CN114479386A - Super-black plastic master batch dispersed with nano carbon black, preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of functional textile chemical fibers, in particular to the technical field of B29, and more particularly relates to a super-black plastic master batch dispersed with nano carbon black, and a preparation method and application thereof. The super-black plastic master batch dispersed with the nano carbon black comprises, by weight, 100 parts of polyester powder and 50-100 parts of carbon black nano color paste. The super-black plastic master batch is added in the preparation process in the form of carbon black nano color paste, and the content of the dispersing agent in the carbon black nano color paste is low, so that the problem of carbon black agglomeration is solved, and the coloring effect is good.

Description

A kind of ultra-black plastic masterbatch dispersed with nano carbon black, preparation method and application thereof

technical field

The invention relates to the field of functional textile chemical fibers, in particular to the technical field of B29, and more particularly, to a super black plastic masterbatch dispersed with nanometer carbon black, a preparation method and an application thereof.

Background technique

Ultra-black fibers refer to fibers with ultra-high absorptivity and very low reflectivity in the visible light range. Because of its ultra-high visible light absorption, the super black fiber has extremely strong covering power. Clothing made of ultra-black fiber can still maintain a good black color when stretched, which can solve the problem of exposing other colors of fabrics made of ordinary black fiber due to external force. Therefore, the market demand for ultra-black fiber is huge and has broad prospects.

The preparation process of super black fiber is mainly printing and dyeing processing method and dope dyeing method. At present, most of the ultra-black fibers on the market are mainly prepared by printing and dyeing processing. Although the color and blackness of the fiber products obtained by this processing method are good, the color fastness is not good. Moreover, the printing and dyeing process seriously pollutes the environment and may affect the human health. The dope dyeing method not only does not produce industrial waste water, but also has low energy consumption for system processing, and more importantly, can solve the problem of color fastness. However, the blackness of this dye-free polyester fiber has not been able to achieve the effect of printing and dyeing, mainly due to the particle size and dispersibility of carbon black in the fiber masterbatch. The dope dyeing method is generally divided into the melt direct spinning method and the chip spinning method. For example, Chinese patent CN111286804A discloses a preparation method of melt direct spinning super black polyester fiber, and the blackness of the prepared fiber can be obviously improved by adding black color paste during the melt direct spinning process. However, because chip spinning is more in line with the needs of current high-speed spinning technology, and also has the characteristics of convenient variety replacement and rapid adjustment of filler content in fibers, the production of dye-free polyester fibers is generally chip spinning. Therefore, spinning mills have put forward higher blackness, better spinnability and longer component life cycle requirements for black masterbatch.

Generally speaking, the smaller the particle size of carbon black in the fiber masterbatch, the better the dispersibility, and the higher the blackness of the fiber produced. For example, in Chinese patents CN110885457A and CN110903611A, carbon black with a primary particle size of 19-20nm is directly added to plastic powder to prepare masterbatches. The masterbatches have been verified by downstream manufacturers, and the blackness of fibers produced with the masterbatches has been significantly improved. However, the smaller the particle size of carbon black, the greater the surface adsorption energy, and the easier it is to agglomerate, resulting in poor dispersibility of carbon black in the masterbatch. The traditional method of dispersing carbon black powder directly in plastic powder cannot solve the problems of nano-carbon black agglomeration and poor dispersibility in the masterbatch, which not only affects the spinnability and component service life, but also affects the fiber blackness. However, the high content of dispersant in the carbon black slurry prepared by the traditional method makes it impossible to dry after mixing with the plastic powder, resulting in the screw slipping during feeding, which cannot meet the production requirements.

Therefore, a new preparation technology of super black masterbatch is required to solve the problems of nano-carbon black agglomeration and dispersibility in masterbatch.

SUMMARY OF THE INVENTION

In view of some problems existing in the prior art, the first aspect of the present invention provides an ultra-black plastic masterbatch dispersed with nano-carbon black. In parts by weight, the preparation raw materials include 100 parts of polyester powder, 50-100 parts of Parts of carbon black nano-color paste.

