CN108503935B - Easy-to-process heat-resistant polyethylene composition and preparation method thereof - Google Patents
Easy-to-process heat-resistant polyethylene composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an easily-processed heat-resistant polyethylene composition and a preparation method thereof. The invention relates to an easy-processing heat-resistant polyethylene composition, which is prepared from the following components in parts by weight: 100 parts of heat-resistant polyethylene resin, 0.2-0.5 part of antioxidant and 0.01-0.03 part of processing aid; the heat-resistant polyethylene resin is a copolymer of ethylene and 1-hexene produced by adopting a gas phase process and a metallocene catalyst, the reaction temperature is 91-93 ℃, and the reaction pressure is 2.0-2.2 MPa. The polyethylene composition has excellent processability, pressure resistance and higher critical shear rate.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an easily-processed heat-resistant polyethylene composition and a preparation method thereof.
Background
A Polyethylene-of-thermoplastic (PE-RT) pipe material is a special Polyethylene material with excellent high temperature resistance and hydrostatic resistance and no need of crosslinking, and is gradually adopted in the plastic pipe industry with high use temperature in recent years, and the product is actively researched and developed at home and abroad. The composite material has the characteristics of excellent stability, good low-temperature impact resistance, hot-melt connection and the like, and is applied to a plurality of fields in China, such as ground heating pipes, solar energy pipes, heating pipe networks and the like. The heat-resistant polyethylene pipe material is mainly applied to the field of floor heating pipes at present, the production speed is high, the pipe material is required to have good processing performance, meanwhile, the energy consumption is required to be low in the processing process so as to reduce the production cost, and finally, the pipe material with smooth inner and outer walls and uniform wall thickness is prepared. At present, the processing performance of PE-RT pipe materials is improved mainly by adding a large amount of processing aids, improving the processing temperature, changing the equipment structure and the like in China, but the processing method has a series of problems of unstable production, reduced product quality, high production cost and the like.
Chinese patent CN102112498A discloses a novel copolymer of ethylene and alpha-olefin having a molecular weight distribution (a) of 930-960kg/m3(ii) a density in the range, (b) a melt index in the range of 0.1 to 3.5G/10min, (c) a melt elastic modulus G' (G "═ 500Pa) in the range of 40 to 150Pa, (d) a ratio η x (0.1)/η (100) of complex dynamic shear viscosity in the range of 1.5 to 5.5.
The novel copolymers of the invention are particularly suitable as heat-resistant polyethylenes, which are used in hot water pipe systems. The novel copolymers can be prepared by using metallocene catalyst systems. Also disclosed are pipes having a time to failure of 500 hours or more, as determined according to ISO1167, at 110 ℃ and 2.6MPa, and comprising a copolymer of ethylene and an alpha-olefin prepared in a single reactor.
The above patents have produced tube materials with narrow molecular weight distribution and low viscosity due to the polymerization process, polyethylene resin, and adjuvant system employed.
Chinese patent CN103160014A discloses a polyethylene resin composition for hot water pipes and a preparation method thereof. The composition is prepared from the following components in parts by weight: 100 parts of heat-resistant polyethylene resin, 0.1-0.6 part of antioxidant, 0.05-0.2 part of acid acceptor and 0.01-0.1 part of processing aid. The antioxidant system composed of the antioxidants is a ternary composite system formed by compounding two hindered phenol antioxidants and a phosphite antioxidant, or a binary composite system formed by compounding a hindered phenol antioxidant and a phosphite antioxidant. The invention is prepared by a general preparation method, has good high-temperature oxidation resistance and water extraction resistance of the auxiliary agent, has excellent long-term hydrostatic strength under the high-temperature condition, can be used for producing pipelines for hot water delivery, and meets the requirement of high-speed processing.
The above patents have adopted polymerization process, polyethylene resin and assistant system, so that the prepared pipe material has narrow molecular weight distribution, low critical shear rate and still needs to be further improved in processing speed.
Disclosure of Invention
The invention aims to provide an easy-to-process heat-resistant polyethylene composition for producing heat-resistant polyethylene pipes, which has wider molecular weight distribution, higher near shear rate and relatively lower molecular weight, and meets the molding requirement of the pipe material under the high-speed traction condition, thereby ensuring that the pipe has smooth appearance and stable size, being beneficial to ensuring the performance and service life of the pipe, improving the production efficiency of products and reducing the production cost; the invention also provides a preparation method thereof.
