CN113831654A - Lining layer material of flexible composite pipe - Google Patents
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- 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
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Abstract
The invention provides an inner liner material of a flexible composite pipe, which comprises the following raw materials in part by weight: 65-70 parts of crosslinked polyethylene (XLPE), 20-25 parts of ethylene-vinyl acetate rubber (EVM), 5-10 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH), 2-5 parts of Maleic Anhydride (MAH), 1-2 parts of dibenzoyl peroxide (BPO), 6910-15 parts of Si6910, 25-35 parts of white carbon black, 10101-2 parts of antioxidant, 1.5-2 parts of anti-aging agent RD, 502-3.5 parts of hydrolysis resistant agent Rhengran P-502, 2-3 parts of dicumyl peroxide (DCP) and 1-2 parts of crosslinking agent TAIC. The invention has the beneficial effects that: according to the invention, poly (vinylidene fluoride-co-hexafluoropropylene) is used for grafting maleic anhydride, and PVDF-HFP-MAH is used for preparing the lining layer material, so that the prepared lining layer rubber material has high tensile strength, medium resistance and high temperature resistance on the premise of keeping the hardness basically unchanged, thereby prolonging the service life of the petroleum transportation pipeline.
Description
Technical Field
The invention relates to the technical field of oilfield transportation, in particular to a lining material of a flexible composite pipe.
Background
At present, in the field of oil field transportation, people always use two types of metal pipelines and non-metal pipelines, wherein the non-metal pipelines comprise a plurality of types, the glass reinforced plastic pipe has high strength and high pressure bearing capacity, but has poor impact resistance and is easy to crack in winter; the steel skeleton plastic pipe has lower pressure bearing capacity and lower use temperature; plastic alloy composite pipes are relatively expensive, and therefore, flexible composite high-pressure delivery pipes with good flexibility, high pressure resistance and corrosion resistance are increasingly emphasized in the petroleum transportation industry.
The flexible composite high-pressure delivery pipe is generally divided into three layers from inside to outside: the inner lining layer, the enhancement layer and the outer protective layer are in direct contact with the inner lining layer in the transportation process of petroleum, so the requirement on the inner lining layer material is severe, the existing inner lining layer material has poor medium permeation resistance, and petroleum and H have poor medium permeation resistance2S and CO2The medium is easy to corrode the enhancement layer of the oil pipeline, and the inner layer collapse phenomenon is caused by sudden pressure reduction or negative pressure condition in the pipeline, so that the service life is short.
Disclosure of Invention
The invention aims to improve the impermeability and corrosion resistance of a nonmetal oil pipeline.
In order to achieve the purpose, the invention provides an inner liner material of a flexible composite pipe, which comprises the following raw materials:
65-70 parts of cross-linked polyethylene (XLPE);
20-25 parts of ethylene-vinyl acetate rubber (EVM);
5-10 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH);
2-5 parts of Maleic Anhydride (MAH);
1-2 parts of dibenzoyl peroxide (BPO);
si6910-15 parts;
25-35 parts of white carbon black;
10101-2 parts of an antioxidant;
1.5-2 parts of an anti-aging agent RD;
502-3.5 parts of hydrolysis resistant agent Rhengran P-502;
2-3 parts of dicumyl peroxide (DCP);
1-2 parts of cross-linking agent TAIC.
Preferably, the preparation raw material of the poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH) comprises the following components:
100 parts of poly (vinylidene fluoride-co-hexafluoropropylene);
2-5 parts of Maleic Anhydride (MAH);
0.3-0.6 part of dibenzoyl peroxide (BPO).
Preferably, the poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH) is prepared by the following steps:
adding poly (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the temperature of the internal mixer is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
step (2); adding dibenzoyl peroxide in batches, adding 50% of dibenzoyl peroxide for the first time, heating the mixing temperature to 160 ℃, mixing for 3min, adding the rest dibenzoyl peroxide for the second time, and mixing for 5 min;
and (3) adding maleic anhydride, and mixing at 180 ℃ for 5-8 min.
