CN106397907A - Modified regenerated polyethylene corrugated pipe material and preparation method thereof - Google Patents

Abstract

The invention discloses a modified regenerated polyethylene corrugated pipe material. The corrugated pipe material comprises the following components in parts by weight: 70-80 parts of a regenerated polyethylene feed pipe material, 10-20 parts of regenerated polyethylene functional master batch, and 15-25 parts of a regenerated polyethylene large hollow container material; wherein the regenerated polyethylene functional master batch comprises the following components in parts by weight: 60-70 parts of a regenerated polyethylene mulch film, 20-30 parts of a regenerated anti-fogging shed film, and 10-30 parts of regenerated polyethylene bottle caps; 3-4 parts of a carbon black master batch, 0.3-0.5 part of an anti-oxidant, and 0.2-0.6 parts of an antifoaming agent. The modified regenerated polyethylene corrugated pipe material totally employs waste and old plastic as a main raw material, so that production cost is reduced, physical properties are excellent, flexural modulus is higher than or equal to 1167MPa, fracture elongation is higher than or equal to 604%, impact strength reaches 39KJ/m<2>, and high rigidity can satisfy high external pressure-bearing requirements; at the same time, high impact strength guarantees flexibility of the material, fracture of the pipe material due to falling off during loading and unloading is avoided, the preparation method of the material is simple and effective, and operationality is high.

Description

A kind of modified regenerated polyethylene bellows material and preparation method thereof

technical field

The invention relates to the technical field of polymer materials, in particular to a modified recycled polyethylene corrugated pipe material and a preparation method thereof.

Background technique

Double-wall corrugated pipe has the advantages of light weight, high strength, and convenient construction. It is widely used in the fields of communication optical cable sheath, building drainage, municipal drainage, low-pressure irrigation of farmland, etc.

Large-diameter drainage and sewage pipes are external pressure-bearing pipes, which require the material to have good rigidity to meet the requirements of bearing external forces. At the same time, in order to meet the needs of transportation and construction, the material is required to have good flexibility. At present, in China, the rigidity of the material is mainly increased by adding modified masterbatches such as talcum powder or calcium carbonate masterbatch, and the production cost is reduced. Embrittlement occurs under the impact of external force, resulting in high damage rate of pipes, unstable use, water leakage and other problems. At the same time, since the double-wall corrugated pipe does not need to meet the 50-year service life requirements of the inner pressure-bearing pipe, many domestic products are currently produced using recycled polyethylene, and the performance of pipe products such as environmental stress cracking resistance, rigidity and toughness balance is poor, often Pipe ruptures contaminate the soil.

Chinese patent CN201210472524 discloses a double-wall corrugated pipe made of LLDPE modified waste HDPE recycled plastic and its method. The double-wall corrugated pipe is composed of an inner layer and an outer layer. The specific steps are as follows: firstly, the waste HDPE plastic is pre-treated and Granulate, and then mix LLDPE resin, HDPE recycled plastic granules, enhanced function masterbatch, carbon black masterbatch and defoamer in proportion, and then process it through extrusion to make double-wall bellows. However, the composition and preparation method of this invention are relatively complicated, and the cost is relatively high. The reinforcing masterbatch used is mainly inorganic substances such as talcum powder or calcium carbonate.

Contents of the invention

An object of the present invention is to provide a modified recycled polyethylene corrugated pipe material with good pressure resistance, excellent impact resistance and low material cost to solve the deficiencies of the prior art.

Another object of the present invention is to provide a method for preparing the above-mentioned modified recycled polyethylene corrugated pipe material.

The present invention realizes the object of the invention through the following technical solutions:

A modified recycled polyethylene corrugated pipe material, comprising the following components by weight: 70-80 parts of recycled polyethylene water supply pipe material, 10-20 parts of recycled polyethylene functional masterbatch and 15-15 parts of recycled polyethylene large hollow container material 25 parts; the density of the regenerated polyethylene PE80 grade polyethylene water supply pipe material is 0.953-0.956g/cm ³ , the melt mass flow rate (5kg) is 0.5-0.6g/10min; the material density of the regenerated polyethylene large hollow container is 0.950-0.957 g/cm ³ , melt mass flow rate (21.6kg) 2.0-2.5g/10min.

