CN116178914A - Binary blending PBT master batch preparation method and blending master batch prepared by same - Google Patents

Abstract

The invention discloses a method for preparing a binary blended PBT masterbatch and the blended masterbatch prepared by the method, wherein the method part includes the following steps: S1: providing PBT particles and ABS particles; S2: cleaning the surface of the ABS particles Modification and dry blending with graphene composite agent to obtain composite ABS particles; S3: blending PBT particles, composite ABS particles and functional additives, extruding and granulating to obtain blended PBT master batches; first pass The ABS particles are modified and compounded with a special graphene composite agent, so that the graphene composite agent can be stably coated on the surface of the ABS particles, which solves the problem of poor dispersion of graphene in the blend system. And further, the ABS particles carrying the graphene composite agent-coated surface can be well blended with the PBT particles to obtain a binary blend.

Description

Preparation method of binary blended PBT masterbatch and blended masterbatch prepared by the method

technical field

The invention relates to the field of PBT masterbatch preparation, in particular to a method for preparing binary blended PBT masterbatch and the blended masterbatch prepared by the method.

Background technique

Since the emergence of polymer materials, people have been paying attention to them, especially some important fibers and engineering plastics, and penetrate into all aspects of people's lives; such as instruments and equipment, building materials or aviation and navigation; among them, PBT is the most important One of engineering plastics, it is widely used in automobiles, fiber protective gear, film materials, mechanical parts and other industries; as for ordinary PBT particles, it is often stored and transported in the form of particles, and the polar ethyl ester group in the molecule of PBT particles There is a large interaction with the carboxyl group, which makes the adjacent PBT molecular chains tighter and the rigidity of the molecular chains increases, which affects the mechanical properties; it greatly limits its application range, therefore, PBT particles are rarely used alone , most of them need to be modified before they can be used;

Commonly used modification methods include the introduction of functional components or the use of multi-component blending. The introduction of functional components can be classified as copolymers, such as toughening monomers, conductive monomers or core-shell composite monomers. It can significantly improve the parameter value of a certain characteristic of PBT materials, but because PBT particles must reach the relevant proportion in the composite components, it is difficult to unify the physical and chemical properties of PBT materials, such as PBT with good flame retardancy and toughness The improvement of fire resistance and fire resistance will be further limited; and the use of multi-component blending refers to the process of mixing two or more homopolymers to form a macroscopically uniform substance, for example, combining PBT particles with PET particles in engineering plastics , PA particles or PP particles are blended to obtain a binary or multi-component blend, which can make the blended PBT material have a certain strength, elastic modulus and heat resistance, and effectively improve the toughness. Because the physical and chemical properties can be relatively balanced , and become the focus of relevant enterprises to explore;

Graphene has a unique structure and form, which can provide good electrical conductivity, high temperature resistance and remarkable heat dissipation performance; many researchers want to apply graphene to the blend system, but graphene has strong hydrophilicity, which is difficult Dispersed in the blend system; without guaranteeing the dispersion of graphene, the total cost of graphene added will be higher than the cost of other substrates. Therefore, introducing graphene into the PBT blend system can maintain graphite The performance advantages of alkene can be used to prepare materials with more balanced physical and chemical properties.

Contents of the invention

Aiming at the above technology, the dispersion problem of graphene further limits the application in the PBT blending system, and the technical problem that the performance advantage of graphene material cannot be reflected, the present invention provides a kind of solution.

To achieve the above object, the invention provides a method for preparing binary blended PBT masterbatch, comprising the following steps:

S1: Provide PBT particles and ABS particles;

S2: modifying the surface of ABS particles, and dry mixing with graphene composite agent to obtain composite ABS particles;

S3: Blend PBT granules, composite ABS granules and functional additives, extrude and granulate to prepare blended PBT master batches;

Among them, the ratio of PBT particles, composite ABS particles and functional additives is 5:4:1.