Preferably, the preparation method of the lining layer material of the flexible composite pipe comprises the following steps:
step (1), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 3-5min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and mixing for 3-5 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 35-40 r/min;
step (2), adding poly (vinylidene fluoride-co-hexafluoropropylene) to graft maleic anhydride (PVDF-HFP-MAH); the mixing temperature is 150-;
adding cross-linked polyethylene (XLPE) for mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, and mixing for 3-4min at the temperature of 160-170 ℃ and at the rotation speed of 40-45r/min;
step (4), the mixed rubber is sliced down by an open mill, and is cut into strips for standby, wherein the temperature of the open mill is 170-175 ℃, and the rotating speed is 40-45r/min;
and (5) adding the strip rubber compound in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 100-200 ℃, the rotating speed of a main machine is 35-45r/min, and the speed of a tractor is 5-8 rpm.
The invention has the beneficial effects that: according to the invention, poly (vinylidene fluoride-co-hexafluoropropylene) is used for grafting maleic anhydride, and PVDF-HFP-MAH is used for preparing the lining layer material, so that the prepared lining layer rubber material has high tensile strength, medium resistance and high temperature resistance on the premise of keeping the hardness basically unchanged, thereby prolonging the service life of the petroleum transportation pipeline.
Drawings
FIG. 1 shows the thickness variation in the media compatibility experiment for different examples.
FIG. 2 shows the mass change in the media compatibility experiment of various examples.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
Example 1:
firstly, preparing poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH)
Weighing 100 parts of poly (vinylidene fluoride-co-hexafluoropropylene), 2 parts of Maleic Anhydride (MAH) and 0.3 part of dibenzoyl peroxide (BPO) according to parts by weight;
step (2), adding poly (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the temperature of the internal mixer is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
adding dibenzoyl peroxide in batches, adding 50% of dibenzoyl peroxide for the first time, heating the mixing temperature to 160 ℃, mixing for 3min, adding the rest dibenzoyl peroxide for the second time, and mixing for 5 min;
and (3) adding maleic anhydride, and mixing at 180 ℃ for 5 min.
Secondly, preparing a lining layer material of the flexible composite pipe
Weighing 65 parts of crosslinked polyethylene (XLPE), 20 parts of ethylene-vinyl acetate rubber (EVM), 5 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH), 2 parts of Maleic Anhydride (MAH), 1 part of dibenzoyl peroxide (BPO), 6910 part of Si6910 part, 25 parts of white carbon black, 10101 parts of antioxidant, 1.5 parts of anti-aging agent RD, Rhengran P-502 parts of anti-hydrolysis agent, 2 parts of dicumyl peroxide (DCP) and 1 part of crosslinking agent TAIC according to parts by weight;
step (2), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 3min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and mixing for 3 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 35 r/min;
step (3), adding poly (vinylidene fluoride-co-hexafluoropropylene) to graft maleic anhydride (PVDF-HFP-MAH); the mixing temperature is 150 ℃, the rotating speed is 40r/min, and the mixing time is 1 min;
adding cross-linked polyethylene (XLPE) and mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, mixing for 3min at 160 ℃ and 40r/min;
step (5), blanking the rubber compound by using an open mill, and cutting into strips for later use, wherein the temperature of the open mill is 170 ℃, and the rotating speed is 40r/min;
and (6) adding the strip rubber compound obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 100 ℃, the rotating speed of a main machine is 35r/min, and the speed of a tractor is 5 rpm.
Example 2:
firstly, preparing poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH)
Weighing 100 parts of poly (vinylidene fluoride-co-hexafluoropropylene), 5 parts of Maleic Anhydride (MAH) and 0.6 part of dibenzoyl peroxide (BPO) according to parts by weight;
step (2), adding poly (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the temperature of the internal mixer is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
adding dibenzoyl peroxide in batches, adding 50% of dibenzoyl peroxide for the first time, heating the mixing temperature to 160 ℃, mixing for 3min, adding the rest dibenzoyl peroxide for the second time, and mixing for 5 min;
and (3) adding maleic anhydride, and mixing at 180 ℃ for 8 min.