In one embodiment, the raw materials for preparing the ultra-black plastic masterbatch dispersed with nano-carbon black further include 0-10 parts by weight of auxiliary agents.

In one embodiment, the type of the polyester powder is not particularly limited, and examples thereof include polybutylene phthalate, polyethylene phthalate, and the like.

Preferably, the melt index of the polyester powder at 265°C/2.16kg is 50-80g/10min, more preferably 60-70g/10min.

Preferably, the melting point of the polyester powder is 250-270°C, such as 250°C, 255°C, 260°C, 265°C, 270°C, and the like.

In this application, polyester powder with a melting point of 250-270° C. has a certain promoting effect on the dispersibility of carbon black.

In one embodiment, the primary particle size of carbon black in the carbon black nano-color paste is 10-18 nm, such as 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm.

Preferably, the concentration of carbon black in the carbon black nano-color paste is 10-30wt%, which can be listed as 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 20wt%, 25wt%, 30wt% %Wait.

In this application, the components other than carbon black in the carbon black nano-color paste are not particularly limited, and can be a wetting agent, a dispersant, a solvent, etc., preferably, the concentration of the dispersant is 1-3wt%, and the specific components are skilled in the art Personnel can make routine selections according to actual needs.

In one embodiment, the carbon black nano-color paste has a viscosity of 7000-8000 cps at 25°C.

In the present application, the primary particle size of carbon black is controlled to be 10-18 nm. When the concentration of the dispersant is low, the excessive growth of carbon black aggregates can be avoided, so that the carbon black nano-color paste in the present application removes carbon black. The types of ingredients and the preparation method of the carbon black nano-color paste do not affect the dispersibility and coloring effect of the carbon black in the present application, which not only saves unnecessary costs, but at the same time, the raw materials are convenient and easy to obtain, and the production efficiency is improved. The form of color paste is mixed and granulated with the polyester powder of the present application, and the obtained ultra-black masterbatch has a low DF value, and the carbon black is more uniformly dispersed, which can realize the ultra-black fiber masterbatch with a low L value. If the primary particle size of carbon black is too large or too small, the dispersion effect of carbon black will be affected, and the stability of the carbon black nano-color paste will be poor at the same time. In addition, when the primary particle size of carbon black is 10-18 nm, even when the concentration of carbon black in the carbon black nano-color paste is kept below 15 wt%, the plastic masterbatch can still obtain better coloring effect.

The auxiliary agents mentioned in this application can be listed as coupling agents, viscosity modifiers, antioxidants, foaming agents, surfactants, plasticizers, cross-linking agents, flame retardants, smoke suppressants, etc. A person skilled in the art can make routine choices.

A second aspect of the present invention provides a method for preparing a super black plastic masterbatch dispersed with nano carbon black, comprising the following steps:

(1) drying after mixing each raw material for preparing super black plastic master batch;

(2) The material obtained in step (1) is put into a twin-screw extruder at 250°C-270°C for extrusion and granulation.

In one embodiment, the preparation method of the ultra-black plastic masterbatch that is dispersed with nano carbon black, comprises the following steps:

(1) put each raw material for preparing super black plastic master batch into the high-speed mixer, heat and stir until the mixed powder is dried;

(2) Put the material obtained in step (1) into a twin-screw extruder for extrusion and granulation: after the mixed material is fully plasticized in the twin-screw, it is uniformly sheared and dispersed by the dispersing element in the twin-screw, and the Die extrusion, water tank cooling, pulling the strands to the pelletizer to cut cylindrical pellets with a length of 3mm±1mm and a diameter of 2.5mm±1.5mm; the twin-screw extruder is equipped with a vacuum device, and the twin-screw extruder is The length-diameter ratio of the machine is not less than 40:1; the process temperature during extrusion is 250℃-270℃.

A third aspect of the present invention provides an application of the super black plastic masterbatch dispersed with nano carbon black in super black fibers.

