Special extrusion-assisting master batch for pipes and preparation method of special extrusion-assisting master batch

Abstract

The invention relates to the technical field of chemical engineering, in particular to a special extrusion-assisting master batch for pipes and a preparation method thereof. The extrusion-assisted master batch is prepared from the following raw materials in parts by weight: 89.5 to 96.9 parts of polyethylene, 0.1 to 0.5 part of an antioxidant, 2 to 7 parts of a fluorine-containing processing aid and 1 to 3 parts of a dispersing agent, wherein the polyethylene is selected from PE100-grade resin powder. While the processability is improved, the situation that the pressure resistance and the stress cracking resistance of the pipe are reduced due to the addition of the extrusion-assisting master batch is avoided.

Description

Technical field:

[0001] The invention relates to the technical field of chemical engineering, and in particular to a special extrusion-aiding masterbatch for pipes and a preparation method thereof. Background technology:

[0002] During pipe production, due to the poor processing performance of the pipe material, sometimes there will be longitudinal scratches on the pipe surface, poor gloss on the pipe surface and material accumulation at the die mouth, which leads to frequent cleaning of the machine and reduces the production quality and efficiency of the pipe.

[0003] The use of fluoroelastomer processing aids (PPA) is widely used in processes with extrusion. They are used as specific lubricants to reduce production energy consumption, increase output and production efficiency, improve product appearance, reduce apparent viscosity, reduce melt fracture, and eliminate die buildup.

[0004] Since fluorine-containing processing aids are mostly in powder form, when they are directly added to polyethylene materials, problems such as difficulty in good dispersion and dust pollution may occur during the processing process. It is necessary to make the fluorine-containing processing aids into a masterbatch to achieve the requirements of improving utilization efficiency and environmental friendliness. Patent CN109135013A provides a fluorine-containing processing masterbatch for high molecular weight polyethylene film, and patent CN105602092 A provides a PPA masterbatch and its preparation method, but the masterbatch matrix resin is not PE100 grade resin. Excessive addition will have an adverse effect on the pressure resistance and stress cracking resistance of the pipe. Therefore, it is necessary to use PE100 grade resin as the base material to produce a special extrusion aid masterbatch for pipes to meet performance requirements. Summary of the invention:

[0005] The technical problem to be solved by the present invention is to provide a special extrusion-aid masterbatch for pipes and a preparation method thereof, which improves the processing performance while avoiding the reduction of the pressure resistance and stress cracking resistance of the pipe due to the addition of the extrusion-aid masterbatch.

[0006] The technical solution adopted by the present invention is: a special extrusion aid masterbatch for pipes, which is composed of the following raw materials and their weight proportions: polyethylene: 89.5-96.9 parts, antioxidant: 0.1-0.5 parts, fluorine-containing processing aid: 2-7 parts, dispersant: 1-3 parts; wherein the polyethylene is PE100 grade resin powder.

[0007] Furthermore, the polyethylene is high-density polyethylene (HDPE), brand: JHM GC100S, with a melt flow rate of 0.27-0.40 g / 10 min at 190°C / 5 kg and a density of 0.9460-0.9500 g / cm 3 .

[0008] Furthermore, the antioxidant is one or a mixture of a hindered phenol antioxidant and a phosphite antioxidant.

[0009] Furthermore, the antioxidant is one or more of 4,4'-thiobis-(3-methyl 6-tert-butylphenol), tris(2,4-di-tert-butylphenyl) phosphite, β-(4-hydroxyphenyl-3,5-di-tert-butyl) propionate, and pentaerythritol tetrakis{β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0010] Furthermore, the dispersant is polyethylene wax, the softening point is greater than 110°C, W n The molecular weight is 1500-2500.

[0011] Furthermore, the fluorine-containing processing aid is a polymer processing aid based on a fluorine-containing high molecular polymer, such as FX5911 and FX9613 from 3M Company, Viton from Chemours, USA TM One or more of FFGB, PPA5301 of Arkema of France, and DAIKINDA910.