The invention relates to an easy-processing heat-resistant polyethylene composition, which is prepared from the following components in parts by weight: 100 parts of heat-resistant polyethylene resin, 0.2-0.5 part of antioxidant and 0.01-0.03 part of processing aid;
the heat-resistant polyethylene resin is a copolymer of ethylene and 1-hexene produced by adopting a gas phase process and a metallocene catalyst, the reaction temperature is 91-93 ℃, and the reaction pressure is 2.0-2.2 MPa; the density of the heat-resistant polyethylene resin is 0.934-0.937g/cm3(ii) a MFR2.16 of 0.70-0.80g/10min, melt flow ratio MFR21.6/MFR2.16 of 33-37; the melt elastic modulus G' (G ═ 500Pa) is 110-170 Pa; the ratio of complex dynamic shear viscosity eta (0.1)/eta (100) is 9.0-10.8, and the weight average molecular weight is 10.2 × 104-12.0×104And a molecular weight distribution index Mw/Mn of 3.7 to 4.1.
Wherein:
the density of the heat-resistant polyethylene resin is 0.934-0.936g/cm3(ii) a MFR2.16 of 0.72-0.76g/10min, melt flow ratio MFR21.6/MFR2.16 of 34-36; the melt elastic modulus G' (G ═ 500Pa) is 120-140 Pa; the ratio of complex dynamic shear viscosity eta (0.1)/eta (100) is 9.4-10.3, and the weight average molecular weight is 10.5 × 104-11.5×104Molecular weight distribution meansThe number Mw/Mn is from 3.8 to 4.0. Where MFR2.16 is the melt mass flow rate under a load of 2.16kg and MFR21.6 is the melt mass flow rate under a load of 21.6 kg.
For heat-resistant polyethylene resins, the density determines the strength of the resin, such as hydrostatic strength, tensile strength, flexural modulus, etc., but too high a density reduces the resistance of the material to slow crack growth and flexibility, etc. The density of the polyethylene resin in the invention is 0.934-0.937g/cm3Preferably 0.934-0.936g/cm3The floor heating plate has good flexibility and is convenient for floor heating construction; MFR and melt flow ratio determine the processability of the resin, MFR2.16 of the resin of the invention is 0.70-0.80g/10min, preferably 0.72-0.76g/10min, melt flow ratio 33-37, preferably 34-36, ensuring the processability and combination properties of the pipe material. The polyethylene resin is polymerized by adopting a gas phase process, the catalyst is a metallocene catalyst sold in the market, and 1-hexene is used as a comonomer.
Polyethylene is a pseudoplastic fluid, when subjected to external force, the flow process of the polyethylene comprises two types of deformation, namely irreversible deformation (viscous flow, expressed by loss modulus G ") and reversible deformation (elastic recovery, expressed by storage modulus G '), G ' at a specific G ' can influence the flow property and the processing adaptability of the material by combining the ratio of complex viscosity at different shear rates, and the melt elastic modulus G ' (G ': 500Pa) of the polyethylene is 110-150Pa, preferably 120-140; the ratio of complex dynamic shear viscosity η | (0.1)/η | (100) is 9.0 to 10.8, preferably 9.4 to 10.3.
The molecular weight and the distribution of the molecular weight influence the processability, the long-term service life and the like of the resin, the molecular weight is small, the distribution of the molecular weight is wide, the processability of the resin is facilitated, the energy consumption in the processing process of the resin can be reduced, but the hydrostatic strength, the flexibility and the like of the resin are reduced due to the fact that the molecular weight is too small and the distribution is too wide, the service life of a pipe material is influenced, and the weight average molecular weight of the resin is 10.2 multiplied by 104-12.0×104Preferably 10.5X 104-11.5×104The molecular weight distribution index Mw/Mn is from 3.7 to 4.1, preferably from 3.8 to 4.0.
When the tube material is in contact with air, it will be oxidized by chemical reaction with oxygen in the airA typical free radical reaction. Antioxidant is added into the pipe material and can react with the oxidized free radical R generated by oxidation in the plastic material.、ROO.Reaction is carried out, and the growth of active chains is interrupted, so that the degradation and aging processes of plastic materials are effectively inhibited or reduced, and the service life of plastic products is prolonged. The antioxidant content of the composition is 0.2-0.5 parts, preferably 0.3-0.4 parts.
The antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 1.
The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione.
The phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or distearyl pentaerythritol diphosphite.
In order to further improve the processing performance of the composition, a small amount of PPA (fluorine-containing high polymer) processing aid can be added, and the addition amount of the processing aid is 0.01-0.03 part, preferably 0.018-0.026 part.