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

(1) the present invention uses the method for wet feeding to improve the dispersibility of carbon black in the master batch, converts the same concentration of carbon black, the L value in the fiber Lab value prepared by the ultra-black plastic master batch of the present invention is relative to the direct addition The L value of fibers prepared from carbon black powder is lower;

(2) The ultra-black masterbatch with 20wt% carbon black concentration made by the present invention has a filter press value not higher than 7Mpa, and adding 5wt% to the fiber can achieve an L value not higher than 18, and adding 10wt% L value is not high at 15;

(3) The present invention solves the problem that the primary particle size of carbon black is less than 19nm and the surface adsorption energy is too large to agglomerate into micron-scale carbon black in storage, thereby affecting the spinnability of the masterbatch, and then prolonging the service life of the spinning assembly;

(4) The carbon black content in the carbon black nano-color paste of the present invention is 10-30wt%, but the dispersant content is only 1-3wt%, which avoids the high dispersant content of the traditional carbon black paste, which cannot be mixed with plastic powder. Complete drying leads to the problem of screw slippage during granulation;

(5) The carbon black content in the carbon black nano-color paste of the present invention is high, resulting in less organic solvent in the remaining raw materials, and the direct heating and mixing drying time of the high-mixer is short, saving time and power consumption. The paste-like carbon black nano-color paste in the application is much lower than the masterbatch made from the paste-like carbon black components, especially the carbon black nano-color paste with a viscosity of 7000-8000cps at 25°C, and the filter pressure value is much lower;

(6) The present invention controls the carbon black content and primary particle size in the carbon black nano-color paste, which can not only solve the problem of deagglomeration of carbon black that cannot be achieved in ordinary carbon black nano-color paste, but also avoid the occurrence of carbon black after a period of storage. The phenomenon of "returning to thickening" can store carbon black nano-color paste more effectively and stably, and use it as needed;

(7) In the present invention, the carbon black nano-color paste, polyester powder, or after adding auxiliary agents, can be directly mixed and dried to enter the granulator. The process is simple, which meets the needs of the current high-speed spinning technology, and also has the advantages of convenient Variety replacement, rapid adjustment of filler content in fibers, etc.

Description of drawings

Figure 1 shows the L values of black polyester fibers obtained by using masterbatches of Examples 1-3 and Comparative Examples 1-3 of the present application with different concentrations.

Detailed ways

The present invention is described below through specific embodiments, but is not limited to the specific examples given below.

Example 1

A super black plastic master batch dispersed with nano carbon black, by weight, the raw materials are as follows:

100 parts of PET powder, 100 parts of carbon black nano-color paste, 1 part of antioxidant.

Wherein, the PET powder was purchased from Sanfangxiang, Jiangsu, and the brand name was CZ5011; the primary particle size of carbon black in the carbon black nano-color paste was 15 nm, and the concentration was 30 wt %.

The preparation method of the ultra-black plastic master batch dispersed with nano carbon black is as follows:

(1) drop each above-mentioned raw material into the high-speed mixer, heat and stir until the mixed powder is dried, and remove the solvent of the nano-color paste;

(2) Put it into a twin-screw extruder for extrusion and granulation: the mixed material is fully plasticized in the twin-screw, sheared and dispersed evenly by the dispersing element in the twin-screw, extruded through a round orifice die, and cooled in a water tank , Pulled to the pelletizer to cut cylindrical pellets with a length of 3mm±1mm and a diameter of 2.5mm±1.5mm; the twin-screw extruder is equipped with a vacuum device, and the length-diameter ratio of the twin-screw extruder is different. Less than 40:1; the process temperature during extrusion is 260°C.

Comparative Example 1

A plastic masterbatch, in parts by weight, the raw materials are as follows:

100 parts of PET powder, 30 parts of nano-carbon black powder, 1 part of antioxidant.

Wherein, the PET powder was purchased from Sanfangxiang, Jiangsu, and the brand name was CZ5011; the model of the nanometer carbon black powder was consistent with the carbon black in the carbon black nanometers used in the examples.

The preparation method of the plastic masterbatch is the same as that in Example 1, except that the step (1) is as follows: put the above-mentioned raw materials into a high-speed mixer, and fully stir and mix.