[0012] Furthermore, the special extrusion-aid masterbatch for pipes is applied to the field of molding and processing of PE100 grade polyethylene pipes.

[0013] A method for preparing a special extrusion-aid masterbatch for pipes, the method comprising the following steps:

[0014] Step 1, mixing: pre-mixing polyethylene, antioxidant, dispersant and fluorine-containing processing aid in a high-speed mixer at a low speed for 2 to 3 minutes, and then mixing at a high speed for 3 to 5 minutes;

[0015] Step 2, extrusion: adding the mixture obtained in step 1 into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 210°C to 230°C, and the screw speed is 80r / min to 150r / min;

[0016] Step 3, pelletizing: the product obtained by extrusion in step 2 is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0017] The beneficial effects of the present invention are:

[0018] The polyethylene in the present invention is selected from PE100 grade resin to avoid excessive addition of different base resins causing a decrease in the pressure resistance and stress cracking resistance of the pipe.

[0019] The antioxidant in the present invention is one or a mixture of hindered phenol antioxidants and phosphite antioxidants. The above antioxidant system can play a good protective role in the preparation process of the masterbatch, avoiding resin degradation caused by high temperature during the preparation and use of the masterbatch, and avoiding negative effects on processing aids.

[0020] The dispersant in the present invention is a by-product wax produced during the production of PE100 grade resin, which ensures that the processing aid is evenly dispersed and avoids negative effects on the performance of the pipe.

[0021] The processing aid in the present invention is preferably a fluorocarbon polymer. During the production and mixing process, the fluorocarbon polymer can not only improve the processing performance of the PE100 resin, but also improve the surface gloss of the pipe product.

[0022] The special extrusion-aiding masterbatch for pipes of the present invention can be added during the production of pipes to improve the surface quality of the pipes, improve the surface gloss of the pipes, reduce the die head pressure of the extruder, reduce the melting temperature, reduce the die precipitates, reduce the number of times of cleaning the machine, reduce the power consumption, and effectively improve the production efficiency.

[0023] While improving the processing performance, it avoids the reduction of the pressure resistance and stress cracking resistance of the pipe due to the addition of the extrusion-aiding masterbatch. Specific implementation method:

[0024] The present invention is further described in detail below with reference to specific embodiments.

[0025] The pipe material used for the extrusion of the comparative examples and embodiments of the present invention is high-density polyethylene HDPE (JHM GC100S powder), provided by Jilin Petrochemical Company, with a melt flow rate (190°C / 5kg) of 0.39g / 10min and a density of 0.9480g / cm 3 , mixed with PE100S antioxidant, and extruded into granules in a twin-screw extruder (without adding extrusion aids), the melt flow rate (190℃ / 5kg) is 0.20g / 10min, and the density is 0.950g / cm 3 .

[0026] The polyethylene used in the masterbatch of the embodiment of the present invention is high-density polyethylene HDPE (JHM GC100S powder), which is provided by Jilin Petrochemical Company. The raw material has good processability, a melt flow rate (190°C / 5kg) of 0.27-0.40g / 10min, and a density of 0.9460-0.9500g / cm 3 .

[0027] The antioxidant used in the embodiment of the present invention is antioxidant 1010.

[0028] The dispersant used in the embodiment of the present invention is polyethylene wax, which is provided by Jilin Petrochemical Company and is a byproduct of the device. It is processed and has a softening point greater than 110° C. and a Wn molecular weight of 1500-2500.

[0029] The fluorinated processing aids used in the embodiments of the present invention are purchased from outside, including FX5911 and FX9613 from 3M Company, Viton from Chemours, USA TM FFGB, PPA5301 from Arkema of France, DAIKIN DA910, etc.

[0030] Comparative Example 1

[0031] Without adding the special extrusion aid masterbatch for pipes, the pipe material was directly processed on the German Battenfeld-Cincinnati pipe extruder. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0032] Example 1

[0033] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0034] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0035] Polyethylene: 92.85 parts;

[0036] Antioxidant (1010): 0.15 parts;

[0037] Fluorine-containing processing aid (FX5911): 5 parts;

[0038] Dispersant (polyethylene wax): 2 parts.