Secondly, preparing a lining layer material of the flexible composite pipe
Weighing 70 parts of crosslinked polyethylene (XLPE), 25 parts of ethylene-vinyl acetate rubber (EVM), 10 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH), 5 parts of Maleic Anhydride (MAH), 2 parts of dibenzoyl peroxide (BPO), Si6915 parts, 35 parts of white carbon black, 10102 parts of antioxidant, 2 parts of anti-aging agent RD, 3 parts of hydrolysis resistant agent Rhengran P-503.5 parts, 3 parts of dicumyl peroxide (DCP) and 2 parts of crosslinking agent TAIC according to parts by weight;
step (2), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 5min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and mixing for 5 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 40r/min;
step (3), adding poly (vinylidene fluoride-co-hexafluoropropylene) to graft maleic anhydride (PVDF-HFP-MAH); the mixing temperature is 160 ℃, the rotating speed is 45r/min, and the mixing time is 1 min;
adding cross-linked polyethylene (XLPE) and mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, and mixing for 4min at 170 ℃ and at a rotation speed of 45r/min;
step (5), blanking the rubber compound by using an open mill, and cutting into strips for later use, wherein the temperature of the open mill is 175 ℃, and the rotating speed is 45r/min;
and (6) adding the strip rubber compound obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 200 ℃, the rotating speed of a main machine is 45r/min, and the speed of a tractor is 8 rpm.
Example 3:
firstly, preparing poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH)
Weighing 100 parts of poly (vinylidene fluoride-co-hexafluoropropylene), 3 parts of Maleic Anhydride (MAH) and 0.4 part of dibenzoyl peroxide (BPO) according to parts by weight;
step (2), adding poly (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the temperature of the internal mixer is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
adding dibenzoyl peroxide in batches, adding 50% of dibenzoyl peroxide for the first time, heating the mixing temperature to 160 ℃, mixing for 3min, adding the rest dibenzoyl peroxide for the second time, and mixing for 5 min;
and (3) adding maleic anhydride, and mixing at 180 ℃ for 7 min.
Secondly, preparing a lining layer material of the flexible composite pipe
Weighing 68 parts of crosslinked polyethylene (XLPE), 24 parts of ethylene-vinyl acetate rubber (EVM), 8 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH), 4 parts of Maleic Anhydride (MAH), 1.2 parts of dibenzoyl peroxide (BPO), 6913 parts of Si, 30 parts of white carbon black, 10101.5 parts of antioxidant, 1.8 parts of antioxidant RD, 1.32 parts of hydrolysis-resistant agent Rhengran P-503.0 parts of dicumyl peroxide (DCP) and 1.5 parts of crosslinking agent TAIC according to parts by weight;
step (2), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 4min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and mixing for 4 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 38 r/min;
step (3), adding poly (vinylidene fluoride-co-hexafluoropropylene) to graft maleic anhydride (PVDF-HFP-MAH); the mixing temperature is 155 ℃, the rotating speed is 42r/min, and the mixing time is 1 min;
adding cross-linked polyethylene (XLPE) and mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, and mixing for 3.5min at 165 ℃ and 43r/min;
step (5), blanking the rubber compound by using an open mill, and cutting into strips for later use, wherein the temperature of the open mill is 173 ℃, and the rotating speed is 42 r/min;
and (6) adding the strip rubber compound obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 150 ℃, the rotating speed of a main machine is 40r/min, and the speed of a tractor is 7 rpm.
