阅读说明：本技术 一种无载体塑料填充母粒的制备方法及其产品 (Preparation method of carrier-free plastic filling master batch and product thereof ) 是由 代少俊 于 2020-06-30 设计创作，主要内容包括：本发明公开了一种无载体塑料填充母粒的制备方法,包括,将凹凸棒土加入去离子水中,加热至60～90℃后,加入偏磷酸搅拌,超声处理1～3h,得到凹凸棒土分散液；向凹凸棒土分散液中添加无机填料,150～250rpm混合1min,后800～2000rpm混合5min,得混合物料；将混合物料放入挤出机常温挤出,挤出压力为2～5MPa,挤出颗粒的直径控制在1～3mm,长径比控制在2～4,将挤出的颗粒在105～170℃下烘干0.5～1.5h,即得到所述无载体塑料填充母粒。本发明采用凹凸棒土作为粘结剂,制备得到的母粒硬度较低,容易在塑料中分散；凹凸棒土作为天然针状纳米材料还可以作为增强填料对塑料复合增强增韧的效果。(The invention discloses a preparation method of carrier-free plastic filling master batch, which comprises the steps of adding attapulgite into deionized water, heating to 60-90 ℃, adding metaphosphoric acid, stirring, and performing ultrasonic treatment for 1-3 hours to obtain attapulgite dispersion liquid; adding an inorganic filler into the attapulgite dispersion liquid, mixing at 150-250 rpm for 1min, and then mixing at 800-2000 rpm for 5min to obtain a mixed material; and (3) putting the mixed material into an extruder for normal temperature extrusion, wherein the extrusion pressure is 2-5 MPa, the diameter of the extruded particles is controlled to be 1-3mm, the length-diameter ratio is controlled to be 2-4, and the extruded particles are dried at the temperature of 105-170 ℃ for 0.5-1.5 h to obtain the carrier-free plastic filling master batch. The attapulgite is used as the binder, and the prepared master batch has low hardness and is easy to disperse in plastics; the attapulgite can be used as a natural needle-shaped nano material and can also be used as a reinforcing filler to reinforce and toughen the plastic composite.)

1. A preparation method of carrier-free plastic filling master batch is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,

adding attapulgite into deionized water, heating to 60-90 ℃, adding metaphosphoric acid, stirring, and performing ultrasonic treatment for 1-3 h to obtain an attapulgite dispersion liquid;

adding an inorganic filler into the attapulgite dispersion liquid, mixing at 150-250 rpm for 1min, and then mixing at 800-2000 rpm for 5min to obtain a mixed material;

and (3) putting the mixed material into an extruder for normal temperature extrusion, wherein the extrusion pressure is 2-5 MPa, the diameter of the extruded particles is controlled to be 1-3mm, the length-diameter ratio is controlled to be 2-4, and the extruded particles are dried at the temperature of 105-170 ℃ for 0.5-1.5 h to obtain the carrier-free plastic filling master batch.

2. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: and adding metaphosphoric acid and stirring, wherein the stirring speed is 800-2000 rpm, and the stirring time is 5-10 min.

3. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: and carrying out ultrasonic treatment for 1-3 h, wherein the ultrasonic power is 1200-2000W, and the temperature is 60-90 ℃.

4. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: the attapulgite is characterized in that the wet sieve residue of a 200-mesh sieve is less than or equal to 2.5 percent, the dry sieve residue of a 100-mesh sieve is less than or equal to 2.0 percent, and the water content is less than or equal to 15 percent.

5. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: and obtaining the attapulgite dispersion liquid, wherein the mass ratio of the attapulgite to the deionized water to the metaphosphoric acid in the attapulgite dispersion liquid is 40: 60-160: 0.5 to 1.

6. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: the inorganic filler comprises one or more of calcium carbonate, titanium dioxide, wollastonite, magnesium hydroxide or aluminum hydroxide.