[0039] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 2 minutes, then at high speed for 3 minutes, and mix well for later use;

[0040] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 220° C., and the screw speed is 140 r / min;

[0041] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0042] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0043] Example 2

[0044] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0045] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0046] Polyethylene: 91.80 parts;

[0047] Antioxidant (1010): 0.20 parts;

[0048] Fluorine-containing processing aid (FX9613): 5 parts;

[0049] Dispersant (polyethylene wax): 3 parts.

[0050] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 3 minutes, then at high speed for 4 minutes, and mix well for later use;

[0051] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 220° C., and the screw speed is 110 r / min;

[0052] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0053] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0054] Example 3

[0055] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0056] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0057] Polyethylene: 93.2 parts;

[0058] Antioxidant (1010): 0.30 parts;

[0059] Fluorinated processing aids (Viton TM FFGB): 4 copies;

[0060] Dispersant (polyethylene wax): 2.5 parts.

[0061] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 2 minutes, then at high speed for 4 minutes, and mix well for later use;

[0062] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 220° C., and the screw speed is 120 r / min;

[0063] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0064] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0065] Example 4

[0066] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0067] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0068] Polyethylene: 92.25 parts;

[0069] Antioxidant (1010): 0.25 parts;

[0070] Fluorine-containing processing aid (PPA5301): 4.5 parts;

[0071] Dispersant (polyethylene wax): 3 parts.

[0072] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 3 minutes, then at high speed for 3 minutes, and mix well for later use;

[0073] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 220° C., and the screw speed is 130 r / min;

[0074] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0075] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0076] Example 5

[0077] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0078] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0079] Polyethylene: 91.85 parts;

[0080] Antioxidant (1010): 0.15 parts;

[0081] Fluorine-containing processing aid (DAIKIN DA910): 5.5 parts;

[0082] Dispersant (polyethylene wax): 2.5 parts.

[0083] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 3 minutes, then at high speed for 3 minutes, and mix well for later use;

[0084] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 220° C., and the screw speed is 130 r / min;

[0085] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0086] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0087] Example 6

[0088] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0089] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0090] Polyethylene: 89.5 parts;

[0091] Antioxidant (1010): 0.5 parts;

[0092] Fluorine-containing processing aid (FX5911): 7 parts;

[0093] Dispersant (polyethylene wax): 3 parts.

[0094] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 2 minutes, then at high speed for 5 minutes, and mix well for later use;

[0095] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, with the extrusion processing temperature being 230° C. and the screw speed being 150 r / min;

[0096] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0097] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0098] Example 7

[0099] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0100] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0101] Polyethylene: 96.9 parts;

[0102] Antioxidant (1010): 0.1 part;

[0103] Fluorine-containing processing aid (FX9613): 2 parts;

[0104] Dispersant (polyethylene wax): 1 part.

[0105] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 2 minutes, then at high speed for 3 minutes, and mix well for later use;

[0106] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 210° C., and the screw speed is 80 r / min;

[0107] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0108] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0109] Example 8

[0110] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0111] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0112] Polyethylene: 94.6 parts;

[0113] Antioxidant (1010): 0.40 parts;

[0114] Fluorinated processing aids (Viton TM FFGB): 3.5 copies;

[0115] Dispersant (polyethylene wax): 1.5 parts.

[0116] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 3 minutes, then at high speed for 4 minutes, and mix well for later use;

[0117] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 215° C., and the screw speed is 100 r / min;

[0118] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0119] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0120] Example 9

[0121] The method for preparing a special extrusion-aid masterbatch for pipes in this embodiment comprises the following steps:

[0122] 1) Ingredients: The raw material composition and weight proportion of the special extrusion-aid masterbatch for pipes in this embodiment are as follows:

[0123] Polyethylene: 95.45 parts;

[0124] Antioxidant (1010): 0.35 parts;

[0125] Fluorine-containing processing aid (PPA5301): 3.0 parts;

[0126] Dispersant (polyethylene wax): 1.2 parts.

