After heating the formula amount of isophorone diisocyanate to 50-60°C, mix it with the mixture A obtained in step (1), and then add the formula amount of nano-ZnO modified dihydroxy polydiphenyl The siloxane was stirred at 130-140°C for 1-3 hours, and then aged at 75-80°C for 10-14 hours to obtain material B;

(3) Add material B into a twin-screw extruder to extrude and granulate to obtain a thermoplastic polyurethane elastomer.

Wherein, in step (1), the vacuum is drawn at 60-80°C under stirring condition, and the temperature can be 60°C, 63°C, 65°C, 67°C, 70°C, 73°C, 75°C, 77°C or 80°C, etc.; In step (2), isophorone diisocyanate is heated to 50-60°C, such as 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C ℃, etc.; in step (2), add the nano-ZnO modified dihydroxy polydiphenylsiloxane in the formula amount and stir at 130-140°C for 1-3h, wherein the temperature can be 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C or 140°C, etc., the time can be 1h, 1.5h, 2h, 2.5h or 3h, etc.; aging at 75-80°C for 10~ 14h, where the temperature can be 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, etc., and the aging time can be 10h, 11h, 12h, 13h or 14h, etc.

In the present invention, the preparation method of the dihydroxy polydiphenylsiloxane modified by the nanometer ZnO is:

(a) dispersing nano-ZnO in dihydroxy polydiphenylsiloxane emulsion, and ultrasonically dispersing for 1-2 hours to obtain a dispersion;

(b) adding the dispersion into a closed container with a reflux condenser and a stirrer, then raising the temperature to 40-50° C., stirring and refluxing for 5-8 hours, to obtain nano-ZnO modified dihydroxy polydiphenylsiloxane;

Preferably, the mass ratio of the nano-ZnO to the dihydroxypolydiphenylsiloxane emulsion is 1:(6-10), preferably 1:8.

In the present invention, the vacuum condition in step (1) is a pressure of -0.4 to -0.2kPa, such as -0.4kPa, -0.35kPa, -0.3kPa, -0.25kPa or -0.2kPa.

Preferably, the stirring rate in step (1) is 1000-1200r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min or 1200r/min, etc.

Preferably, the stirring rate in step (2) is 1000-1200r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min or 1200r/min, etc.

In the present invention, in the step (3), the temperature of the feeding section of the twin-screw extruder is set at 130-140°C, such as 130°C, 132°C, 134°C, 136°C, 138°C or 140°C.

Preferably, in step (3), the temperature of the mixing section of the twin-screw extruder is set at 160-170°C, such as 160°C, 162°C, 164°C, 166°C, 168°C or 170°C.

Preferably, in step (3), the temperature of the extrusion section of the twin-screw extruder is set at 170-180°C, such as 170°C, 172°C, 174°C, 176°C, 178°C or 180°C.

Preferably, in step (3), the head temperature of the twin-screw extruder is set at 170-180°C, such as 170°C, 172°C, 174°C, 176°C, 178°C or 180°C.

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

In the present invention, a mixture of fluorine-containing polyether diol and 1,4-butylene adipate diol is used as a polymer polyol to act synergistically to improve the waterproof and oil-proof performance of the target product, so that it has excellent waterproof and permeable properties. Wet performance, not only prevent the penetration of water droplets, but also ensure the free penetration of water vapor, and can be used in harsh environments; at the same time, adding nano-ZnO modified dihydroxy polydiphenyl siloxane and hydroxyethyl acrylate Improve the antibacterial properties of thermoplastic polyurethane elastomers and make them have good mechanical properties, so that the water absorption rate of thermoplastic polyurethane elastomers (soaked in cold water for 10 days) ≤ 2%, the common bacteria inhibition rate ≥ 95%, and the tensile strength is maintained at 85MPa, the elongation at break reaches 810%, and the rebound rate reaches 85%.

Detailed ways

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. Those skilled in the art should understand that the examples are only used to help understand the present invention, and should not be regarded as specific limitations on the present invention.

Each embodiment in the present invention adopts following method to carry out performance test:

Water absorption test: first place the sample in an oven at 60°C to dry to a constant weight, then immerse it in cold water for 10 days, take it out, wipe off the surface water and weigh it, and calculate the water absorption of the sample from the mass difference before and after immersion.