Further, the regenerated polyethylene functional masterbatch is made of the following components by weight: 60-70 parts of regenerated polyethylene mulch film; 20-30 parts of regenerated anti-fog drop shed film; 10-30 parts of regenerated polyethylene bottle cap ; 3-4 parts of carbon black masterbatch; 0.3-0.5 parts of antioxidant; 0.2-0.6 parts of defoamer.

Further, the density of the regenerated polyethylene film is 0.917-0.925g/cm ³ , the melt mass flow rate (2.16kg) is 2.3-2.6g/10min, and the ash content is <2%; the regenerated anti-fog shed Film, the main component is EVA, with a relative content of 75%-85%; LLDPE, with a relative content of 15-25%, and an ash content <2%; the regenerated polyethylene bottle cap, with a density of 0.950-0.960g/cm ³ , melt The mass flow rate (2.16kg) is 3-4g/10min, and the ash content is <2%.

Further, the antioxidant is a compound of hindered phenolic antioxidant and phosphite antioxidant, the weight ratio of the two is 1:1; the hindered phenolic antioxidant is four [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester or β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate; Phosphate antioxidants are tris(2,4-di-tert-butylphenyl)phosphite or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

Further, the defoamer is calcium oxide, which can effectively eliminate moisture and gas in recycled plastics, and improve the stability and elongation of the composition.

Further, the carbon black concentration is 45-50%.

Further, the recycled polyethylene water supply pipe material is PE80 grade or PE100 grade.

A preparation method for the above-mentioned modified recycled polyethylene corrugated pipe material, comprising the following steps:

(1) Recycled plastic pretreatment

Weigh the recycled polyethylene mulch film, the recycled anti-fog drop shed film and the recycled polyethylene bottle cap in proportion, and add the three kinds of recycled plastics to the high-speed mixer after cleaning, separating, drying and crushing;

(2) Raw material mixing

Add the carbon black masterbatch, antioxidant and defoamer in proportion to the mixture in step (1) for stirring and mixing. The mixing conditions are: the stirring speed is 2000-2500 rpm, the stirring time is 6-10min, and the stirring temperature 50-60°C;

(3) Masterbatch granulation

The homogeneously mixed material in step (2) is added to a twin-screw extruder for melting, plasticizing, extruding and granulating;

(4) Preparation of modified special materials

20-30 parts of functional masterbatch are added to the recycled polyethylene corrugated pipe material, and the modified recycled polyethylene corrugated pipe material is obtained after mixing by a high-speed mixer.

Further, in the step (2), the antioxidant is dissolved in methanol or ethanol at 60°C before mixing; in the step (3), the screw aspect ratio of the twin-screw extruder is 30-33; There are 0-3 sections of shear blocks, including 0-1 section of reverse shear blocks; the granulation temperature is 175-190°C; the stirring speed in the step (4) is 1500-2000 rpm, and the stirring time is 3 -5min, the stirring temperature is 30-40°C.

Further, in the step (3), the screw aspect ratio of the twin-screw extruder is 30, there is one shear block in the screw combination, and the granulation temperature is 190°C.

The advantage of the modified regenerated polyethylene corrugated pipe material of the present invention is that the blended material of regenerated polyethylene corrugated pipe material and functional masterbatch is used as the main raw material, and all waste plastics are used as the main raw material, which reduces the production cost and has remarkable economic benefits , but still has high elongation at break, impact strength and flexural modulus, flexural modulus ≥ 1167MPa, elongation at break ≥ 604%, impact strength up to 39KJ/m ² , the flexural modulus of bellows material is high It has high rigidity to meet the high external pressure requirements, and the high impact strength ensures the flexibility of the material, which can prevent the pipe from breaking due to falling during loading and unloading.

detailed description

Below in conjunction with embodiment the present invention is described in further detail.

Example 1

Modified recycled polyethylene corrugated pipe material, including the following components by weight: 75 parts of recycled PE80 grade polyethylene water supply pipe material, 15 parts of recycled polyethylene functional masterbatch, 15 parts of recycled polyethylene large hollow container material; Polyethylene functional masterbatch is made of the following components by weight: 68 parts of recycled polyethylene mulch film, 23 parts of recycled anti-fog drop shed film, 14 parts of recycled polyethylene bottle cap, 3.5 parts of carbon black masterbatch, 0.4 parts of antioxidant part and 0.4 part of calcium oxide, the carbon black masterbatch concentration is 48%, and each 0.2 part of antioxidant 1076 and 168.