As an improved solution of the present invention, in step S2, the surface improvement step of ABS particles includes:

Flat pressing: Press the ABS particles into an oval shape through a flat pressing machine;

Grinding: Grinding the ABS particles that have completed the flat pressing step through a sand mill;

Ionization: The ABS particles that have completed the grinding step are ionized through a plasma processor to obtain a rough porous surface.

As an improved solution of the present invention, in the flat pressing step, first adjust the upper pressing surface of the flat pressing machine to fit the surface of the ABS granules, and the parameters of the flat pressing machine are:

The first extrusion stage: pressing pressure: 8N, holding time: 10min;

The second extrusion stage: pressing pressure: 10N, holding time: 10min;

The third extrusion stage: pressing pressure: 12N, holding time: 10min;

The fourth extrusion stage: pressing pressure: 8N, holding time: 10min.

The fifth extrusion stage: pressing pressure: 4N, holding time: 5min.

As a kind of improvement scheme of the present invention, in step S2, the preparation step of graphene composite agent comprises:

A: Obtain graphene oxide, configure it into a 4-5% aqueous solution, and obtain graphene slurry;

B: The graphene slurry is subjected to high-speed shearing to obtain a graphene dispersion;

C: Mix and stir the graphene dispersion liquid and the crosslinking agent in proportion, and spray dry at 100-120° C. to obtain the graphene composite agent.

As an improvement of the present invention, in step B, in the high-speed shear stage, it is also necessary to add a pH regulator so that the pH range of the graphene dispersion is between 6-8

As an improvement of the present invention, the pH regulator is ammonia water with an ammonia content of 21%.

As an improvement of the present invention, in step B, it is also necessary to maintain the temperature of the graphene slurry below 30° C. during the high-speed shearing stage.

As an improvement of the present invention, in step S2, the time for dry mixing is 30-60 minutes.

As an improved solution of the present invention, in step S3, by blending PBT particles and composite ABS particles with functional additives through a mixer, the blending parameters are: temperature 300°C, rotor speed 120r/ min, and the kneading time is 15-20min; after the blending is completed, put the blend into a single-screw extruder for extrusion and granulation to obtain a blended PBT masterbatch.

Also provided is a blending masterbatch, which is produced according to any one of the above preparation methods.

The beneficial effects of the present invention are: compared with the prior art, the present invention provides a method for preparing binary blended PBT masterbatches and the blended masterbatches prepared by the method, wherein the method part includes the following steps: S1: Provide PBT particles and ABS particles; S2: modify the surface of ABS particles, and dry mix with graphene composite agent to obtain composite ABS particles; S3: blend PBT particles, composite ABS particles and functional additives Mixing, extruding and granulating to obtain a blended PBT masterbatch; wherein, the ratio of PBT granules, composite ABS granules and functional additives is 5:4:1. ; Firstly, by modifying the ABS particles and compounding them with a special graphene compounding agent, the graphene compounding agent can be stably coated on the surface of the ABS particles, solving the poor dispersion of graphene in the blend system problem, and further enable good blending of the ABS particles carrying the graphene composite agent-coated surface with the PBT particles to obtain a binary blend.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

Detailed ways

In order to express the present invention more clearly, the present invention will be further described below in conjunction with the accompanying drawings.

In the following description, general example details are given in order to provide a deeper understanding of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. It should be understood that the specific examples are only used to explain the present invention, not to limit the present invention.

It should be understood that when the terms "comprising" and/or "comprising" are used in this specification, they indicate the presence of features, integers, steps, operations, elements or components, but do not exclude the presence or addition of one or more other features. , whole, step, operation, element, component or their combination.

