Antifouling and antibacterial thermoplastic polyurethane elastomer and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane elastomers, and specifically relates to an antifouling and antibacterial thermoplastic polyurethane elastomer and a preparation method thereof. The antifouling and antibacterial thermoplastic polyurethane elastomer is prepared by reacting 40-65wt.% of a polyol, 20-40wt.% of a diisocyanate and 5-15wt.% of a chain extender, and then adding an antifouling and antibacterial agent accounting for 5-15% of the mass of the polyol and an anti-aging agent accounting for 0.5-1% of the mass of the polyol, wherein the antifouling and antibacterial agent is obtained by reacting modified silicone and an acylanilide antibacterial agent under the action of an initiator. The antifouling and antibacterial thermoplastic polyurethane elastomer prepared by the present invention greatly improves the antifouling and sterilization effects of TPU itself, and effectively improves the antibacterial effect and action duration of the organic antibacterial agent, and has no effect on the mechanical properties of TPU itself.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane elastomers, and in particular relates to an antifouling and antibacterial thermoplastic polyurethane elastomer and a preparation method thereof. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a common chemical material with the characteristics of high strength, good toughness, good aging resistance, good weather resistance, etc. It also has many excellent functions such as windproof and cold resistance. It is widely used in automotive interiors, clothing, casters, seals and other fields.

[0003] However, ordinary TPU materials have poor antifouling effect, poor water resistance and mildew resistance, which are necessary for products in many fields, such as TPU shoes, mobile phone cases, electronic accessories and other products, which require TPU materials to have good antifouling and mildew resistance. Therefore, how to improve the antifouling and mildew resistance of TPU has become the focus of research in the industry.

[0004] For example, patent CN115181411A discloses an anti-fouling super-barrier TPU film, which uses anti-fouling resin, barrier emulsion, waterproofing agent and other components to achieve a good anti-fouling effect. However, excessive addition will damage the mechanical and processing properties of TPU itself.

[0005] Patent CN114671991A discloses a method for synthesizing antibacterial TPU particles, which uses nano zinc oxide and nano silver in combination with modified graphene to make the product resistant to mildew, but its preparation process is complicated and is not suitable for large-scale continuous industrial production.

[0006] Therefore, it is necessary to develop a TPU material with good antifouling and mildew resistance effects. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an antifouling and antibacterial thermoplastic polyurethane elastomer, which greatly improves the antifouling and sterilization effects of TPU itself, and effectively improves the antibacterial effect and action duration of organic antibacterial agents, and has no effect on the mechanical properties of TPU itself. The present invention also provides a preparation method thereof, which has a simple process and efficient production.

[0008] The antifouling and antibacterial thermoplastic polyurethane elastomer of the present invention is prepared by reacting 40-65wt.% of polyol, 20-40wt.% of diisocyanate and 5-15wt.% of chain extender, and then adding 5-15% of antifouling and antibacterial agent and 0.5-1% of anti-aging agent.

[0009] In the present invention, the polyol is a polyether polyol or a polyester polyol, and its molecular weight is 1000-2000.

[0010] Preferably, the polyether polyol is one or more of polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol-propylene oxide copolymer.

[0011] Preferably, the polyester polyol is one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polyethylene adipate-butylene adipate diol, and polybutylene adipate-hexylene adipate diol.

[0012] In the present invention, the diisocyanate is diphenylmethane diisocyanate.

[0013] In the present invention, the chain extender is one or more of ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol.

[0014] In the present invention, the anti-aging agent is a mixture of antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 2:(1-3).

[0015] In the present invention, the antifouling and antibacterial agent is obtained by reacting modified organic silicon and acylanilide antibacterial agent in a mass ratio of 1:(1-2) under the action of an initiator.

[0016] Preferably, the modified silicone is dihydroxy polydimethylsiloxane.

[0017] Preferably, the acylanilide antibacterial agent is furamide.

[0018] Preferably, the initiator is a cationic initiator, preferably hexafluoroantimonate; the amount of the initiator used is 0.1-0.5% of the total mass of the modified organosilicon and the acylanilide antibacterial agent.

[0019] As a preferred embodiment, the preparation method of the antifouling and antibacterial agent is as follows:

[0020] The modified organic silicon and the acylanilide antibacterial agent are mixed in proportion, the temperature is raised to 80-90° C., an initiator is added, and the mixture is stirred and kept warm for 3-4 hours to obtain an antifouling antibacterial agent.