The material density of recycled PE80 grade polyethylene water supply pipe is 0.955g/cm ³ , and the melt mass flow rate (5kg) is 0.55g/10min; the material density of recycled polyethylene large hollow container is 0.954g/cm ³ , and the melt mass flow rate (21.6kg ) 2.3g/10min; the density of recycled polyethylene film is 0.924g/cm ³ , the melt mass flow rate (2.16kg) is 2.4g/10min, and the ash content is 1.1%; the relative content of EVA in the recycled anti-fog drop shed film is 80%, LLDPE The relative content is 20%, the ash content is 1.2%; the recycled polyethylene bottle cap has a density of 0.951g/cm ³ , a melt mass flow rate (2.16kg) of 3.9g/10min, and an ash content of 1.4%.

The preparation method is as follows:

(1) Recycled plastic pretreatment

Weigh the regenerated polyethylene mulch film, the regenerated anti-fog shed film and the regenerated polyethylene bottle cap respectively according to the above-mentioned parts by weight, and add the three kinds of regenerated plastics into a high-speed mixer after being cleaned, separated, dried and pulverized;

(2) Raw material mixing

After the antioxidant is dissolved in methanol or ethanol at 60°C, the carbon black masterbatch, antioxidant and calcium oxide are added in proportion to the mixture in step (1) and stirred evenly. The stirring speed is 2400 rpm, and the stirring time is 8min, the stirring temperature is 52°C;

(3) Masterbatch granulation

Add the homogeneously mixed materials in step (2) to a twin-screw extruder for melting, plasticizing, extruding and granulating. block, the highest temperature for granulation is 190°C.

(4) Preparation of modified special materials

Add the regenerated polyethylene functional masterbatch in the above parts by weight to the regenerated polyethylene corrugated pipe material, mix it with a high-speed mixer, and stir at 32°C at a speed of 1500 rpm for 3 minutes to obtain a modified regenerated polyethylene corrugated pipe pipe material.

Example 2

Modified recycled polyethylene corrugated pipe material, including the following components by weight: 72 parts of recycled PE100 grade polyethylene water supply pipe material, 13 parts of recycled polyethylene functional masterbatch, 23 parts of recycled polyethylene large hollow container material; Polyethylene functional masterbatch is made of the following components by weight, 66 parts of recycled polyethylene mulch film, 27 parts of recycled anti-fog drop shed film, 23 parts of recycled polyethylene bottle cap, 3.5 parts of carbon black masterbatch, 0.5 parts of antioxidant part and 0.4 part of calcium oxide, the carbon black masterbatch concentration is 48%, each 0.25 part of antioxidant 1076 and antioxidant 168.

The material density of recycled PE100 grade polyethylene water supply pipe is 0.958g/cm ³ , and the melt mass flow rate (5kg) is 0.30g/10min; the material density of recycled polyethylene large hollow container is 0.953g/cm ³ , and the melt mass flow rate (21.6kg ) 2.1g/10min; the density of recycled polyethylene film is 0.924g/cm ³ , the melt mass flow rate (2.16kg) is 2.4g/10min, and the ash content is 1.1%; the relative content of EVA in the recycled anti-fog drop shed film is 85%, LLDPE The relative content is 15%, the ash content is 1.2%; the recycled polyethylene bottle cap has a density of 0.951g/cm ³ , a melt mass flow rate (2.16kg) of 3.9g/10min, and an ash content of 1.4%.

The preparation method is as follows:

(1) Recycled plastic pretreatment

Weigh the regenerated polyethylene mulch film, the regenerated anti-fog shed film and the regenerated polyethylene bottle cap respectively according to the above-mentioned parts by weight, and add the three kinds of regenerated plastics into a high-speed mixer after being cleaned, separated, dried and pulverized;

(2) Raw material mixing

After the antioxidant is dissolved in methanol or ethanol at 60°C, the carbon black masterbatch, antioxidant and calcium oxide are added to the mixture in step (1) in proportion to stir and mix evenly. The stirring speed is 2500 rpm, and the stirring time is 8min, the stirring temperature is 57°C;

(3) Masterbatch granulation

Add the homogeneously mixed material in step (2) to a twin-screw extruder for melting, plasticizing, extruding and granulating. block, the highest temperature for granulation is 190°C.