7. The method for preparing the carrier-free plastic filling masterbatch according to claim 6, wherein the method comprises the following steps: the inorganic filler is characterized in that the shape is spherical, and the grain diameter is not less than 800 meshes.

8. The method for preparing the carrier-free plastic filling masterbatch according to claim 1, wherein the method comprises the following steps: adding an inorganic filler into the attapulgite dispersion liquid, wherein the mass ratio of the inorganic filler to the attapulgite dispersion liquid is 100: 5 to 25.

Technical Field

The invention belongs to the technical field of plastic processing, and particularly relates to a preparation method of carrier-free plastic filling master batch and a product thereof.

Background

The plastic filling master batch is applied to plastics, can reduce the raw material cost of plastic products, saves synthetic plastics, brings economic benefits for enterprises, and is favored by the plastic processing industry. The conventional plastic filling calcium master batch is prepared from plastic, a coupling agent, a lubricant, an inorganic filler and the like. At present, equipment such as a double-screw extruder or an internal mixer is usually adopted for producing the filling master batch, and the carrier-filled master batch is prepared by high-temperature melting plasticization and mixing, cooling and granulation, wherein the defects of the method are as follows: 1) the prepared filling master batch needs to be added with a certain amount of plastic as a carrier, the content of the inorganic filler is difficult to exceed 80%, and in order to enable the plastic and the inorganic filler to be uniformly dispersed and form particles, preheating, melting, plasticizing and mixing processes are needed, and then cooling granulation is carried out, so that energy is greatly wasted, the manufacturing cost of the product is increased, and the filling master batch is not suitable for future low-carbon and economic social requirements; 2) the preparation equipment and the process method of the master batch are only suitable for the filling master batch which uses plastic as a matrix carrier, so that the prepared filling master batch is only suitable for being added into a filling product compatible with a master batch matrix, and the universality of the filling master batch is poor. For example, conventional plastic masterbatch uses non-polar polyolefin as a carrier, has poor dispersibility in polar polymers such as polyester and nylon, and is easily decomposed at the processing temperature of polyester and nylon. Patent CN 106832399B adopts polypropylene alcohol as a dispersing agent and an adhesion agent to prepare a graphene composite polypropylene alcohol master batch, the content of inorganic filler in the master batch can reach more than 90%, although the master batch does not adopt conventional polyolefin as a carrier, the used polypropylene alcohol is also one of high molecules, the master batch is only suitable for polar high molecules such as polyester or nylon, and the universality is poor; and the content of the inorganic filler in the master batch still does not reach 100 percent.

The carrier-free master batch is a hotspot of the research of the prior plastic filling master batch, the carrier-free master batch refers to that no plastic is used, but an adhesive is used for bonding inorganic filler into granules, and the master batch has good universality because no plastic is used as a carrier. Patent CN102504334B discloses a method for preparing a talcum powder filling master batch with high content and wide universality by taking 3-5% (weight ratio) of water as a diluent and 1-3% (weight ratio) of sodium silicate as an adhesive and stirring at normal temperature and carrying out double-rod pressure granulation, but the chemical action exists between the adhesive and a filler, so that the obtained master batch has high hardness, and poor dispersibility in plastics is caused; the master batch also contains components which do not act on plastics, such as sodium silicate and the like, namely the filler content of the master batch is less than 100 percent.

Disclosure of Invention

This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.

The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.

Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method and a product of plastic filling master batch with the inorganic filler content of 100 percent, proper hardness, good dispersibility and wide universality.

