KR20240099660A - Compounding method of super-engineering plastic resin and Super-engineering plastic manufactured by the same - Google Patents

Abstract

The present invention relates to a method of compounding a polymer resin, and more broadly, to a method of compounding a super engineering plastic resin containing a high content of an inorganic filler, and to a super engineering plastic manufactured by this method.

Description

Compounding method of super-engineering plastic resin and Super-engineering plastic manufactured by the same}

The present invention relates to a method for efficiently compounding a super engineering plastic resin containing a high content of inorganic filler and to super engineering plastic manufactured by this method.

Compared to industrial plastics, the demand for super engineering plastics, which are superior in strength, elasticity, and heat resistance, and have properties close to those of metals or ceramics, is increasing. These super engineering plastics are lightweight, have excellent mechanical properties, and are widely used in various fields. It is used as a material, and various fillers are applied to improve the physical properties required for specific applications. For example, molded products made from resin using reinforced fibers are lightweight and have excellent mechanical properties, so they are used for sporting goods and aerospace applications. It is widely used for general industrial purposes, etc.

In this way, super engineering plastic is a material with excellent heat resistance and a very high glass transition temperature and melting temperature. In order to increase strength and heat resistance and provide special physical properties, various fillers are compounded using an extruder. During pounding, the processing temperature range of super engineering plastic resin is very high, and since it is a crystalline material, when filler is supplied in large quantities in a short period of time, rapid cooling of the super engineering plastic resin occurs internally, increasing the torque of the extruder and There was a problem that equipment was strained and the impregnation and mixing properties between the melted super engineering plastic resin and the filler were greatly reduced due to rapid cooling.

In the case of PEKK (poly ether ketone ketone), which has a high melting temperature (Tm) and a processing temperature that is only slightly higher than the melting temperature, especially during compounding processing in winter or cold weather, fiber ( When fiber is supplied and compounded, the temperature (energy) inside the extruder is lowered (lost) due to the supply of fiber that has already cooled to ambient temperature, which lowers fiber impregnation and increases extruder torque and resin pressure. , this causes the fibers to undergo resistance and become single yarns, shortening the fiber length of the final compounded product, which causes a problem in that mechanical properties are reduced.

Korean Patent No. 10-1969613 (announcement date 2019.04.16) Korean Patent Publication No. 10-2019-0094827 (publication date 2019.08.14)

The present invention provides a compounding method that can produce super engineering plastic containing a high content of inorganic filler by impregnating super engineering resin and inorganic filler using a twin screw extruder and preventing rapid cooling of the super engineering resin that occurs during kneading. We would like to provide

The present invention to solve the above-mentioned problems is a method of compounding a super engineering plastic resin, in the production of fiber-reinforced polyaryl ether ketone (PAEK, poly aryl ether ketone) plastic using a twin screw extruder, The twin screw extruder is equipped with a side feeder equipped with a preheater, and the preheater consists of an electric heater or a heating medium oil device formed surrounding the outside of the barrel of the side feeder. Molten PAEK plastic resin is supplied to the resin supply part of the screw extruder, and inorganic filler is supplied to the side feeder to produce fiber-reinforced PAEK plastic resin in which the molten PAEK plastic resin and inorganic filler are mixed.

As a preferred embodiment of the present invention, the PAEK plastic resin may include one or more selected from poly ether ether ketone (PEEK) resin, poly ether ketone ketone (PEKK) resin, and poly ether ketone (PEK) resin.

In a preferred embodiment of the present invention, the inorganic filler is one or more inorganic fiber-based fillers selected from glass chopped fiber (GCF), carbon chopped fiber (CCF), and aramid fiber; and talc; It may include one or more types selected from among.

As a preferred embodiment of the present invention, the inorganic fiber-based filler includes an epoxy resin emulsion, a polyurethane film former, an epoxy silane coupling agent, and an aminosilane couple. It may be coated with a sizing agent containing one or more selected from aminosilane coupling agent, non-ionic lubricant, acetic acid, boric acid, and water. there is.

As a preferred embodiment of the present invention, the fiber-reinforced PAEK plastic resin may include 5 to 60% by weight of the inorganic filler and the remaining amount of the PAEK plastic resin.

In a preferred embodiment of the present invention, the temperature of the inorganic filler supplied from the side feeder to the twin screw extruder may be 50 to 200°C.

As a preferred embodiment of the present invention, the temperature of the inorganic filler supplied from the side feeder to the twin screw extruder and the temperature of the molten PAEK plastic resin may satisfy Equation 1 below.

[Equation 1]

210℃ ≤ A-B ≤ 280℃

In Equation 1, A is the temperature of the molten PAEK plastic resin (°C), and B is the temperature of the inorganic filler supplied to the twin screw extruder (°C).