Antibacterial performance test: A certain amount of bacterial liquid is evenly dropped on the sample, and the sample is contacted with the bacteria for a certain period of time to calculate the reduction rate of the number of bacteria, that is, the antibacterial rate.

Physical and mechanical performance test: The mechanical performance is tested on the LJ-500 tensile testing machine according to GB/T1040-1979, and the tensile rate is 200mm/min.

Example 1:

(1) Preparation of nano-ZnO modified dihydroxy polydiphenylsiloxane:

Disperse nano-ZnO in dihydroxypolydiphenylsiloxane emulsion (wherein the mass ratio of nano-ZnO and dihydroxypolydiphenylsiloxane emulsion is 1:8), and ultrasonically disperse for 1.5h to obtain a dispersion Add the dispersion liquid into a closed container with a reflux condenser and a stirrer, then raise the temperature to 45°C, stir and reflux for 6 hours, and obtain nano-ZnO modified dihydroxy polydiphenylsiloxane;

(2) Preparation of thermoplastic polyurethane elastomer:

Add 45 parts of polymeric polyol, 12 parts of 1,4-butanediol and 7 parts of hydroxyethyl acrylate into the container sequentially (wherein, in the fluorine-containing polyether diol, m=4, n ₁ =4, n ₂ = 5, n ₃ =4, the mass ratio of fluorine-containing polyether diol to 1,4-butanediol adipate diol in the polymer polyol is 4:1), vacuumize at 1100r/min at 70°C to -0.3kPa to obtain mixture A; after heating 35 parts of isophorone diisocyanate to 55°C, mix it with mixture A, and then add 12 parts of nano-ZnO modified dihydroxy polydiphenylsiloxane Alkane was stirred at 135°C at a rate of 1100r/min for 2h, and then aged at 77°C for 12h to obtain material B; material B was added to a twin-screw extruder to extrude and granulate to obtain a thermoplastic polyurethane elastomer (wherein, two The feeding section temperature, mixing section temperature, extrusion section temperature and die temperature of the screw extruder are 135°C, 165°C, 175°C and 175°C).

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Example 2:

(1) Preparation of nano-ZnO modified dihydroxy polydiphenylsiloxane:

Dispersing nano-ZnO in dihydroxypolydiphenylsiloxane emulsion (wherein, the mass ratio of nano-ZnO and dihydroxypolydiphenylsiloxane emulsion is 1:10), and ultrasonically dispersing for 2 hours, to obtain a dispersion; Add the dispersion liquid into a closed container with a reflux condenser and a stirrer, then raise the temperature to 50 ° C, stir and reflux for 5 hours, and obtain nano-ZnO modified dihydroxy polydiphenylsiloxane;

(2) Preparation of thermoplastic polyurethane elastomer:

Add 47 parts of polymeric polyol, 13 parts of 1,4-butanediol and 8 parts of hydroxyethyl acrylate into the container sequentially (wherein, in the fluorine-containing polyether diol, m=3, n ₁ =3, n ₂ = 3, n ₃ =3, the mass ratio of fluorine-containing polyether diol to 1,4-butanediol adipate diol in the polymer polyol is 5:1), vacuumize at 1000r/min at 80°C to -0.2kPa to obtain mixture A; after heating 37 parts of isophorone diisocyanate to 60°C, mix it with mixture A, and then add 13 parts of nano-ZnO modified dihydroxy polydiphenylsiloxane Alkane was stirred at 130°C at a rate of 1200r/min for 3h, and then aged at 80°C for 10h to obtain material B; material B was added to a twin-screw extruder to extrude and granulate to obtain a thermoplastic polyurethane elastomer (wherein, two The feeding section temperature, mixing section temperature, extrusion section temperature and die temperature of the screw extruder are 130°C, 160°C, 170°C and 170°C).