Example 4:
firstly, preparing a lining layer material of a flexible composite pipe
Weighing 68 parts of crosslinked polyethylene (XLPE), 24 parts of ethylene-vinyl acetate rubber (EVM), 8 parts of poly (vinylidene fluoride-co-hexafluoropropylene), 4 parts of Maleic Anhydride (MAH), 1.2 parts of dibenzoyl peroxide (BPO), 6913 parts of Si, 30 parts of white carbon black, 10101.5 parts of antioxidant, 1.8 parts of antioxidant RD, 2.5 parts of hydrolysis resistant agent Rhengran P-503.0 parts, 2.5 parts of dicumyl peroxide (DCP) and 1.5 parts of crosslinking agent TAIC according to parts by weight;
step (2), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 4min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and mixing for 4 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 38 r/min;
adding poly (vinylidene fluoride-co-hexafluoropropylene) in the step (3), wherein the mixing temperature is 155 ℃, the rotating speed is 42r/min, and the mixing time is 1 min;
adding cross-linked polyethylene (XLPE) and mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, and mixing for 3.5min at 165 ℃ and 43r/min;
step (5), blanking the rubber compound by using an open mill, and cutting into strips for later use, wherein the temperature of the open mill is 173 ℃, and the rotating speed is 42 r/min;
and (6) adding the strip rubber compound obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 150 ℃, the rotating speed of a main machine is 40r/min, and the speed of a tractor is 7 rpm.
Example 5:
firstly, preparing a lining layer material of a flexible composite pipe
Weighing 68 parts of crosslinked polyethylene (XLPE), 24 parts of ethylene-vinyl acetate rubber (EVM), 12 parts of Maleic Anhydride (MAH), 1.2 parts of dibenzoyl peroxide (BPO), 6913 parts of Si, 30 parts of white carbon black, 10101.5 parts of antioxidant, 1.8 parts of antioxidant RD, 2.5 parts of hydrolysis-resistant agent Rhengran P-503.0 parts of dicumyl peroxide (DCP) and 1.5 parts of crosslinking agent TAIC according to parts by weight;
step (2), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 4min, adding dibenzoyl peroxide (BPO) and 4 parts of Maleic Anhydride (MAH), and mixing for 4 min; the temperature of the internal mixer is 150 ℃, and the rotating speed is 38 r/min;
adding 8 parts of maleic anhydride; the mixing temperature is 155 ℃, the rotating speed is 42r/min, and the mixing time is 1 min;
adding cross-linked polyethylene (XLPE) and mixing, adding Si69, white carbon black, antioxidant 1010 and antioxidant RD, and mixing for 3.5min at 165 ℃ and 43r/min;
step (5), blanking the rubber compound by using an open mill, and cutting into strips for later use, wherein the temperature of the open mill is 173 ℃, and the rotating speed is 42 r/min;
and (6) adding the strip rubber compound obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding, wherein the screw temperature of the double-screw extruder is 150 ℃, the rotating speed of a main machine is 40r/min, and the speed of a tractor is 7 rpm.
The materials produced in examples 1-5 were tested and the results are shown in Table 1 and the accompanying drawings.
As can be seen from the comparison between examples 1-3 and examples 4-5, the tensile strength of the material prepared by the method is 100% higher than that of the material prepared by only using poly (vinylidene fluoride-co-hexafluoropropylene) and maleic anhydride, the hardness of the material can be basically kept the same, the thickness change and the quality change of the medium compatibility experiment of the material prepared by the method are very small, and the temperature resistance of the material prepared by the method is about 30% higher than that of the material prepared by only using poly (vinylidene fluoride-co-hexafluoropropylene) and maleic anhydride.
TABLE 1
Claims (10)
1. The inner liner material of the flexible composite pipe is characterized in that the preparation raw materials of the inner liner material comprise the following components:
65-70 parts of cross-linked polyethylene (XLPE);
20-25 parts of ethylene-vinyl acetate rubber (EVM);
5-10 parts of poly (vinylidene fluoride-co-hexafluoropropylene) grafted maleic anhydride (PVDF-HFP-MAH);
2-5 parts of Maleic Anhydride (MAH);
1-2 parts of dibenzoyl peroxide (BPO);
si6910-15 parts;
25-35 parts of white carbon black;
10101-2 parts of an antioxidant;
1.5-2 parts of an anti-aging agent RD;
502-3.5 parts of hydrolysis resistant agent Rhengran P-502;
2-3 parts of dicumyl peroxide (DCP);
1-2 parts of cross-linking agent TAIC.