(4) Preparation of modified special materials

Add the regenerated polyethylene functional masterbatch in the above parts by weight to the regenerated polyethylene corrugated pipe material, mix it with a high-speed mixer, and stir at 32°C at a speed of 1500 rpm for 3 minutes to obtain a modified regenerated polyethylene corrugated pipe pipe material.

Example 3

Modified recycled polyethylene corrugated pipe material, including the following components by weight: 80 parts of recycled PE80 grade polyethylene water supply pipe material, 19 parts of recycled polyethylene functional masterbatch, 24 parts of recycled polyethylene large hollow container material; Polyethylene functional masterbatch is made of the following components by weight, 69 parts of recycled polyethylene mulch film, 22 parts of recycled anti-fogging shed film, 29 parts of recycled polyethylene bottle cap, 3.5 parts of carbon black masterbatch, 0.5 parts of antioxidant part and 0.4 part of calcium oxide, the carbon black masterbatch concentration is 48%, each 0.25 part of antioxidant 1076 and antioxidant 168.

The material density of recycled PE80 grade polyethylene water supply pipe is 0.953g/cm ³ , and the melt mass flow rate (5kg) is 0.50g/10min; the material density of recycled polyethylene large hollow container is 0.956g/cm ³ , and the melt mass flow rate (21.6kg ) 2.1g/10min; the density of recycled polyethylene film is 0.925g/cm ³ , the melt mass flow rate (2.16kg) is 2.0g/10min, and the ash content is 1.1%; the relative content of EVA in the recycled anti-fog drop shed film is 77%, LLDPE The relative content is 23%, the ash content is 1.2%; the recycled polyethylene bottle cap has a density of 0.955g/cm ³ , a melt mass flow rate (2.16kg) of 3.2g/10min, and an ash content of 1.4%.

Preparation method: each component is added according to the above weight parts, and the conditions such as stirring rotation speed, stirring time and stirring temperature and other process parameters are exactly the same as those in Example 2.

The modified regenerated polyethylene corrugated pipe material that will be made by embodiment 1, embodiment 2 and embodiment 3 will carry out following performance test: Oxidation induction time (OIT) is tested by GB/T 19466.6-2009, adopts aluminum cup; The tensile yield stress and elongation at break are tested according to GB/T1040.2-2006, the sample is pressed, and the tensile speed is 50mm/min; the environmental stress cracking resistance (ESCR) is tested according to GB/T1842-2008, and the thickness of the sample is 2mm ; Flexural modulus is tested according to GB/T 9341-2008; Charpy notched impact strength is tested according to GB/T1043.1-2008, type A notch, 23°C. The test performance results are shown in Table 1:

Table 1 Physical properties of modified recycled polyethylene corrugated pipe materials

performance unit Example 1 Example 2 Example 3 Yield Strength MPa 23.9 24.4 24.7 elongation at break % 604 629 645 Flexural modulus MPa 1167 1227 1241 Impact strength KJ/ ^m2 32 33 35 Oxidation induction time, 200℃ min 33 35 39 ESCR, 100%TX-10, 50℃, F ₀ h 296 283 311

It can be seen from Table 1 that the physical properties of the modified recycled polyethylene drainage pipe material are good, the flexural modulus is ≥1167MPa, the elongation at break is ≥604%, and the impact strength can reach 39KJ/m ² . The drainage pipe requires high rigidity to meet For external pressure requirements, the high flexural modulus of the material indicates its high rigidity; in order to meet the loading and unloading requirements and prevent the pipe from breaking when it falls, the material is required to have high flexibility, that is, impact strength.

What have been described above are only some embodiments of the present invention. For those skilled in the art, without departing from the inventive concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention.