As a preferred embodiment of the present invention, the temperature of the molten PAEK plastic resin supplied to the feeder of the twin screw extruder may be 350 to 400°C.

Another object of the present invention is to provide a super engineering plastic containing the super engineering plastic resin manufactured by the compounding method described above.

As a preferred embodiment of the present invention, the super engineering plastic may be in the form of pellets and/or chips.

The compounding method of the super engineering plastic resin of the present invention is not affected by seasonal and ambient temperature changes, prevents strain on equipment such as twin screw extruders that may occur during the compounding process, and contains a high content of inorganic filler. We can provide high quality super engineering plastics.

Figure 1 shows a schematic diagram of a twin screw extruder used to manufacture the fiber-reinforced PAEK resin and super engineering plastic of the present invention.
Figure 2 shows TAG measurement data of GCF (glass chopped filler), an inorganic filler used in Example 1.
Figure 3 shows TAG measurement data of CCF (carbon chopped filler), an inorganic filler used in Example 2.

Hereinafter, in the compounding method of the super engineering plastic resin of the present invention, as schematically shown in FIG. 1, compounding is performed using a twin screw extruder equipped with a side feeder through which inorganic filler is supplied. Existing twin screw extruders have a high processing temperature, and during compression and compounding processing of super engineering plastic resins where the difference between the melt temperature and processing temperature is not large, if excessive amounts of inorganic additives are fed through the side feeder, the molten resin Rapid cooling may cause deterioration in processability, mechanical strength, and quality. In contrast, the twin screw compressor of the present invention can prevent these problems by using a twin screw extruder equipped with a side feeder capable of heating.

That is, the super engineering plastic resin compounding method of the present invention is a method of manufacturing fiber-reinforced poly aryl ether ketone (PAEK) plastic using a twin screw extruder, wherein the twin screw extruder is a preheater. A side feeder equipped with is provided.

In addition, the preheater is composed of an electric heater or a heating medium oil device formed surrounding the outside of the barrel of the side feeder.

When the molten PAEK plastic resin is supplied to the resin supply part of the twin screw extruder, the molten PAEK plastic resin is moved in the direction of the side feeder by the screw, and an inorganic filler is supplied from the side feeder to impregnate the molten PAEK plastic resin. and kneading to produce fiber-reinforced PAEK plastic resin, and then extruding it into strands and pelletizing it to produce super engineering plastic.

The PAEK plastic resin serving as the resin supply unit may include at least one selected from poly ether ether ketone (PEEK) resin, poly ether ketone ketone (PEKK) resin, and poly ether ketone (PEK) resin.

Additionally, the temperature of the molten PAEK plastic resin supplied to the supply unit of the twin screw extruder may be 300°C or higher, preferably 350 to 400°C.

The inorganic filler may include at least one inorganic fiber-based filler selected from glass chopped fiber (GCF), carbon chopped fiber (CCF), and aramid fiber; and talc; It may contain one or more types selected from among, and preferably may contain an inorganic fiber-based filler.

In addition, the inorganic fiber-based filler includes an epoxy resin emulsion, a polyurethane film former, an epoxy silane coupling agent, an aminosilane coupling agent, It may be coated with a non-ionic lubricant, acetic acid, boric acid, and water.

The temperature of the inorganic filler may be 50 to 250°C, preferably 100 to 200°C, and more preferably 120 to 150°C.

The barrel of the side feeder is preheated by a preheater, and the barrel of the side feeder can be preheated so that the temperature of the inorganic filler supplied from the side feeder to the twin screw extruder satisfies Equation 1 below.

[Equation 1]

210°C ≤ A-B ≤ 280°C, preferably 230°C ≤ A-B ≤ 280°C

In Equation 1, A is the temperature of the molten PAEK plastic resin (°C), and B is the temperature of the inorganic filler supplied to the twin screw extruder (°C). At this time, if the temperature value of A-B is less than 210℃, there may be a problem of sizing agent being lost from the inorganic filler due to thermal decomposition of the sizing agent treated with the inorganic filler, and if the temperature value of A-B exceeds 280℃, the PAEK plastic resin and the inorganic filler may be damaged. The temperature difference between the fillers is too large, and low-temperature fiber bundles are supplied through the side feeder, which cools the PAKK plastic resin inside the extruder cylinder. As a result, the impregnation between fiberized resins is lowered, which reduces the mechanical strength of the composite material. There may be.

In addition, the preferred temperature that satisfies Equation 1 of the molten PAEK plastic resin supplied to the feed section of the twin screw extruder may be 350 to 400°C.