The preparation method of the easy-processing heat-resistant polyethylene composition comprises the following steps:
(1) putting the heat-resistant polyethylene resin, the antioxidant and the processing aid agent into a mixer, and stirring and mixing;
(2) and adding the uniformly mixed materials into a double-screw extruder for melting, plasticizing, extruding and granulating.
Wherein:
in the step (1), stirring at a rotation speed of 200-;
in the step (2), the length-diameter ratio of the screw is 31-35:1, and the processing temperature is 180-.
The invention has the following beneficial effects:
the polyethylene composition has excellent processability, pressure resistance and higher critical shear rate. Critical shear rate (200 ℃) is more than or equal to 300s-1The impact strength of the simply supported beam gap is more than or equal to 33kJ/m2Hydrostatic test at extrusion speed of 28m/min or more at 20 deg.C and 9.9MPa>2887h。
Detailed Description
The present invention is further described below with reference to examples.
Examples 1 to 5
The compounding ratio components of the easy-to-process heat-resistant polyethylene composition for the production of the heat-resistant polyethylene pipe are shown in table 1.
The density is measured according to GB/T1033.2-2010 by a D method after boiling for 30 minutes; the melt Mass Flow Rate (MFR) was tested according to GB/T3682-2000 with a load of 2.16 kg; the molecular weight and the distribution thereof adopt a Gel Permeation Chromatography (GPC) method, 2 chromatographic columns are connected in series, the solvent and the mobile phase are both 1,2, 4-trichlorobenzene (containing 0.1 percent of antioxidant 2, 6-dibutyl-p-cresol), the column temperature is 150 ℃, the dissolution is carried out for 4 hours, the flow rate is 1.0ml/min, and a narrow distribution polystyrene standard sample is adopted for universal calibration; the storage modulus, the energy consumption modulus and the complex shear viscosity of the material adopt rotational rheology, the diameter is 25mm parallel plates, the gap between the parallel plates is 1mm, and the temperature is 10 ℃ at 190 DEG C-1The dynamic frequency range to 100rad/s was tested for Frequency Sweep (FS) by selecting appropriate strain levels.
TABLE 1 EXAMPLES 1-5 easy-to-process Heat-resistant polyethylene compositions (in parts by weight)
The preparation method comprises the following steps:
a) placing heat-resistant polyethylene resin, an antioxidant and a processing aid into a high-low speed mixer, stirring and mixing, stirring at a low speed of 300 revolutions per minute for 2min, stirring at a high speed of 1200 revolutions per minute for 3min, and stirring at a temperature lower than 40 ℃;
b) and adding the uniformly mixed materials into a double-screw extruder for melting, plasticizing, extruding and granulating. The length-diameter ratio of the screw is 33:1, and the processing temperature is 200 ℃.
Comparative examples 1 to 4
Comparative examples 1-4 are comparative pipe compositions comparing various performance designs of the inventive compositions. The composition components are formulated as shown in table 2:
TABLE 2 polyethylene resin compositions of comparative examples 1 to 4 (in parts by weight)
The preparation method comprises the following steps:
a) placing heat-resistant polyethylene resin, an antioxidant and a processing aid into a high-low speed mixer, stirring and mixing, stirring at a low speed of 300 revolutions per minute for 2min, stirring at a high speed of 1200 revolutions per minute for 3min, and stirring at a temperature lower than 40 ℃;
b) and adding the uniformly mixed materials into a double-screw extruder for melting, plasticizing, extruding and granulating. The length-diameter ratio of the screw is 33:1, and the processing temperature is 200 ℃.
Example 6
Performance test experiment
The notch impact strength is tested according to GB/T1043.1-2008, a ground heating pipe machining test with the specification of phi 20 x 2.0mm is respectively carried out on domestic equipment and imported equipment at 23 ℃ for the A-shaped notch, and the machining speed and the current are recorded; after preparing the composition into a pipe with the specification of phi 20 x 2.0mm, testing the hydrostatic strength of the pipe according to GB/T18252-2000; the capillary rheological property is tested according to GB/T25278-2010, the critical shear rate of the tube material is obtained, and the test temperature is 200 ℃.
The results of the performance tests are shown in tables 3-4.
Table 3 examples 1-5 performance test results
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Impact strength of simply supported beam gap, kJ/m2 | 38 | 41 | 36 | 36 | 33 |
| Critical shear rate, s-1 | 350 | 300 | 400 | 500 | 400 |
| Extrusion processing speed, m/min | 33 | 29 | 36 | 40 | 38 |
| Extrusion processing Current, A | 63 | 56 | 72 | 75 | 73 |
| Hydrostatic strength (20 ℃, 9.9MPa), h | >2887 | >2887 | >2887 | >2887 | >2887 |
Note: the pipe processing technology comprises the following steps: the cylinder is 170 ℃ plus 195 ℃, and the head is 215 ℃ plus 195 ℃; comparative examples 1-2 are domestic pipe production lines, and comparative examples 3-4 are import pipe production lines; the hydrostatic strength (20 ℃, 9.9MPa) meets the requirements of the national standard GB/T28799.2-2012.