Claims (10)

1. A modified regenerated polyethylene bellows material, characterized in that it comprises the following components by weight: 70-80 parts of regenerated polyethylene water supply pipe material, 10-20 parts of regenerated polyethylene functional masterbatch and regenerated polyethylene 15-25 parts of large hollow container material; the density of the regenerated polyethylene PE80 grade polyethylene water supply pipe material is 0.953-0.956g/cm ³ , and the melt mass flow rate (5kg) is 0.5-0.6g/10min; the regenerated polyethylene large hollow The container material density is 0.950-0.957g/cm ³ , and the melt mass flow rate (21.6kg) is 2.0-2.5g/10min. 2. The modified regenerated polyethylene corrugated pipe material according to claim 1, wherein the regenerated polyethylene functional masterbatch is made of the following components by weight: 60-70 parts of regenerated polyethylene mulch; 20-30 parts of anti-fog shed film; 10-30 parts of recycled polyethylene bottle cap; 3-4 parts of carbon black masterbatch; 0.3-0.5 parts of antioxidant; 0.2-0.6 parts of defoamer. 3. The modified regenerated polyethylene corrugated pipe material according to claim 2, characterized in that the regenerated polyethylene film has a density of 0.917-0.925g/cm ³ and a melt mass flow rate (2.16kg) of 2.3 ～2.6g/10min, ash content<2%; the main component of the regenerated anti-fog drip shed film is EVA, with a relative content of 75%-85%; LLDPE, with a relative content of 15-25%, ash content<2%; The recycled polyethylene bottle cap has a density of 0.950-0.960g/cm ³ , a melt mass flow rate (2.16kg) of 3-4g/10min, and an ash content of <2%. 4. The modified regenerated polyethylene corrugated pipe material according to claim 2, wherein the antioxidant is a compound of hindered phenolic antioxidant and phosphite antioxidant, both The weight ratio is 1:1; the hindered phenolic antioxidant is tetrakis[β-(3,5 di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester or β(3,5 di-tert-butyl Base-4-hydroxyphenyl) octadecyl propionate; the phosphite antioxidant is three (2,4-di-tert-butylphenyl) phosphite or bis(2,4-di-tert Butylphenyl) pentaerythritol diphosphite. 5. The modified regenerated polyethylene corrugated pipe material according to claim 2, wherein the defoamer is calcium oxide. 6. The modified recycled polyethylene corrugated pipe material according to claim 2, characterized in that the carbon black concentration is 45-50%. 7. The modified regenerated polyethylene corrugated pipe material according to claim 1, characterized in that, the regenerated polyethylene water supply pipe material is PE80 grade or PE100 grade. 8. The preparation method of the modified regenerated polyethylene corrugated pipe material according to any one of claims 1 to 7, characterized in that it comprises the following steps: (1) Recycled plastic pretreatment Weigh the recycled polyethylene mulch film, the recycled anti-fog drop shed film and the recycled polyethylene bottle cap in proportion, and add the three kinds of recycled plastics to the high-speed mixer after cleaning, separating, drying and crushing; (2) Raw material mixing Add the carbon black masterbatch, antioxidant and defoamer in proportion to the mixture in step (1) for stirring and mixing. The mixing conditions are: the stirring speed is 2000-2500 rpm, the stirring time is 6-10min, and the stirring temperature 50-60°C; (3) Masterbatch granulation The homogeneously mixed material in step (2) is added to a twin-screw extruder for melting, plasticizing, extruding and granulating; (4) Preparation of modified special materials 20-30 parts of functional masterbatch are added to the recycled polyethylene corrugated pipe material, and the modified recycled polyethylene corrugated pipe material is obtained after mixing by a high-speed mixer. 9. the preparation method of modified regenerated polyethylene bellows material according to claim 8, is characterized in that, In the step (2), the antioxidant is dissolved in methanol or ethanol at 60°C before mixing; In the step (3), the screw length-to-diameter ratio of the twin-screw extruder is 30 to 33; there are 0-3 sections of shear blocks in the screw combination, including 0-1 section of reverse shear blocks; the granulation temperature is 175-190°C; In the step (4), the stirring speed is 1500-2000 rpm, the stirring time is 3-5min, and the stirring temperature is 30-40°C. 10. the preparation method of modified regenerated polyethylene bellows material according to claim 9, is characterized in that, the screw aspect ratio of twin-screw extruder in described step (3) is 30, and there is 1 in screw combination Segment shear block, granulation temperature is 190°C.