As described above, the inorganic filler supplied to the twin screw extruder can be impregnated and kneaded into the molten PAEK plastic resin to produce fiber-reinforced PAEK plastic resin.

Then, the fiber-reinforced PAEK plastic resin is extruded into strands by an extruder, and then a specific type of fiber-reinforced PAEK plastic, that is, super engineering plastic, is manufactured.

The specific form may be in the form of a pellet, chip, granule, or powder, and is preferably pelletized to produce fiber-reinforced PAEK plastic in the form of a pellet.

The fiber-reinforced PAEK plastic resin may include 5 to 60% by weight of the inorganic filler and the remaining amount of the PAEK plastic resin, and preferably includes 10 to 40% by weight of the inorganic filler and the remaining amount of the PAEK plastic resin. can do.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.

[Example]

Example 1: Preparation of fiber-reinforced PAEK plastic (super engineering plastic)

Fiber-reinforced PEKK plastic was manufactured under the following conditions using a twin-screw extruder equipped with a side feeder (screw diameter 25 mm, L/D = 44), and a photo of the twin-screw extruder is shown in Figure 1A. An electric ceramic heater is provided surrounding the outside of the barrel of the side feeder.

After manufacturing powder by polymerizing PEKK resin with a T/I ratio of 80/20, the cylinder temperature of the twin-screw extruder is sequentially raised to 330~390℃ from the hopper to the die to prepare for extrusion, and then the twin-screw extruder is used to prepare powder. It was put into the resin supply part of the extruder, and the screw rotation speed of the extruder was set to 300 rpm. Resin was supplied in a fixed quantity using a loss in weight feeder at a rate of 7 kg/hr, and GCF (sizing agent) sized with an epoxy silane coupling agent (sizing agent) was supplied through a side feeder preheated to 150°C. Glass fiber chopped, Jushi's product name ECS13-03) was supplied. The TGA analysis data of the GCF is shown in Figure 2, and the barrel of the side feeder was heat treated by a preheater to maintain 150°C, and the temperature of the GCF supplied to the twin screw extruder through the connection feeder was preheated to 120°C.

In addition, the amount of PAEK plastic resin supplied to the resin supply part and the amount of inorganic filler supplied to the side feeder are supplied at 3 kg/hr, and an impregnation and kneading process is performed to produce 30% by weight of sized GCF, which is an inorganic filler, and the remaining amount. A fiber-reinforced PAEK plastic resin containing PEKK plastic resin was manufactured, and then extruded into strands, which were then pelletized to produce super engineering plastic.

Example 2

Fiber-reinforced PAEK plastic resin was manufactured using the same method and conditions as in Example 1, and then extruded to form strands and then pelletized to produce super engineering plastic, but instead of the GCF, a polyurethane film former was used. Fiber-reinforced PAEK plastic resin and super engineering plastic were manufactured using CCF (carbon chopped fiber, product name: Aceca 6PU) sized using former). And, the TGA analysis data of the CCF is shown in Figure 3.

Comparative Example 1

GCF sized in the same manner as in Example 1 is supplied to a side feeder to manufacture a palletized super engineering plastic containing fiber-reinforced PAEK plastic resin containing 30% by weight of GCF and the remaining amount of PEKK plastic resin, Super engineering plastic was manufactured by supplying sized GCF without heat treatment through the side feeder.

Comparative Example 2

CCF sized in the same manner as in Example 2 is supplied to a side feeder to manufacture a palletized super engineering plastic containing fiber-reinforced PAEK plastic resin containing 30% by weight of CCF and the remaining amount of PEKK plastic resin, Super engineering plastic was manufactured by supplying sized CCF to the side feeder without heat treatment.

Experimental Example 1: Measurement of physical properties of super engineering plastic

The tensile strength, flexural strength, and notched impact strength of the super engineering plastics manufactured in Examples 1 to 2 and Comparative Examples 1 to 2 were measured, and the results are shown in Table 1 below. shown in

At this time, tensile strength was measured according to ISO 527, bending strength according to ISO 178, and impact strength according to ISO 179.

division Side feeder heat treatment/
Inorganic filler content tensile strength
(Mpa) bending strength
(Mpa) impact strength
(kJ/㎡) Comparative Example 1 No heating / GCF 30% by weight 197 283 3.4 Example 1 Preheat treatment at 150℃ /GCF 30% by weight 210 290 4.5 Comparative Example 2 No heating /CCF 30% by weight 265 371 4.2 Example 2 Preheat treatment at 150℃ /CCF 30% by weight 280 380 5.0

Looking at the physical property measurement results of the super engineering plastics manufactured in the Examples and Comparative Examples in Table 1, Examples 1 and 2, which are super engineering plastics manufactured by heat treatment when supplying inorganic filler through a side feeder, are Comparative Examples. When compared with each of Comparative Example 1 and Comparative Example 2, it was confirmed that there was an increase in the overall excellent physical properties in tensile strength, bending strength, and impact strength.