Commonly used modification methods include the introduction of functional components or the use of multi-component blending. The introduction of functional components can be classified as copolymers, such as toughening monomers, conductive monomers or core-shell composite monomers. It can significantly improve the parameter value of a certain characteristic of PBT materials, but because PBT particles must reach the relevant proportion in the composite components, it is difficult to unify the physical and chemical properties of PBT materials, such as PBT with good flame retardancy and toughness The improvement of fire resistance and fire resistance will be further limited; and the use of multi-component blending refers to the process of mixing two or more homopolymers to form a macroscopically uniform substance, for example, combining PBT particles with PET particles in engineering plastics , PA particles or PP particles are blended to obtain a binary or multi-component blend, which can make the blended PBT material have a certain strength, elastic modulus and heat resistance, and effectively improve the toughness. Because the physical and chemical properties can be relatively balanced , and become the direction that relevant enterprises focus on exploring;

Graphene has a unique structure and form, which can provide good electrical conductivity, high temperature resistance and remarkable heat dissipation performance; many researchers want to apply graphene to the blend system, but graphene has strong hydrophilicity, which is difficult Dispersed in the blend system; without guaranteeing the dispersion of graphene, the total cost of graphene added will be higher than the cost of other substrates. Therefore, introducing graphene into the PBT blend system can maintain graphite The performance advantages of alkene can be used to prepare materials with more balanced physical and chemical properties.

In order to solve the above-mentioned technical problems, the present invention provides a method for preparing binary blended PBT masterbatches and the blended masterbatches prepared by the method, please refer to accompanying drawing 1, the method part includes the following steps:

S1: Provide PBT particles and ABS particles;

S2: modifying the surface of ABS particles, and dry mixing with graphene composite agent to obtain composite ABS particles;

S3: Blend PBT granules, composite ABS granules and functional additives, extrude and granulate to prepare blended PBT master batches.

First, by modifying the ABS particles and compounding them with a special graphene compounding agent, the graphene compounding agent can be stably coated on the surface of the ABS particles, solving the problem of poor dispersion of graphene in the blend system problems, and further enable the ABS particles with the coated surface of the graphene composite agent to be well blended with the PBT particles to obtain a binary blend;

In order to better understand the solution of the present invention, further elaborate in conjunction with specific implementation steps:

In this embodiment, the purpose is to make the graphene component form a good coordination state with the ABS raw material, and can and can be further blended with the PBT raw material to obtain a binary material:

Therefore, in step S2 of the present embodiment, the surface improvement step of ABS particles includes:

Flat pressing: Press the ABS particles into an ellipse through a flat pressing machine; since the ABS particles are cylindrical in the raw material stage, with a height of 8mm, although the structure is relatively uniform, the angular structure at both ends and the rough and uneven surface are directly The adhesion of the affected graphene components, through the flat pressing stage, makes the ABS particles deform to a certain extent, but it will not be destroyed, resulting in a larger contact area;

Grinding: The ABS particles that have completed the flat pressing step are ground through a sand mill; the surface of the ABS particles can be ground into a smooth surface; the medium of the sand mill is made of zirconia beads with a diameter of 0.1mm, and the grinding time It is 120min, which can further make the surface of ABS particles smooth and stable. If the types of grinding media are different, or the diameter is too large or too small, or the grinding time is insufficient, the required ABS particles will not be able to meet the follow-up and The combination of graphene raw materials;

Ionization: The ABS particles that have completed the grinding step are ionized through a plasma processor to obtain a rough porous surface; after the ABS particles enter the plasma processor, because the ABS particles have completed the grinding process, the edges and edges of the ABS particles are effectively eliminated. Irregular surface, the plasma treats the surface with a certain radio frequency power to form a rough and porous surface. The power of the plasma processor is 1600-1800W, the gas feeding speed is 205-300cc/min, and the gas uses CF4 and O2 , The temperature of the feed is between 50-60°C.