[0127] 2) Mixing: pre-mix PE100 powder, antioxidant, polyethylene wax and fluorine-containing processing aid in a high-speed mixer at low speed for 2 minutes, then at high speed for 5 minutes, and mix well for later use;

[0128] 3) Extrusion: Add the mixture obtained in step 2) into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 210° C., and the screw speed is 90 r / min;

[0129] 4) Pelletizing: The product obtained by extrusion in step 3) is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

[0130] The obtained special extrusion aid masterbatch for pipes was mixed with pipe materials at a rate of 0.5%, and the pipes were processed on a pipe extruder of Battenfeld-Cincinnati, Germany. The processing temperature of the barrel and the die were set at 210°C. The specification of the processed pipe was DN32mm / SDR11. The short-term hydrostatic strength test standard was based on the national standard GB / T 6111. The specific process performance results are shown in Table 1.

[0131] Table 1 Specific process performance results

[0132]

[0133]

[0134] As shown in Table 1, the extrusion-aid masterbatch prepared by the present invention has the advantages of improving the surface quality and gloss of the pipe and reducing the longitudinal scratches of the product, and can prevent the die from being easily accumulated. While improving the processing performance, it avoids the decrease of the pressure resistance and stress cracking resistance of the pipe due to the addition of the extrusion-aid masterbatch.

[0135] It can be understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A special extrusion-aiding masterbatch for pipes, characterized in that: The extrusion-aiding masterbatch is composed of the following raw materials and their weight proportions: polyethylene: 89.5-96.9 parts, antioxidant: 0.1-0.5 parts, fluorine-containing processing aid: 2-7 parts, dispersant: 1-3 parts; wherein the polyethylene is PE100 grade resin powder.

2. The extrusion-aiding masterbatch for pipes according to claim 1, characterized in that: The polyethylene is high-density polyethylene (HDPE), brand: JHM GC100S, with a melt flow rate of 0.27-0.40 g / 10 min at 190°C / 5 kg and a density of 0.9460-0.9500 g / cm 3 .

3. The extrusion-aiding masterbatch for pipes according to claim 1, characterized in that: The antioxidant is one or a mixture of a hindered phenol antioxidant and a phosphite antioxidant.

4. The extrusion-aiding masterbatch for pipes according to claim 1, characterized in that: The antioxidant is one or more of 4,4'-thiobis-(3-methyl 6-tert-butylphenol), tris(2,4-di-tert-butylphenyl)phosphite, β-(4-hydroxyphenyl-3,5-di-tert-butyl)propionic acid n-octadecyl alcohol ester and tetrakis{β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid}pentaerythritol ester.

5. The extrusion-aiding masterbatch for pipes according to claim 1, characterized in that: The dispersant is polyethylene wax, the softening point is greater than 110°C, W n The molecular weight is 1500-2500.

6. The extrusion-aiding masterbatch for pipes according to claim 1, characterized in that: The fluorine-containing processing aid is a polymer processing aid based on a fluorine-containing high molecular polymer, such as FX5911 and FX9613 from 3M, Viton from Chemours, USA, TM One or more of FFGB, PPA5301 of Arkema of France, and DAIKIN DA910.

7. The extrusion-aiding masterbatch for pipes according to claims 1-6, characterized in that: Applied in the forming and processing of PE100 grade polyethylene pipes.

8. A method for preparing a special extrusion-assisted masterbatch for pipes according to claims 1-6, characterized in that: The method comprises the following steps: Step 1, mixing: pre-mixing polyethylene, antioxidant, dispersant and fluorine-containing processing aid in a high-speed mixer at a low speed for 2 to 3 minutes, and then mixing at a high speed for 3 to 5 minutes; Step 2, extrusion: adding the mixture obtained in step 1 into a twin-screw extruder for mixing and extrusion, the extrusion processing temperature is 210°C to 230°C, and the screw speed is 80r / min to 150r / min; Step 3, pelletizing: the product obtained by extrusion in step 2 is cooled and pelletized to obtain the extrusion-aid masterbatch for pipes.

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