The masterbatch prepared in the above-mentioned example and Comparative Example 1 was mixed with white cut pellets (white pure PET masterbatch) at a ratio of 2:14, and a 1400-mesh filter screen was used to test the spinning filterability. The spinning filter pressure value of the embodiment was 2.94. Mpa, the 11min spinning filter pressure value of Comparative Example 1 exceeds the standard (≥10Mpa), which can indicate that the super black masterbatch in the example has better dispersibility in the masterbatch.

Example 2

A plastic master batch, the specific embodiment is the same as that of Example 1, the difference is that the primary particle size of carbon black in the carbon black nano-color paste is 10 nm.

The preparation method of plastic masterbatch is the same as that in Example 1.

Example 3

A plastic master batch, the specific embodiment is the same as that of Example 1, the difference is that the primary particle size of carbon black in the carbon black nano-color paste is 18 nm.

The preparation method of plastic masterbatch is the same as that in Example 1.

Comparative Example 2

A plastic master batch, the specific embodiment is the same as that of Example 1, the difference is that the primary particle size of carbon black in the carbon black nano-color paste is 20 nm.

The preparation method of plastic masterbatch is the same as that in Example 1.

Comparative Example 3

A plastic master batch, the specific embodiment is the same as that of Example 1, the difference is that the primary particle size of carbon black in the carbon black nano-color paste is 30 nm.

The preparation method of plastic masterbatch is the same as that in Example 1.

The masterbatch prepared in the above Example 2-3 and Comparative Example 2-3 was mixed with white cut pellets (white pure PET masterbatch) at a ratio of 2:14, and a 1400-mesh filter screen was used to test the spinning filterability.

The masterbatches prepared in the above-mentioned examples 1-3 and comparative examples 1-3 were mixed with white cut pellets (white pure PET masterbatch) according to the weight additions of 2%, 4%, 6%, 8% and 10%, respectively. For black polyester fibers with 200D/96F specifications, the L value of the produced fibers was tested by a colorimeter. The results are shown in Table 1 and Figure 1.

Table 1

Claims (10)

1. The super-black plastic master batch dispersed with the nano carbon black is characterized in that the raw materials for preparing the super-black plastic master batch comprise, by weight, 100 parts of polyester powder and 50-100 parts of carbon black nano color paste.

2. The ultra-black plastic masterbatch dispersed with nano-carbon black according to claim 1, wherein the carbon black in the carbon black nanopigment has a primary particle size of 10 to 18 nm.

3. The ultra-black plastic masterbatch dispersed with nano-carbon black according to claim 2, wherein the concentration of carbon black in the carbon black nanopaste is 10 to 30 wt%.

4. The ultra-black plastic masterbatch dispersed with nano-carbon black of claim 3, wherein the carbon black nano-color paste further comprises 1-3 wt% of a dispersant.

5. The ultra-black plastic masterbatch dispersed with carbon black according to any one of claims 1 to 4, wherein the polyester powder has a melt index of 50 to 80g/10min at 265 ℃/2.16 kg.

6. The ultra-black plastic masterbatch dispersed with nano-carbon black of claim 5, wherein the melting point of the polyester powder is 250-270 ℃.

7. The nano-carbon black-dispersed ultra-black plastic masterbatch according to claim 5, wherein the raw material for preparing the nano-carbon black-dispersed ultra-black plastic masterbatch further comprises 0 to 10 parts by weight of an auxiliary agent, and the part by weight of the auxiliary agent does not comprise 0.

8. The nano carbon black-dispersed ultra-black plastic masterbatch according to claim 7, wherein the auxiliary agent is one or more selected from a coupling agent, a viscosity modifier, an antioxidant, a foaming agent, a surfactant, a plasticizer, a crosslinking agent, a flame retardant and a smoke suppressant.

9. The preparation method of the nano carbon black dispersed ultra-black plastic master batch according to any one of claims 1 to 8, which comprises the following steps:

(1) mixing the raw materials for preparing the ultra-black plastic master batch and drying;

(2) and (2) putting the material obtained in the step (1) into a double-screw extruder, and extruding and granulating at the temperature of 250-270 ℃.

10. Use of the ultra black plastic masterbatch dispersed with carbon black according to any one of claims 1 to 8 in ultra black fiber.

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