In order to cause mechanical rupture of ABS particles during the flat pressing stage, resulting in unpredictable problems, in the flat pressing step, the ABS particles are laid flat in the pressing jig, and then the upper pressing surface of the flat pressing machine and the ABS are adjusted. For the surface bonding of particles, the parameters of the flat press are:

The first extrusion stage: pressing pressure: 8N, holding time: 10min;

The second extrusion stage: pressing pressure: 10N, holding time: 10min;

The third extrusion stage: pressing pressure: 12N, holding time: 10min;

The fourth extrusion stage: pressing pressure: 8N, holding time: 10min;

The fifth extrusion stage: pressing pressure: 4N, holding time: 5min;

In the above-mentioned pressing stage, the force required for pressing is firstly increased step by step. From the first to the third extrusion stage, the force on the ABS particles is smooth and increases linearly step by step, which will not cause the ABS particles to cause mechanical damage due to excessive initial force. However, in the subsequent fourth and fifth extrusion stages, the ABS particles recover a certain shape due to their own elasticity, and the overall shape is close to ellipse, and the fourth and fifth extrusion stages also gradually become smaller. , will not cause excessive rebound due to sudden disappearance of force, resulting in poor deformation.

The following is a hydrophilic test of the above-mentioned surface-treated ABS particles, and the obtained test results are shown in Table 1:

Table 1

serial number deal with Surface contact angle between pure water and ABS particles sample 1 blank 86.2° sample 2 surface modification 12.6° sample 3 surface modification 12.9°

It is not difficult to know from the above table 1 that after surface modification, the surface contact angle of pure water on ABS particles becomes significantly smaller, showing high hydrophilicity, which can serve as the basis for subsequent coating of graphene components.

In the present embodiment, by processing the graphene oxide raw material: specifically, in step S2, the preparation steps of the graphene composite agent include:

A: Obtain graphene oxide, configure it into a 4-5% aqueous solution, and obtain graphene slurry; graphene oxide is the oxidation product of graphene. More active functional groups are added, which can form better effects with crosslinking agents and additives in the follow-up. In this stage, the selected oxidation degree of graphene oxide is between 5-9%, and the highly oxidizable graphite oxide Alkenes have more reactive functional groups;

B: The graphene slurry is subjected to high-speed shearing to obtain a graphene dispersion; the preparation method of graphene oxide is pickled with high-concentration hydrochloric acid or sulfuric acid, so that the pH of graphene oxide is usually between 1.5 and 4.0, showing Acidity, even if it is prepared into a related aqueous solution, acidity cannot be effectively neutralized. If high-speed shearing is used directly for shearing, graphene oxide cannot be effectively opened and dispersed due to being in an acidic environment; therefore, high-speed shearing In the cutting stage, it is also necessary to add a pH regulator so that the pH range of the graphene oxide dispersion is between 6-8, and the pH is adjusted to be weakly alkaline, and the viscosity of the graphene oxide slurry will increase as the degree of dispersion increases. It becomes larger and larger, and the viscosity can reach 30000-40000CP, but with the further increase of the degree of dispersion, it will drop to about 10000CP, and judge whether the graphene slurry is effectively dispersed and modulated into graphene dispersion by this viscosity. liquid; in a more optimal solution, the pH regulator is ammonia water with an ammonia content of 21%, which is weakly alkaline and has high economic value, and will not introduce interfering media to affect subsequent blending; it is worth noting that , graphene oxide will generate heat during the dispersion process, and the temperature can reach 50-60 ° C. At this temperature, due to the influence of the large π bond of graphene oxide, it is easy to agglomerate, which further limits the oxidation. Dispersion of graphene, therefore, in the high-speed shear stage, the cavity containing the graphene slurry is cooled by means of an ice bath, which can effectively keep the graphene slurry below 30°C and further maintain Dispersion effect, no agglomeration;

C: Mix and stir the graphene dispersion liquid and the cross-linking agent in proportion, and spray dry at 100-120°C to obtain the graphene composite agent; the cross-linking agent uses a silane coupling agent, and the specific model of the silane coupling agent can be: KH902, KH560, KH540, KH550, KH580, KH792, KH901, KH791, etc., the mixing ratio of graphene oxide and cross-linking agent is 10:1, and the cross-linking agent can modify the graphene dispersion to improve the ASB Particle cohesion; drying and collecting the powdered graphene composite agent at 100-120°C can further avoid the influence of moisture;

Because the graphene composite agent is powdery, the particle size of the ABS particles is larger than the particle diameter of the graphene composite agent even through the frosting treatment, so it is most suitable to use the dry mixing form for mixing. In step S2, the graphene The content of the compounding agent is enough to evenly coat the surface of the ABS particles, and the dry mixing time is 30-60 minutes; after dry mixing, the composite ABS particles whose surfaces are coated with the graphene compounding agent are obtained.