Table 4 comparative examples 1-4 performance test results
| Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Impact strength of simply supported beam gap, kJ/m2 | 28 | 24 | 58 | 33 |
| Critical shear rate, s-1 | 200 | 250 | 150 | 250 |
| Maximum extrusion processing speed, m/min | 24 | 22 | 26 | 29 |
| Extrusion processing Current, A | 61 | 66 | 66 | 69 |
| Hydrostatic strength (20 ℃, 9.9MPa), h | 1207 | >2887 | 2001 | >2887 |
Note: the pipe processing technology comprises the following steps: the cylinder is 170 ℃ plus 195 ℃, and the head is 215 ℃ plus 195 ℃; comparative examples 1-2 are domestic pipe production lines, and comparative examples 3-4 are import pipe production lines.
As can be seen from the comparison of the performance test results in tables 3-4, the materials of examples 1-5 have higher critical shear rate and excellent processability, and can meet the requirements of high-speed processing and the use requirements of PE-RT pipe materials.
Claims (10)
1. An easy-processing heat-resistant polyethylene composition is characterized by being prepared from the following components in parts by weight: 100 parts of heat-resistant polyethylene resin, 0.2-0.5 part of antioxidant and 0.01-0.03 part of processing aid;
the heat-resistant polyethylene resin is a copolymer of ethylene and 1-hexene produced by adopting a gas phase process and a metallocene catalyst, the reaction temperature is 91-93 ℃, and the reaction pressure is 2.0-2.2 MPa; the density of the heat-resistant polyethylene resin is 0.934-0.937g/cm3(ii) a MFR2.16 of 0.70-0.80g/10min, melt flow ratio MFR21.6/MFR2.16 of 33-37; under the conditions that G ' ' = 500Pa and the temperature is 190 ℃, the melt elastic modulus G ' is 110-170 Pa; at 190 deg.C, the ratio of complex dynamic shear viscosity eta (0.1)/eta (100) is 9.0-10.8, and the weight average molecular weight is 10.2 × 104-12.0×104And a molecular weight distribution index Mw/Mn of 3.7 to 4.1.
2. The easy-to-process heat resistant polyethylene composition according to claim 1, characterized in that: the density of the heat-resistant polyethylene resin is 0.934-0.936g/cm3(ii) a MFR2.16 of 0.72-0.76g/10min, melt flow ratio MFR21.6/MFR2.16 of 34-36; under the conditions that G ' ' = 500Pa and the temperature is 190 ℃, the melt elastic modulus G ' is 120-140 Pa; at 190 deg.C, the ratio of complex dynamic shear viscosity eta (0.1)/eta (100) is 9.4-10.3, and the weight average molecular weight is 10.5 × 104-11.5×104And a molecular weight distribution index Mw/Mn of 3.8 to 4.0.
3. The easy-to-process heat resistant polyethylene composition according to claim 1, characterized in that: the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant, and the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 1.
4. The easy-to-process heat resistant polyethylene composition according to claim 3, characterized in that: the hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione.
5. The easy-to-process heat resistant polyethylene composition according to claim 3, characterized in that: the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or distearyl pentaerythritol diphosphite.
6. The easy-to-process heat resistant polyethylene composition according to claim 1,3, 4 or 5, characterized in that: 0.3-0.4 part of antioxidant.
7. The easy-to-process heat resistant polyethylene composition according to claim 1, characterized in that: the processing aid is a fluorine-containing high polymer processing aid PPA.
8. The easy-to-process heat resistant polyethylene composition according to claim 1 or 7, characterized in that: the dosage of the processing aid is 0.018-0.026 parts.
9. A method for preparing a easy-to-process heat resistant polyethylene composition according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) putting the heat-resistant polyethylene resin, the antioxidant and the processing aid into a mixer, and stirring and mixing;
(2) and adding the uniformly mixed materials into a double-screw extruder for melting, plasticizing, extruding and granulating.
10. The method of producing a easy-to-process heat resistant polyethylene composition according to claim 9, characterized in that: in the step (1), stirring at a rotation speed of 200-; in the step (2), the length-diameter ratio of the screw is 31-35:1, and the processing temperature is 180-.
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