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Example 3:

(1) Preparation of nano-ZnO modified dihydroxy polydiphenylsiloxane:

Disperse nano-ZnO in dihydroxypolydiphenylsiloxane emulsion (wherein, the mass ratio of nano-ZnO and dihydroxypolydiphenylsiloxane emulsion is 1:6), and ultrasonically disperse for 1 hour to obtain a dispersion; Add the dispersion into a closed container with a reflux condenser and a stirrer, then raise the temperature to 40°C, stir and reflux for 8 hours to obtain nano-ZnO-modified dihydroxypolydiphenylsiloxane;

(2) Preparation of thermoplastic polyurethane elastomer:

Add 43 parts of polymeric polyol, 11 parts of 1,4-butanediol and 6 parts of hydroxyethyl acrylate into the container sequentially (wherein, in the fluorine-containing polyether diol, m=6, n ₁ =6, n ₂ = 6, n ₃ =6, the mass ratio of fluorine-containing polyether diol to 1,4-butanediol adipate diol in the polymer polyol is 3:1), vacuumize at 1200r/min at 60°C to -0.4kPa to obtain mixture A; after heating 33 parts of isophorone diisocyanate to 50°C, mix it with mixture A, and then add 11 parts of nano-ZnO modified dihydroxy polydiphenylsiloxane Alkane was stirred at 140°C at a rate of 1000r/min for 1h, and then aged at 75°C for 14h to obtain material B; material B was added to a twin-screw extruder to extrude and granulate to obtain a thermoplastic polyurethane elastomer (wherein, two The feeding section temperature, mixing section temperature, extrusion section temperature and die temperature of the screw extruder are 140°C, 170°C, 180°C and 180°C).

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Example 4:

In addition to step (2), the consumption of polymerized polyol is 40 parts, the consumption of isophorone diisocyanate is 30 parts, the consumption of 1,4-butanediol is 10 parts, the consumption of hydroxyethyl acrylate is 5 parts and Except that the amount of nano-ZnO modified dihydroxypolydiphenylsiloxane is 10 parts, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Example 5:

In addition to step (2), the consumption of polymerized polyol is 50 parts, the consumption of isophorone diisocyanate is 40 parts, the consumption of 1,4-butanediol is 15 parts, the consumption of hydroxyethyl acrylate is 10 parts and Except that the amount of nano-ZnO modified dihydroxypolydiphenylsiloxane is 15 parts, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 1:

Except that only fluorine-containing polyether diols are used for polymerizing polyols, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 2:

Except that only 1,4-butylene adipate diol is used for polymerizing polyol, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 3:

Except that the mass ratio of fluorine-containing polyether diol and 1,4-butanediol adipate diol in the polymerized polyol is 1:1, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 4:

Except that the mass ratio of fluorine-containing polyether diol to 1,4-butanediol adipate diol in the polymerized polyol is 10:1, other steps are the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 5:

Except that no nano-ZnO modified dihydroxy polydiphenylsiloxane was added, other steps were the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 6:

Except that the nano-ZnO modified dihydroxy polydiphenylsiloxane was replaced with nano-ZnO, other steps were the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 7:

Except that the added amount of nano-ZnO modified dihydroxy polydiphenylsiloxane was 1 part, other steps were the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 8:

Except that the added amount of nano-ZnO modified dihydroxy polydiphenylsiloxane was 20 parts, other steps were the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Comparative example 9:

Except not adding hydroxyethyl acrylate, other steps are all the same as in Example 1.

The performance test of the prepared thermoplastic polyurethane elastomer was carried out, and the test results are listed in Table 1.

Table 1: Performance test table for thermoplastic polyurethane elastomers of Examples 1-5 and Comparative Examples 1-9

As can be seen from the results of comparative examples 1-9 of comprehensive examples 1-5, the present invention uses the mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol as both of polymerized polyols. Synergistic effect to improve the waterproof and oil-proof performance of the target product, so that it has excellent waterproof and moisture-permeable performance, which can not only prevent the penetration of water droplets, but also ensure the free penetration of water vapor, and can be used in harsh environments; at the same time, adding nano ZnO-modified dihydroxypolydiphenylsiloxane and hydroxyethyl acrylate improve the antibacterial properties of thermoplastic polyurethane elastomers, and make them have good mechanical properties, so that the water absorption of thermoplastic polyurethane elastomers (soaked in cold water for 10 days) ≤2%, the inhibition rate of common bacteria is ≥95%, and the tensile strength is maintained at 85MPa, the elongation at break reaches 810%, and the rebound rate reaches 85%.