In this embodiment, in step S3, the PBT particles and composite ABS particles are blended with functional additives through a mixer. The blending parameters are: temperature 300°C, rotor speed 120r/min, mixing The kneading time is 15-20 minutes, and the functional auxiliary agent can be antioxidant 168 or antioxidant 1010; after the blending is completed, put the blend into a single-screw extruder for extrusion and granulation to obtain a blended PBT masterbatch;

The blending masterbatch is prepared in combination with the specific method and procedure below:

Example 1:

S1: Provide PBT particles and ABS particles;

S2: modify the surface of the ABS particles, and prepare a graphene composite agent for dry mixing;

A0: The specific steps of surface modification of ABS particles are as follows:

A1: Flat pressing: Press the ABS particles into an oval shape through a flat pressing machine;

The flat pressing process is: lay the ABS granules on a flat surface in the pressing jig, and then adjust the upper pressing surface of the flat press to fit the surface of the ABS granules;

The first extrusion stage: pressing pressure: 8N, holding time: 10min;

The second extrusion stage: pressing pressure: 10N, holding time: 10min;

The third extrusion stage: pressing pressure: 12N, holding time: 10min;

The fourth extrusion stage: pressing pressure: 8N, holding time: 10min.

The fifth extrusion stage: pressing pressure: 4N, holding time: 5min.

A2: Grinding: The ABS particles that have completed the flat pressing step are ground through a sand mill; the medium of the sand mill is zirconia beads with a diameter of 0.1 mm, and the grinding time is 120 minutes.

A3: Ionization: The ABS particles that have completed the grinding step are ionized through a plasma processor to obtain a rough porous surface; the power of the plasma processor is 1600-1800W, the gas feed rate is 205-300cc/min, and the gas is CF4 and O2, the temperature of the feed is between 50-60°C.

B0: The preparation steps of graphene composite agent are:

B1: Obtain 15g of graphene oxide, configure it into a 4-5% aqueous solution, and obtain graphene slurry;

B2: Move the graphene slurry to a stirring tank for high-speed shearing to obtain a graphene dispersion; and in the high-speed shearing stage, the stirring tank needs ice bath treatment, and by adding ammonia water, the pH range of the graphene dispersion is obtained 7.0-7.5;

B3: Mix and stir the graphene dispersion and the cross-linking agent at a ratio of 10:1, spray dry at 120°C, collect the powder, and obtain the graphene composite agent; the cross-linking agent is KH550;

C0: Dry-mix the ABS particles obtained in step A3 and the graphene composite agent obtained in step B3. The dry-mixing time is 60 minutes, and it can be operated under room temperature adjustment:

S3: 100 parts of PBT granules, 80 parts of composite ABS granules and 10 parts of functional additives were blended, extruded and granulated, and the blended PBT masterbatch sample of Example 1 was obtained;

Comparative example:

100 parts of PBT granules, 80 parts of ABS granules and 10 parts of functional additives were blended, extruded and granulated to prepare comparative samples;

And the detection carried out to the embodiment 1 blending PBT masterbatch sample that makes, gained result is as follows table 2:

Table 2

sample Surface resistance (Ω) 40℃ Notched Impact Strength (KJ/m ² ) UL-94 Shrinkage% comparative example 10 ⁸ 13 V0 0.3-0.5 Example 1 10 ³ 20 V0 0.2-0.3

It is not difficult to know from Table 2 that compared with the comparative example, the surface resistance of Example 1 has been greatly improved, showing the high conductivity of graphene raw materials, and effectively improving the impact strength; and in terms of flame retardancy, there is no Clearly reduced, reaching the existing level; with the synergistic effect of surface modification, the shrinkage rate is further reduced in the subsequent kneading and molding.