[0021] The method for preparing the antifouling and antibacterial thermoplastic polyurethane elastomer of the present invention comprises the following steps:

[0022] The polyol and the chain extender are mixed and vacuum dehydrated to a moisture content of less than 300 ppm. The polyol and the chain extender are then added to the first zone of a twin-screw extruder with 14 temperature zones for reaction. An antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder. After underwater granulation, an antifouling and antibacterial thermoplastic polyurethane elastomer is obtained.

[0023] Preferably, the rotation speed of the twin-screw extruder is 240-300 r / min.

[0024] Preferably, the temperature of the temperature zones 1-7 of the twin-screw extruder is 200-240°C, the temperature of the temperature zones 8-14 is 120-150°C, and the temperature of the underwater granulation part is 160-190°C.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The present invention uses modified silicone and acylanilide antibacterial agent to react under the action of an initiator to obtain an antifouling antibacterial agent, thereby improving the heat resistance and long-term antibacterial and hydrolysis-resistant effect of the acylanilide antibacterial agent, and can be directly added to a twin-screw extruder to participate in granulation;

[0027] (2) Compared with the conventional process of adding antibacterial agents after melting TPU particles, the present invention introduces antifouling antibacterial agents in the process of producing TPU particles, thereby avoiding the loss of mechanical properties of TPU itself due to secondary processing. The prepared TPU not only has antifouling and mildew resistance, solving the problem that existing TPU products are not resistant to dirt when used in special working environments or daily life, but also has good mechanical properties and can be widely used in product fields such as shoe materials, mobile phone cases, and electronic accessories;

[0028] (3) The present invention adopts a twin-screw extruder for production, thereby achieving continuous production with low cost, high efficiency, safety and environmental protection. DETAILED DESCRIPTION

[0029] The present invention is further described below with reference to the examples. The raw materials used in the examples, unless otherwise specified, are all commercially available conventional raw materials; the process methods used in the examples, unless otherwise specified, are all conventional methods in the art.

[0030] Example 1

[0031] The invention discloses an antifouling and antibacterial thermoplastic polyurethane elastomer, which is prepared by reacting 65wt.% of polyethylene adipate glycol (Mn=2000), 22wt.% of diphenylmethane diisocyanate and 13wt.% of 1,4-butanediol, and then adding an antifouling and antibacterial agent accounting for 15% of the mass of the polyethylene adipate glycol and an anti-aging agent (antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 2:1) accounting for 1% of the mass of the polyethylene adipate glycol.

[0032] The specific preparation process is as follows:

[0033] (1) Dihydroxy polydimethylsiloxane and furamide were mixed in a mass ratio of 1:2, heated to 80° C., 0.5% of cationic initiator hexafluoroantimonate was added, and the mixture was stirred and kept warm for 3 h to prepare an antifouling and antibacterial agent;

[0034] (2) Polyethylene adipate glycol and 1,4-butanediol are mixed and vacuum dehydrated to a water content of less than 300 ppm, and then added with diphenylmethane diisocyanate to the first zone of a twin-screw extruder with 14 temperature zones for reaction, and an antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder, and underwater granulation is performed to obtain an antifouling and antibacterial thermoplastic polyurethane elastomer; wherein the rotation speed of the twin-screw extruder is 260 r / min, the temperature of the 1-7 temperature zones is 220° C., the temperature of the 8-14 temperature zones is 120° C., and the temperature of the underwater granulation part is 170° C.

[0035] Example 2

[0036] The invention discloses an antifouling and antibacterial thermoplastic polyurethane elastomer. The elastomer is prepared by reacting 56wt.% of polybutylene adipate diol (Mn=2000), 33wt.% of diphenylmethane diisocyanate and 11wt.% of ethylene glycol, and then adding an antifouling and antibacterial agent accounting for 10% of the mass of the polybutylene adipate diol and an anti-aging agent (antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 1:1) accounting for 0.5% of the mass of the polybutylene adipate diol.

[0037] The specific preparation process is as follows:

[0038] (1) Dihydroxy polydimethylsiloxane and furamide were mixed in a mass ratio of 1:1, heated to 80° C., 0.3% cationic initiator hexafluoroantimonate was added, and the mixture was stirred and kept warm for 3 h to prepare an antifouling and antibacterial agent;

[0039] (2) After mixing polybutylene adipate diol and ethylene glycol, vacuum dehydration is performed until the water content is less than 300 ppm, and then the mixture is added with diphenylmethane diisocyanate to the first zone of a twin-screw extruder having 14 temperature zones for reaction, and an antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder, and underwater granulation is performed to obtain an antifouling and antibacterial thermoplastic polyurethane elastomer; wherein the rotation speed of the twin-screw extruder is 260 r / min, the temperature of the 1-7 temperature zones is 220° C., the temperature of the 8-14 temperature zones is 120° C., and the temperature of the underwater granulation part is 170° C.

