CN111393744A

CN111393744A - TPE material with antibacterial conductivity and preparation method thereof

Info

Publication number: CN111393744A
Application number: CN202010224684.9A
Authority: CN
Inventors: 童贤涛; 潘文强; 周家辉
Original assignee: Nanjing Jingjinyuan Technical Industry Co ltd
Current assignee: Nanjing Jingjinyuan Technical Industry Co ltd
Priority date: 2020-03-26
Filing date: 2020-03-26
Publication date: 2020-07-10
Anticipated expiration: 2040-03-26
Also published as: CN111393744B

Abstract

The invention discloses a TPE material with antibacterial conductivity and a preparation method thereof, wherein the TPE material is prepared from the following raw materials in parts by weight: 10-20 parts of SEBS rubber elastomer; 10-20 parts of mineral oil; 20-30 parts of polypropylene; 5-10 parts of polypropylene antibacterial master batch; 10-20 parts of carbon nanotubes; 15-25 parts of a filler; 3-8 parts of SBS rubber elastomer; 0.2-0.5 part of an auxiliary agent; wherein, the carbon nano tube needs to be subjected to surface treatment. The TPE material with antibacterial conductivity has good antibacterial property and conductivity under the condition of ensuring the mechanical property of the TPE material.

Description

TPE material with antibacterial conductivity and preparation method thereof

Technical Field

The invention belongs to the field of elastomer materials, and particularly relates to a TPE material with antibacterial conductivity and a preparation method thereof.

Background

The TPE has good mechanical properties, diversified processing modes, and the advantages of environmental protection, comfortable touch feeling, strong designability and the like, so that the TPE is more and more widely applied to medical treatment. In many medical devices, TPE materials can be used as slip-resistant, shock-resistant, cladding, etc. materials, even for the core functional components. At present, in the medical equipment with conductive performance, the conductive material is mainly metal, but the use of metal material has some disadvantages: firstly, the comfort is not good enough, and secondly, the material cannot be reused, which leads to the waste of resources, therefore, a conductive material with certain comfort and reusability is needed to replace the metal material. The TPE, as a relatively compatible elastomer, can be used as a suitable substitute material after having conductivity, and as a material of medical equipment, it is also required to have antibacterial property, so that a TPE material having both conductivity and antibacterial property is required.

In the prior art, a TPE material with antibacterial property is used as medical equipment, and on the other hand, the prior art that a polymer is added by utilizing a carbon nano tube to have conductivity is also provided; however, when the antibacterial property and the electric conductivity are integrated in the TPE material, a large amount of conductive components and antibacterial components agglomerate and cannot be compatible, so that the electric conductivity and the antibacterial property of the material are reduced, and even the mechanical properties of the material are affected.

Chinese patent publication No. CN110835465A discloses preparation and application of a nylon/carbon nanotube master batch for improving material conductivity, in which carbon nanotubes are acidified, surface chemical grafting modification of the carbon nanotubes can be achieved by using a silane coupling agent, and physical coating modification of the carbon nanotubes can be achieved by using a polyether surfactant, so that the property of the carbon nanotubes that are easy to self-aggregate can be effectively changed by using two types of modifiers together, namely grafting and coating. However, the structure of the carbon nanotube is damaged to a certain extent after the carbon nanotube is acidized, the mechanical and electrical properties of the carbon nanotube are reduced, and meanwhile, when the carbon nanotube is dispersed in a TPE material which needs to integrate antibacterial and electric conduction, the problems that a large amount of conductive components and antibacterial components are agglomerated and cannot be compatible cannot be solved.

Disclosure of Invention

The invention aims to provide a TPE material with antibacterial conductivity aiming at the requirements of the conductivity and antibacterial property of some medical equipment and the defects of the prior art, and the TPE material meets the requirement that the TPE material has good antibacterial property and conductivity under the condition of ensuring the mechanical property of the TPE material.

Another object of the present invention is to provide a method for preparing the above TPE material.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the TPE material with antibacterial conductivity is prepared from the following raw materials in parts by weight: 10-20 parts of SEBS rubber elastomer; 10-20 parts of mineral oil; 20-30 parts of polypropylene; 5-10 parts of polypropylene antibacterial master batch; 10-20 parts of carbon nanotubes; 15-25 parts of a filler; 3-8 parts of SBS rubber elastomer; 0.2-0.5 part of an auxiliary agent;

wherein the carbon nanotube is subjected to surface treatment.