Examples 3 to 4 and Comparative Examples 3 to 4

Super engineering plastics were manufactured in the same manner as in Example 1, but the preheating temperature of the side feeder was changed and the supplied inorganic filler was supplied at different temperatures as shown in Table 2 below. At this time, the temperature of the PEKK resin when mixed with the inorganic filler in the twin screw extruder was about 375°C.

Experimental Example 2: Measurement of physical properties of super engineering plastic

The physical properties of the super engineering plastics prepared in Examples 3 to 4 and Comparative Examples 3 to 4 were measured in the same manner as Experiment 1, and the results are shown in Table 2 below.

division Inorganic filler temperature/
Inorganic filler content PEKK
resin temperature tensile strength
(Mpa) bending strength
(Mpa) impact strength
(kJ/㎡) Example 1 120℃ /
GCF 30% by weight 380℃ 210 290 4.5 Example 3 100℃/
GCF 30% by weight 207 280 4.2 Example 4 160℃/GCF 30% by weight 213 284 4.3 Comparative Example 3 70℃/GCF 30% by weight 199 284 3.5 Comparative Example 4 210℃/
GCF 30% by weight 173 238 3.0

Looking at the physical property measurement results in Table 2, Example 3 had relatively superior tensile strength and impact strength compared to Comparative Example 3, and Example 4 had overall physical property measurement results compared to Comparative Example 4. showed high results.

In the case of Comparative Example 3, where the temperature difference with the PEKK resin exceeded 280°C, low-temperature fiber bundles were supplied through the side feeder to cool the PEKK molten resin inside the extruder cylinder, lowering the impregnation between fiberized resins and improving the mechanical properties of the composite material. It is believed that this resulted in lowering the intensity. In addition, in the case of Comparative Example 4, where the temperature difference with the PEKK resin was less than 200°C, the sizing agent component treated with the inorganic filler was thermally decomposed, causing loss of the inorganic filler, GCF, on the surface, and as a result, the physical properties of the manufactured PEKK composite material were damaged. It is believed to have decreased.

Claims (7)

In the production of fiber-reinforced polyaryl ether ketone (PAEK) plastic using a twin screw extruder,
The twin screw extruder is equipped with a side feeder equipped with a preheater,
The preheater consists of an electric heater or a heating medium oil device formed surrounding the outside of the barrel of the side feeder,
Molten PAEK plastic resin is supplied to the resin supply part of the twin screw extruder.
A compounding method of super engineering plastic resin, characterized in that the fiber-reinforced PAEK plastic resin is manufactured by supplying an inorganic filler to the side feeder and mixing the molten PAEK plastic resin and the inorganic filler.
The method of claim 1, wherein the PAEK plastic resin includes at least one selected from poly ether ether ketone (PEEK) resin, poly ether ketone ketone (PEKK) resin, and poly ether ketone (PEK) resin,
The inorganic filler may include at least one inorganic fiber-based filler selected from glass chopped fiber (GCF), carbon chopped fiber (CCF), and aramid fiber; and talc; A method of compounding a super engineering plastic resin comprising one or more selected from among.
The method of claim 2, wherein the inorganic fiber-based filler is:
Epoxy resin emulsion, polyurethane film former, epoxy silane coupling agent, aminosilane coupling agent, non-ionic lubricant. , A method of compounding a super engineering plastic resin, characterized in that it is coated with a sizing agent containing at least one selected from acetic acid, boric acid, and water.
The method of claim 1, wherein the fiber reinforced PAEK plastic resin,
A method of compounding a super engineering plastic resin, comprising 5 to 60% by weight of the inorganic filler and the remaining amount of the PAEK plastic resin.
The method of compounding super engineering plastic resin according to claim 1, wherein the temperature of the inorganic filler supplied from the side feeder to the twin screw extruder is 50 to 200°C.
The compounding method of super engineering plastic resin according to claim 5, wherein the temperature of the inorganic filler supplied from the side feeder to the twin screw extruder and the temperature of the molten PAEK plastic resin satisfy the following Equation 1.
[Equation 1]
210℃ ≤ AB ≤ 280℃
In Equation 1, A is the temperature of the molten PAEK plastic resin (°C), and B is the temperature of the inorganic filler supplied to the twin screw extruder (°C).
A super engineering plastic comprising a super engineering plastic resin manufactured by the compounding method of any one of claims 1 to 6.