The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow process can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. a thermoplastic polyurethane elastomer, is characterized in that, described thermoplastic polyurethane elastomer is mainly prepared by following component by weight: Wherein, the polymer polyol is a mixture of fluorine-containing polyether diol and 1,4-butanediol adipate diol. 2. thermoplastic polyurethane elastomer according to claim 1, is characterized in that, described thermoplastic polyurethane elastomer is mainly prepared by following components by weight: 3. The thermoplastic polyurethane elastomer according to claim 1 or 2, characterized in that, the thermoplastic polyurethane elastomer is mainly prepared by the following components in parts by weight: 4. according to the thermoplastic polyurethane elastomer described in any one of claim 1-3, it is characterized in that, fluorine-containing polyether diol and adipate 1,4-butylene glycol ester diol in the polymer polyol The mass ratio of (3-5):1, preferably 4:1. 5. The thermoplastic polyurethane elastomer according to any one of claims 1-4, wherein the molecular structure of the fluorine-containing polyether diol is: Wherein, m=3~6, n ₁ =3~6, n ₂ =3~6, n ₃ =3~6; Preferably, the molecular weight of the fluorine-containing polyether diol is 1500-2000. 6. according to the thermoplastic polyurethane elastomer described in any one of claim 1-5, it is characterized in that, the preparation method of the dihydroxy polydiphenylsiloxane of described nanometer ZnO modification is: (a) dispersing nano-ZnO in dihydroxy polydiphenylsiloxane emulsion, and ultrasonically dispersing for 1-2 hours to obtain a dispersion; (b) adding the dispersion into a closed container with a reflux condenser and a stirrer, then raising the temperature to 40-50° C., stirring and refluxing for 5-8 hours, to obtain nano-ZnO modified dihydroxy polydiphenylsiloxane; Preferably, the mass ratio of the nano-ZnO to the dihydroxypolydiphenylsiloxane emulsion is 1:(6-10), preferably 1:8. 7. according to the preparation method of the thermoplastic polyurethane elastomer described in any one of claim 1-6, it is characterized in that, described method comprises the following steps: (1) Put the polymerized polyol, 1,4-butanediol and hydroxyethyl acrylate in the formula into the container in sequence, and vacuumize at 60-80°C under stirring conditions to obtain the mixture A; (2) After heating the formula amount of isophorone diisocyanate to 50-60°C, mix it with the mixture A obtained in step (1), and then add the formula amount of nano-ZnO modified dihydroxy polydiphenyl The siloxane was stirred at 130-140°C for 1-3 hours, and then aged at 75-80°C for 10-14 hours to obtain material B; (3) Add material B into a twin-screw extruder to extrude and granulate to obtain a thermoplastic polyurethane elastomer. 8. preparation method according to claim 7, is characterized in that, the preparation method of the dihydroxy polydiphenylsiloxane of described nanometer ZnO modification is: (a) dispersing nano-ZnO in dihydroxy polydiphenylsiloxane emulsion, and ultrasonically dispersing for 1-2 hours to obtain a dispersion; (b) adding the dispersion into a closed container with a reflux condenser and a stirrer, then raising the temperature to 40-50° C., stirring and refluxing for 5-8 hours, to obtain nano-ZnO modified dihydroxy polydiphenylsiloxane; Preferably, the mass ratio of the nano-ZnO to the dihydroxypolydiphenylsiloxane emulsion is 1:(6-10), preferably 1:8. 9. The preparation method according to claim 7 or 8, characterized in that, the vacuum condition in step (1) is pressure -0.4～-0.2kPa; Preferably, the stirring speed in step (1) is 1000～1200r/min; Preferably, the stirring rate in step (2) is 1000-1200 r/min. 10. The preparation method according to any one of claims 7-9, characterized in that, in the step (3), the temperature of the feeding section of the twin-screw extruder is set to be 130-140°C; Preferably, the temperature of the mixing section of the twin-screw extruder is set to be 160-170°C in step (3); Preferably, in step (3), the temperature of the extrusion section of the twin-screw extruder is set to be 170-180°C; Preferably, in step (3), the head temperature of the twin-screw extruder is set at 170-180°C.