[0040] Example 3

[0041] The invention discloses an antifouling and antibacterial thermoplastic polyurethane elastomer, which is prepared by reacting 40wt.% of polybutylene adipate diol (Mn=1000), 42wt.% of diphenylmethane diisocyanate and 18wt.% of 1,6-hexanediol, and then adding an antifouling and antibacterial agent accounting for 5wt.% of the mass of the polybutylene adipate diol and an anti-aging agent (antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 2:3) accounting for 1wt.% of the mass of the polybutylene adipate diol.

[0042] The specific preparation process is as follows:

[0043] (1) Dihydroxy polydimethylsiloxane and furamide were mixed in a mass ratio of 1:1.5, heated to 80° C., added with 0.1% cationic initiator hexafluoroantimonate, and stirred and kept warm for 3 h to prepare an antifouling and antibacterial agent;

[0044] (2) Polybutylene adipate diol and 1,6-hexanediol are mixed and vacuum dehydrated to a water content of less than 300 ppm, and then added with diphenylmethane diisocyanate to the first zone of a twin-screw extruder with 14 temperature zones for reaction, and an antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder, and underwater granulation is performed to obtain an antifouling and antibacterial thermoplastic polyurethane elastomer; wherein the rotation speed of the twin-screw extruder is 260 r / min, the temperature of the 1-7 temperature zones is 220° C., the temperature of the 8-14 temperature zones is 120° C., and the temperature of the underwater granulation part is 170° C.

[0045] Example 4

[0046] The invention discloses an antifouling and antibacterial thermoplastic polyurethane elastomer. The elastomer is prepared by reacting 40wt.% of polytetramethylene ether glycol (Mn=1000), 42wt.% of diphenylmethane diisocyanate and 18wt.% of 1,4-butanediol, and then adding an antifouling and antibacterial agent accounting for 5wt.% of the mass of the polytetramethylene ether glycol and an anti-aging agent (antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 2:3) accounting for 1wt.% of the mass of the polytetramethylene ether glycol.

[0047] The specific preparation process is as follows:

[0048] (1) Dihydroxy polydimethylsiloxane and furamide were mixed in a mass ratio of 1:1, heated to 80° C., 0.3% cationic initiator hexafluoroantimonate was added, and the mixture was stirred and kept warm for 3 h to prepare an antifouling and antibacterial agent;

[0049] (2) After mixing polytetrahydrofuran ether diol and 1,4-butanediol, vacuum dehydration is performed until the water content is less than 300 ppm, and then the mixture is added with diphenylmethane diisocyanate to the first zone of a twin-screw extruder having 14 temperature zones for reaction, and an antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder, and underwater granulation is performed to obtain an antifouling and antibacterial thermoplastic polyurethane elastomer; wherein the rotation speed of the twin-screw extruder is 260 r / min, the temperature of the 1-7 temperature zones is 220° C., the temperature of the 8-14 temperature zones is 120° C., and the temperature of the underwater granulation part is 170° C.

[0050] Example 5

[0051] The invention discloses an antifouling and antibacterial thermoplastic polyurethane elastomer, which is prepared by reacting 56wt.% of polypropylene glycol (Mn=2000), 33wt.% of diphenylmethane diisocyanate and 11wt.% of ethylene glycol, and then adding an antifouling and antibacterial agent accounting for 10% of the mass of the polypropylene glycol and an anti-aging agent (antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 1:1) accounting for 0.5% of the mass of the polypropylene glycol.

[0052] The specific preparation process is as follows:

[0053] (1) Dihydroxy polydimethylsiloxane and furamide were mixed in a mass ratio of 1:1, heated to 80° C., 0.3% cationic initiator hexafluoroantimonate was added, and the mixture was stirred and kept warm for 3 h to prepare an antifouling and antibacterial agent;

[0054] (2) After mixing polypropylene glycol and ethylene glycol, vacuum dehydration is performed until the water content is less than 300 ppm, and then the mixture is added with diphenylmethane diisocyanate to the first zone of a twin-screw extruder having 14 temperature zones for reaction, and an antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder, and underwater granulation is performed to obtain an antifouling and antibacterial thermoplastic polyurethane elastomer; wherein the rotation speed of the twin-screw extruder is 260 r / min, the temperature of the 1-7 temperature zones is 220° C., the temperature of the 8-14 temperature zones is 120° C., and the temperature of the underwater granulation part is 170° C.