2. A material for an inner liner of a flexible composite pipe according to claim 1, wherein the poly (vinylidene fluoride-co-hexafluoropropylene) -grafted maleic anhydride (PVDF-HFP-MAH) is prepared from the following raw materials:
100 parts of poly (vinylidene fluoride-co-hexafluoropropylene);
2-5 parts of Maleic Anhydride (MAH);
0.3-0.6 part of dibenzoyl peroxide (BPO).
3. A material for an inner liner of a flexible composite pipe according to claim 2, wherein the poly (vinylidene fluoride-co-hexafluoropropylene) -grafted maleic anhydride (PVDF-HFP-MAH) is prepared by the steps of:
adding poly (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the temperature of the internal mixer is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
adding dibenzoyl peroxide in batches, and adjusting the mixing temperature and time;
and (3) adding maleic anhydride, adjusting the temperature and time, and blanking.
4. The material for the inner liner of the flexible composite pipe as claimed in claim 3, wherein 50% dibenzoyl peroxide is added for the first time in step (2), the mixing temperature is raised to 170 ℃, the mixing is carried out for 3min, and the rest dibenzoyl peroxide is added for the second time and the mixing is carried out for 5 min.
5. The inner lining material of the flexible composite pipe as claimed in claim 3 or 4, wherein the mixing temperature in the step (3) is 180 ℃ and the mixing time is 5-8 min.
6. A method for preparing the material of the inner liner of the flexible composite pipe according to claim 1, which comprises the following steps:
step (1), adding EVM into an internal mixer, adding an anti-hydrolysis agent Rhengran P-50 and an antioxidant 1010, mixing for 3-5min, adding dibenzoyl peroxide (BPO) and Maleic Anhydride (MAH), and continuously mixing for 3-5 min;
step (2), adding poly (vinylidene fluoride-co-hexafluoropropylene) to graft maleic anhydride (PVDF-HFP-MAH);
adding cross-linked polyethylene (XLPE) and mixing, and adding Si69, white carbon black, antioxidant 1010 and antioxidant RD;
step (4), blanking the rubber compound by using an open mill, and cutting into strips for later use;
and (5) adding the strip mixed rubber obtained in the step (4) into a double-screw extruder, adding dicumyl peroxide (DCP) and a cross-linking agent TAIC, and extruding.
7. The method for preparing the material of the inner liner of the flexible composite pipe according to claim 6, wherein:
the temperature of the internal mixer in the step (1) is 150 ℃, and the rotating speed is 35-40 r/min;
the mixing time in the step (2) is 1min, the mixing temperature is 150-;
the mixing time in the step (3) is 3-4min, the mixing temperature is 160-170 ℃, and the rotating speed is 40-45r/min;
in the step (4), the temperature of the open mill is 170-175 ℃, and the rotating speed is 40-45r/min;
in the step (5), the screw temperature of the double-screw extruder is 100-.
8. The flexible composite pipe liner material of claim 6 or 7, wherein the poly (vinylidene fluoride-co-hexafluoropropylene) -grafted maleic anhydride (PVDF-HFP-MAH) is made from:
100 parts of poly (vinylidene fluoride-co-hexafluoropropylene);
2-5 parts of Maleic Anhydride (MAH);
0.3-0.6 part of dibenzoyl peroxide (BPO).
9. The flexible composite pipe liner material according to claim 6 or 7, wherein the poly (vinylidene fluoride-co-hexafluoropropylene) -grafted maleic anhydride (PVDF-HFP-MAH) is prepared by the following steps:
adding the (vinylidene fluoride-co-hexafluoropropylene) into an internal mixer, wherein the mixing temperature is 160 ℃, the rotating speed is 80r/min, and the time is 5 min;
adding dibenzoyl peroxide in batches, and adjusting the mixing temperature and time;
and (3) adding maleic anhydride, adjusting the temperature and time, and blanking.
10. The inner liner material of the flexible composite pipe as claimed in claim 9, wherein 50% dibenzoyl peroxide is added for the first time in step (2), the mixing temperature is raised to 170 ℃, the mixing time is 3min, the remaining dibenzoyl peroxide is added for the second time, the mixing time is 5min, the mixing temperature in step 3 is 180 ℃, and the mixing time is 5-8 min.
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