The advantages of the present invention are:

First, by modifying the ABS particles and compounding them with a special graphene compounding agent, the graphene compounding agent can be stably coated on the surface of the ABS particles, solving the problem of poor dispersion of graphene in the blend system Problems, and further enable good blending of ABS particles with graphene-coated composite agent-coated surface with PBT particles to obtain a binary blend with balanced comprehensive physical and chemical properties.

The above disclosures are only a few specific embodiments of the present invention, but the present invention is not limited thereto, and any changes conceivable by those skilled in the art shall fall within the protection scope of the present invention.

Claims (10)

1. a kind of binary blending PBT masterbatch preparation method is characterized in that, comprises the following steps: S1: Provide PBT particles and ABS particles; S2: modifying the surface of the ABS particles, and dry mixing with the graphene composite agent to obtain composite ABS particles; S3: Blending the PBT granules and the composite ABS granules with functional additives, extruding and granulating to prepare blended PBT masterbatches; Wherein, the ratio of the PBT particles, the composite ABS particles and the functional auxiliary agent is 5:4:1. 2. binary blending PBT master batch preparation method according to claim 1, is characterized in that, in step S2, the surface improvement step of described ABS particle comprises: Flat pressing: press the ABS particles into an oval shape by a flat pressing machine; Grinding: Grinding the ABS particles that have completed the flat pressing step through a sand mill; Ionization: the ABS particles that have completed the grinding step are ionized by a plasma processor to obtain a rough porous surface. 3. binary blending PBT masterbatch preparation method according to claim 2 is characterized in that, in flat pressing step, first adjusts the upper pressing surface of described flat pressing machine and the surface of described ABS granule is bonded, The parameters of the flat press are: The first extrusion stage: pressing pressure: 8N, holding time: 10min; The second extrusion stage: pressing pressure: 10N, holding time: 10min; The third extrusion stage: pressing pressure: 12N, holding time: 10min; The fourth extrusion stage: pressing pressure: 8N, holding time: 10min; The fifth extrusion stage: pressing pressure: 4N, holding time: 5min. 4. binary blending PBT master batch preparation method according to claim 1, is characterized in that, in step S2, the preparation step of described graphene composite agent comprises: A: Obtain graphene oxide, configure it into a 4-5% aqueous solution, and obtain graphene slurry; B: subjecting the graphene slurry to high-speed shearing to obtain a graphene dispersion; C: mixing and stirring the graphene dispersion liquid and the crosslinking agent in proportion, and spray drying at 100-120° C. to obtain the graphene composite agent. 5. binary blending PBT masterbatch preparation method according to claim 4 is characterized in that, in step B, in high-speed shear stage, also need will add pH adjuster so that the Graphene dispersion The pH range is between 6-8. 6. binary blending PBT masterbatch preparation method according to claim 5, is characterized in that, described pH regulator is the ammoniacal liquor that ammonia content is 21%. 7. The preparation method of binary blended PBT masterbatch according to claim 6, characterized in that, in step B, it is also necessary to keep the temperature of the graphene slurry less than 30°C in the high-speed shear stage. 8. The method for preparing binary blended PBT masterbatch according to claim 1, characterized in that, in step S2, the time of dry mixing is 30-60min. 9. binary blending PBT masterbatch preparation method according to claim 1, is characterized in that, in step S3, by said PBT particle, described composite ABS particle are carried out blending and described functional aid through Blending in a mixer, the blending parameters are: temperature 300°C, rotor speed 120r/min, mixing time 15-20min; after the blending is completed, put the blend into a single-screw extruder for extrusion Granulating to obtain the blended PBT master batch. 10. A blending masterbatch, characterized in that it is produced according to the preparation method described in any one of claims 1-9.

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