Furthermore, the melt index of the SEBS rubber elastomer is 5-15g/10min, and the molecular weight is 29-32 ten thousand.

Further, the mineral oil has a kinematic viscosity at 40 ℃ of 40-60mm²/s。

Further, the melt index of the polypropylene is 10-20g/10min, and the hardness is 70-90R.

Further, the antibacterial component of the polypropylene antibacterial master batch is a nano inorganic antibacterial agent, and the nano inorganic antibacterial agent is one or more of nano copper ions, nano zinc ions and nano silver ions; the melt index of the polypropylene antibacterial masterbatch is 1-10g/10 min.

Further, the particle size of the carbon nano tube is 1-70nm, the average length is 1-80 μm, and the carbon nano tube is one or two of a double-wall carbon nano tube and a multi-wall carbon nano tube.

Further, the filler is ultrafine calcium carbonate with the mesh number of 1000-1200;

the melt index of the SBS elastomer is 3-8g/10min, and the hardness is 60-80A.

Further, the effective components of the auxiliary agent are hindered phenol antioxidant and phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1-2: 1;

further, the hindered phenol antioxidant is tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.

A preparation method of a TPE material with antibacterial conductivity comprises the following steps:

(1) weighing raw materials according to a proportion;

(2) surface treatment of the carbon nano tube, namely putting the carbon nano tube weighed in the step (1) into an o-dichlorobenzene supersaturated solution of an amide β nucleating agent, performing ultrasonic dispersion, performing suction filtration, repeatedly washing with deionized water, thoroughly washing off the o-dichlorobenzene solvent, finally putting the washed carbon nano tube into an oven for drying, wherein the dried product is the carbon nano tube with the surface coated with β nucleating agent;

(3) adding the SEBS rubber and the SBS rubber weighed in the step (1) into a stirring kettle, adding mineral oil, stirring for 5-7min to enable the mineral oil to be fully and uniformly absorbed by the rubber, and taking out for later use;

(4) adding the filler weighed in the step (1), the modified carbon nano tube obtained in the step (2) and the auxiliary agent into a stirring kettle, stirring for 3-5min to fully disperse the materials, and taking out for later use;

(5) adding the polypropylene and the polypropylene antibacterial master batch weighed in the step (1) into a stirring kettle, stirring for 3-5min, fully mixing, and taking out for later use;

(6) respectively feeding the mixed materials obtained in the steps (3), (4) and (5) into a double-screw extruder through 1#, 2# and 3# weightlessness scales, wherein the extrusion temperature is 170-;

(7) and (4) sequentially carrying out bracing, water cooling, air cooling, grain cutting and packaging on the extruded material obtained in the step (6), thus obtaining the antibacterial conductive TPE material.

Further, the ultrasonic dispersion time in the step (2) is 3 hours, the temperature of the oven is 90 ℃, and the drying time is 3 hours;

the zone temperatures of the twin-screw extruder are 170 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, 210 ℃, the head temperature is 190 ℃ and the vacuum degree is-0.05 to-0.07 Mpa respectively.

The invention has the beneficial effects that:

1. the material with the conductivity and the antibacterial property is obtained by the specific formula materials and the proportion on the premise of meeting the mechanical property required by daily use, the volume resistance of the material is less than 100 omega, the antibacterial rate is more than 94.3 percent and can reach 98.9 percent at most, and the material has better antibacterial property and conductivity.

2. The invention adopts a non-covalent bond method to modify the carbon nano tube, namely, the β nucleating agent which coats polypropylene on the surface of the carbon nano tube improves the dispersibility of the carbon nano tube through pi-pi conjugation, meanwhile, β nucleating agent induces polypropylene components to form β crystal form, β crystal form polypropylene crystal grains are smaller, the crystallinity is higher, the crystal grains are distributed more uniformly, and the space structure arrangement of the carbon nano tube in a system is facilitated.

3. According to the invention, the β nucleating agent of polypropylene is coated on the surface of the carbon nano tube, the β nucleating agent induces the polypropylene component to form a β crystal form, and under the synergistic effect of mineral oil, after the phenomena of self-aggregation and mutual aggregation are avoided, the compatibility among the components is better, the antibacterial property and the conductivity of the material are more uniform, the performance of the TPE material is improved, the problem that the antibacterial property and the conductivity are difficult to be compatible is solved, and the antibacterial property and the conductivity of the TPE are improved.