[0055] Comparative Example 1

[0056] The only difference between this comparative example and Example 1 is that no antifouling and antibacterial agent is added to the raw material composition.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Example 1 is that the modified silicone and the acylanilide antibacterial agent are mixed at high temperature without initiating the reaction with an initiator.

[0059] The thermoplastic polyurethane elastomers prepared in the examples and comparative examples were subjected to performance tests, wherein the hardness was tested with reference to the standard ASTM D2240; the tensile strength was tested with reference to the standard ASTM D882; the antifouling property was tested with reference to the standard GB / T 30159; the 7-day sterilization rate and the 30-day sterilization rate were tested with reference to the standard QB / T 2591-2003 (using Escherichia coli as the sample). The test results are shown in Table 1.

[0060] Table 1 Performance test results

[0061] project Hardness / Shore Tensile strength / Mpa Molding time / s Antifouling / grade 7-day sterilization rate / % 30-day sterilization rate / % Example 1 85A 38 12 4 90 82 Example 2 91A 43 8 4.5 93 85 Example 3 60D 51 5 5 96 87 Example 4 60D 49 6 5 96 88 Example 5 91A 41 10 4.5 91 83 Comparative Example 1 85A 32 16 2.5 46 30 Comparative Example 2 85A 35 14 3.5 82 54

[0062] As can be seen from Table 1, the invention adds the modified antifouling antibacterial agent to TPU, which greatly improves the antifouling and sterilization effects of TPU itself, and effectively improves the antibacterial effect and action duration of the organic antibacterial agent, and has no effect on the mechanical properties of TPU itself. Secondly, the antifouling antibacterial agent after being acted on by the initiator can improve the long-term antibacterial effect of the acylanilide antibacterial agent.

Claims

1. An antifouling and antibacterial thermoplastic polyurethane elastomer, characterized in that: The method is prepared by reacting 40-65wt.% of polyol, 20-40wt.% of diisocyanate and 5-15wt.% of chain extender, and then adding 5-15wt.% of antifouling and antibacterial agent and 0.5-1wt.% of anti-aging agent. The antifouling and antibacterial agent is obtained by reacting modified silicone and acylanilide antibacterial agent in a mass ratio of 1:(1-2) under the action of an initiator; the modified silicone is dihydroxy polydimethylsiloxane; and the acylanilide antibacterial agent is furamide.

2. The antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 1, characterized in that: The polyol is a polyether polyol or a polyester polyol, and its molecular weight is 1000-2000; The polyether polyol is one or more of polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol-propylene oxide copolymer; The polyester polyol is one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polyethylene adipate-butylene adipate diol, and polybutylene adipate-hexylene adipate diol.

3. The antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 1, characterized in that: The diisocyanate is diphenylmethane diisocyanate.

4. The antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 1, characterized in that: The chain extender is one or more of ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol.

5. The antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 1, characterized in that: The anti-aging agent is a mixture of antioxidant 1010 and ultraviolet absorber UV-1 in a mass ratio of 2:(1-3).

6. The antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 1, characterized in that: The initiator is a cationic initiator, and the amount used is 0.1-0.5% of the total mass of the modified organic silicon and the acylanilide antibacterial agent.

7. A method for preparing the antifouling and antibacterial thermoplastic polyurethane elastomer according to any one of claims 1 to 6, characterized in that: The following steps are involved: The polyol and the chain extender are mixed and vacuum dehydrated to a moisture content of less than 300 ppm. The polyol and the chain extender are then added to the first zone of a twin-screw extruder with 14 temperature zones for reaction. An antifouling and antibacterial agent and an anti-aging agent are added to the tenth zone of the twin-screw extruder. After underwater granulation, an antifouling and antibacterial thermoplastic polyurethane elastomer is obtained.

8. The method for preparing the antifouling and antibacterial thermoplastic polyurethane elastomer according to claim 7, characterized in that: The temperature of the 1-7 temperature zones of the twin-screw extruder is 200-240°C, the temperature of the 8-14 temperature zones is 120-150°C, and the temperature of the underwater granulation part is 160-190°C.