In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of carrier-free plastic filling master batches comprises the steps of adding attapulgite into deionized water, heating to 60-90 ℃, adding metaphosphoric acid, stirring, and carrying out heating ultrasonic treatment for 1-3 hours to obtain an attapulgite dispersion liquid; adding an inorganic filler into the dispersion liquid attapulgite dispersion liquid, mixing at 150-250 rpm for 1min, and then mixing at 800-2000 rpm for 5min to obtain a mixed material; and (3) putting the mixed material into an extruder for normal temperature extrusion, wherein the extrusion pressure is 2-5 MPa, the diameter of the extruded particles is controlled to be 1-3mm, the length-diameter ratio is controlled to be 2-4, and the extruded particles are dried at the temperature of 105-170 ℃ for 0.5-1.5 h to obtain the carrier-free plastic filling master batch.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: and adding metaphosphoric acid and stirring, wherein the stirring speed is 800-2000 rpm, and the stirring time is 5-10 min.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: and carrying out ultrasonic treatment for 1-3 h, wherein the ultrasonic power is 1200-2000W, and the temperature is 60-90 ℃.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: the attapulgite has the characteristics that the wet sieve residue of a 200-mesh sieve is less than or equal to 2.5 percent, the dry sieve residue of a 100-mesh sieve is less than or equal to 2.0 percent, and the water content is less than or equal to 15 percent.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: and obtaining the attapulgite dispersion liquid, wherein the mass ratio of the attapulgite to the deionized water to the metaphosphoric acid in the attapulgite dispersion liquid is 40: 60-160: 0.5 to 1.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: the inorganic filler comprises one or more of calcium carbonate, titanium dioxide, wollastonite, magnesium hydroxide or aluminum hydroxide.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: the inorganic filler is characterized in that the shape is spherical, and the grain diameter is not less than 800 meshes.

As a preferred scheme of the preparation method of the carrier-free plastic filling master batch, the preparation method comprises the following steps: adding an inorganic filler into the attapulgite dispersion liquid, wherein the mass ratio of the inorganic filler to the attapulgite dispersion liquid is 100: 5 to 25.

The invention has the beneficial effects that:

(1) the invention adopts the attapulgite as the binder, does not add any macromolecular component, has the content of the inorganic filler reaching 100 percent, has good universality and low cost compared with the plastic carrier master batch, can be used for nonpolar plastics and polar macromolecules, and does not have the problem of pyrolysis.

(2) Compared with the master batch prepared by using sodium silicate as a binder, the attapulgite used in the invention has small binding power, low master batch hardness and good dispersibility in plastics, because the principle of binding the inorganic filler by the sodium silicate has chemical binding action besides dehydration binding action, the principle is as follows: na (Na)₂SiO+CO₂+HO＝H₂SiO₃+Na₂CO₃The silicic acid is dehydrated and newly precipitated under the action of water on the surface of the inorganic fillerColloidal SiO₂Binding the particles together; because the inorganic fillers are bonded together through chemical bonds, the obtained master batch has high hardness and is not easy to disperse in a plastic matrix, and the attapulgite prepared by the invention is used as a binder and has only dehydration and bonding effects and no chemical bonding effect.

(3) The carrier-free plastic filling master batch obtained in the invention has excellent performance and composite reinforcing and toughening effects on plastics, because the attapulgite is adopted in the invention, the attapulgite is a needle-shaped material with the diameter of 20-70 nm and the length of about 1 micron, the bonded inorganic filler is spherical particles, when the master batch is added into the plastics, when the plastics are subjected to external force, the rigid spherical particles cause the matrix plastics to be silvered and absorb energy, and thus the toughening effect is achieved; the needle-shaped particles are easy to be directionally arranged according to a certain direction in the processing process, so that the strength of the plastic in the directional direction is improved, and other master batches only have one filler and only have a single reinforcing or toughening effect.

(4) The master batch obtained in the invention only uses two materials: the attapulgite clay is not only a binder but also a reinforcing agent, namely all components in the master batch have effects on plastics, the content of the filler reaches 100 percent, and the equipment and the process used in the master batch preparation process are simple, the method is mature, the implementation is convenient, and the popularization is easy.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

The attapulgite and the commercially available colloidal attapulgite in the invention have the wet sieve residue of 200 meshes of less than or equal to 2.5 percent, the dry sieve residue of 100 meshes of less than or equal to 2.0 percent and the water content of less than or equal to 15 percent; other raw materials, which are not specifically described, are all commercially available.