4. According to the invention, the polypropylene component is induced to form the β crystal form by the β nucleating agent, so that the toughness of the polypropylene component is increased, and meanwhile, the compatibility among the components is better, and the carbon nano tube and the nano antibacterial agent are uniformly dispersed, so that the problem of reduction of the mechanical property of the TPE material caused by incompatibility of the components is avoided.

5. According to the invention, during preparation, the material is divided into three components according to the form of the material, and the three components are proportionally added into the double screws by adopting a weightlessness scale, so that the components can be uniformly mixed in proportion and in form to the maximum extent, the components of the material are further uniform, and the performance of the material is optimized.

Detailed Description

In order to better understand the technical content of the invention, specific embodiments are specifically described.

All used in the following examples are: the melt index of the SEBS rubber elastomer is 10g/10min, and the molecular weight is 30 ten thousand; the kinematic viscosity of the mineral oil at 40 ℃ is 48mm²S; the melt index of the polypropylene is 14g/10min, and the hardness is 85R; the melt index of the polypropylene antibacterial master batch is 6g/10 min; the inorganic antibacterial agent in the polypropylene antibacterial master batch is a silver ion antibacterial agent; the carbon nano tube is a multi-wall carbon nano tube, the average particle size is 50nm, and the average length is 70 mu m; the melt index of the SBS elastomer is 4g/10min, and the hardness is 66A; the filler is ultrafine calcium carbonate with the mesh number of 1000-1200; the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant in the auxiliary agent is 2: 1.

Example 1

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 1.

TABLE 1

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in the table 1;

(2) surface treatment of the carbon nano tube, namely putting the carbon nano tube weighed in the step (1) into an o-dichlorobenzene supersaturated solution of an amide β nucleating agent, performing ultrasonic dispersion for 3 hours, performing suction filtration, repeatedly washing with deionized water, thoroughly washing off the o-dichlorobenzene solvent, finally putting the washed carbon nano tube into a 90 ℃ oven for drying for 3 hours, wherein the dried product is the carbon nano tube with the surface coated with β nucleating agent;

(4) adding the filler weighed in the step (1), the modified carbon nano tube obtained in the step (2) and the auxiliary agent into a stirring kettle, stirring for 4min to fully disperse the materials, and taking out for later use;

(5) adding the polypropylene and the polypropylene antibacterial master batch weighed in the step (1) into a stirring kettle, stirring for 4min, fully mixing, and taking out for later use;

(6) feeding the mixed materials obtained in the steps (3), (4) and (5) into a double-screw extruder through No. 1, No. 2 and No. 3 weightless scales respectively, wherein the zone temperature of the double-screw extruder is 170 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, 210 ℃, 190 ℃ of the head temperature, and the vacuum degree is-0.07 Mpa;

The particles obtained above were injection molded into specimens and then subjected to performance testing, to which the results are shown in Table 2.

TABLE 2

Example 2

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 3.

TABLE 3

Name of raw materials	Parts by mass
		SEBS rubber elastomer	20
Mineral oil	13
		Polypropylene	22
Polypropylene antibacterial masterbatch	5
		Carbon nanotube	20
Filler material	17
		SBS rubber elastomer	3
Auxiliary agent	0.4

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in the table 3;

(6) feeding the mixed materials obtained in the steps (3), (4) and (5) into a double-screw extruder by a No. 1, No. 2 and No. 3 weightless scale respectively, wherein the zone temperature of the double-screw extruder is 170 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, 210 ℃, 190 ℃ of the head temperature, and the vacuum degree is-0.06 Mpa;

The obtained pellets were injection molded into specimens and subjected to performance testing, and the results are shown in Table 4.

TABLE 4

Example 3

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 5.

TABLE 5

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in the table 5;

The obtained pellets were injection-molded into specimens and then subjected to performance tests, to conclude that they are shown in Table 6.

TABLE 6

Example 4

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 7.

TABLE 7

Name of raw materials	Parts by mass
		SEBS rubber elastomer	14
Mineral oil	16
		Polypropylene	27
Polypropylene antibacterial masterbatch	10
		Carbon nanotube	10
Filler material	15
		SBS rubber elastomer	8
Auxiliary agent	0.3

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in Table 7;

(6) feeding the mixed materials obtained in the steps (3), (4) and (5) into a double-screw extruder by a No. 1, No. 2 and No. 3 weightless scale respectively, wherein the zone temperature of the double-screw extruder is 170 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, 210 ℃, 190 ℃ of the head temperature, and the vacuum degree is-0.05 Mpa;

The obtained pellets were injection-molded into specimens and then subjected to performance tests, to conclude that they are shown in Table 8.

TABLE 8

Example 5

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 9.

TABLE 9

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in Table 9;

The obtained pellets were injection-molded into specimens and then subjected to performance tests, leading to the results shown in Table 10.

Watch 10

Comparative example 1

The components and the contents thereof are as follows: the raw material composition in this example is shown in table 11.

TABLE 11

Name of raw materials	Parts by weight
		SEBS rubber elastomer	20
Mineral oil	20
		Polypropylene	30
Filler material	22
		SBS rubber elastomer	8
Auxiliary agent	0.3

The preparation method comprises the following steps:

(1) weighing raw materials according to the proportion given in Table 11;

(2) adding the SEBS rubber and the SBS rubber weighed in the step (1) into a stirring kettle, adding mineral oil, stirring for 5-7min to enable the mineral oil to be fully and uniformly absorbed by the rubber, and taking out for later use;

(3) adding the filler and the auxiliary agent weighed in the step (1) into a stirring kettle, stirring for 4min to fully disperse the materials, and taking out for later use;

(4) feeding the mixed materials obtained in the steps (2) and (3) and the weighed polypropylene in the step (1) into a double-screw extruder through a No. 1, No. 2 and No. 3 weightless scale respectively, wherein the zone temperature of the double-screw extruder is 170 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, 210 ℃, 190 ℃ of the head temperature, and the vacuum degree is-0.06 Mpa;

(5) and (4) sequentially carrying out bracing, water cooling, air cooling, grain cutting and packaging on the extruded material obtained in the step (4), thus obtaining the antibacterial conductive TPE material.

The obtained pellets were injection-molded into specimens and then subjected to performance tests, to conclude that they are shown in Table 12.

TABLE 12

From the performance test results of the materials obtained in examples 1 to 5, that is, tables 2, 4, 6, 8 and 10, it can be seen that the volume resistance of the material obtained in the invention is less than 100 Ω, and meanwhile, the antibacterial rate is greater than 94.3%, and can be up to 98.9%, and the material has better antibacterial property and conductivity, and from the performance test table 12 of comparative example 1, the material integrates the conductive antibacterial property, and simultaneously, the mechanical properties of the TPE material are ensured, even the tensile strength can be improved by 20%, the elongation at break can be improved by 13%, and the material has excellent mechanical properties.

Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims

1. The TPE material with antibacterial and conductive performances is characterized by comprising the following raw materials in parts by weight: 10-20 parts of SEBS rubber elastomer; 10-20 parts of mineral oil; 20-30 parts of polypropylene; 5-10 parts of polypropylene antibacterial master batch; 10-20 parts of carbon nanotubes; 15-25 parts of a filler; 3-8 parts of SBS rubber elastomer; 0.2-0.5 part of an auxiliary agent;

wherein the carbon nanotube is subjected to surface treatment.

2. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the melt index of the SEBS rubber elastomer is 5-15g/10min, and the molecular weight is 29-32 ten thousand.

3. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the kinematic viscosity of the mineral oil at 40 ℃ is 40-60mm²/s。

4. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the melt index of the polypropylene is 10-20g/10min, and the hardness is 70-90R.

5. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the antibacterial component of the polypropylene antibacterial master batch is a nano inorganic antibacterial agent, and the nano inorganic antibacterial agent is one or more of nano copper ions, nano zinc ions and nano silver ions; the melt index of the polypropylene antibacterial masterbatch is 1-10g/10 min.

6. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the carbon nano tube has the particle size of 1-70nm and the average length of 1-80 mu m, and is one or two of a double-wall carbon nano tube and a multi-wall carbon nano tube.

7. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the filler is ultrafine calcium carbonate with the mesh number of 1000-1200;

the melt index of the SBS elastomer is 3-8g/10min, and the hardness is 60-80A.

8. The TPE material with antibacterial and electric conductivity as claimed in claim 1, wherein: the effective components of the auxiliary agent are hindered phenol antioxidant and phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1-2: 1;

the hindered phenol antioxidant is tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.

9. A method for preparing a TPE material with antibacterial and electric conductivity as claimed in any one of claims 1-8, wherein the method comprises the following steps:

(1) weighing raw materials according to a proportion;

10. The method for preparing a TPE material with antibacterial and electric conductivity as claimed in claim 9, wherein: the ultrasonic dispersion time in the step (2) is 3 hours, the temperature of the oven is 90 ℃, and the drying time is 3 hours;