A pipe material with high heat-resistance creep and shape memory and a preparation method thereof

Abstract

The present invention relates to a pipe material with high heat-resistant creep and shape memory and a preparation method thereof. The pipe material is composed of 100 parts by weight of a polybutene-based resin, 0.1-5 parts by weight of an antioxidant, 0-15 parts by weight of a dye, 0.01-5 parts by weight of an initiator, and 0.02-10 parts by weight of a co-initiator. The pipe material of the present invention can be prepared by a melt extrusion method. The pipe material after melt extrusion has good oil resistance, high temperature creep resistance, and shape memory function, and can be used for long-distance trenchless pipe repair of hot and cold water pipes and oil pipelines.

Description

Technical Field

[0001] The invention relates to the field of new materials for pipeline lining layers, in particular to a high heat-resistant creep pipeline lining material with a memory function and a preparation method thereof. Background Art

[0002] Creep refers to the phenomenon that materials slowly produce plastic deformation as the loading time increases under stress. High temperature creep refers to the phenomenon that materials slowly produce plastic deformation as the loading time increases under temperature T≥(0.3~0.5)t (t is the melting point, temperature is T) and stress far below the yield strength. Most polymer materials undergo large plastic deformation near (0.3~0.5) times the melting point temperature, which seriously affects the dimensional stability of the product.

[0003] Chinese patents CN 105175859 A and CN 108774377 B disclose an inner lining material for a flexible composite pipe. The inner lining material is made of polymer-based materials, including high-density polyethylene, polyester thermoplastic polyurethane elastomer, ethylene propylene rubber, etc., and has good sealing, corrosion resistance and high barrier properties, and can be used to prepare the inner lining of the flexible composite pipe.

[0004] Chinese patent CN 107987416 A discloses a shape memory composite material, which contains 100 parts of PVC resin, 3.0-20 parts of plasticizer, 1.0-5.0 parts of stabilizer, 1.0-3.0 parts of lubricant, 5.0-30 parts of filler, and 1.0-15 parts of impact modifier. The obtained material can restore its original shape at a specific temperature.

[0005] At present, there is no publicly reported pipeline material that has both high heat-resistant creep performance and shape memory function. Summary of the invention

[0006] In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a pipeline material that has both high heat-resistant creep performance and shape memory function, which can be used in a high temperature environment of 90-100°C.

[0007] The second object of the present invention is to provide a pipeline material with good oil resistance.

[0008] A shape memory pipe material with high heat-resistance creep and a preparation method thereof, the technical solution adopted by the present invention is:

[0009] The pipeline material contains the following components in parts by weight: 100 parts of polybutene-based resin, 0.1-5 parts of antioxidant, 0-15 parts of dye, 0-15 parts of filler, 0.01-5 parts of initiator and 0.02-10 parts of auxiliary initiator.

[0010] In the pipeline material of the present invention, the polybutene-based resin is high isotactic polybutene-1 and high isotactic polybutene kettle alloy, wherein the weight ratio of high isotactic polybutene-1 and high isotactic polybutene kettle alloy is 0-100:100-0, and the weight average molecular weight of the polybutene-based resin is 500,000-1,000,000.

[0011] In the pipeline material of the present invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 264, antioxidant 2264, antioxidant 2264S, antioxidant MB, antioxidant D, antioxidant H, antioxidant RD, antioxidant AW, antioxidant DOD, antioxidant NBC, antioxidant 4010, antioxidant 4-1-NA, etc.

[0012] In the pipeline material of the present invention, the dye is selected from one or two or more of titanium dioxide, zinc oxide, cadmium red, zinc yellow, and carbon black; the filler is selected from one or two or more of titanium dioxide, carbon black, white carbon black, calcium carbonate, magnesium hydroxide, calcium hydroxide, graphene, kaolin, talc, and montmorillonite.

[0013] In the pipeline material of the present invention, the initiator is selected from peroxide initiators: peroxide ketal, dibenzoyl peroxide (BPO), diisopropylbenzene peroxide (DCP), di-tert-butyl peroxide isopropylbenzene, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, di(2,4-dichlorobenzoyl) peroxide, azo initiators, diethylenetriamine (DTA), tert-butyl perbenzoate (TPB), methylenebis(o-chloroaniline) (MOCA), and one or more of silane initiators.

[0014] In the pipeline material of the present invention, the co-initiator is selected from one or more of triallyl isocyanurate (TIAC), triallyl cyanurate (TAC), ethylene glycol dimethacrylate (EDMA), divinylbenzene (DVB), trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), styrene, maleic anhydride, pentaerythritol tetraacrylate, benzoquinone, hydroquinone, 1,2-polybutadiene, and thiourea.

[0015] The method for preparing the high heat-resistant creep shape memory pipe material of the present invention is prepared by the following steps:

[0016] (1) 100 parts of a polybutene-based resin, 0.1-5 parts of an antioxidant, 0-15 parts of a dye, 0-15 parts of a filler, 0.01-5 parts of an initiator, and 0.02-10 parts of a co-initiator are mixed in a high-speed mixer at a mixing temperature of 60-120° C., a rotating speed of 500-1500 rpm, and a mixing time of 2-30 minutes to obtain a uniformly dispersed mixed material;

[0017] (2) adding the mixed material prepared in step (1) into a screw extruder, wherein the screw rotation frequency is 5-15 Hz, the temperature of the first zone of the screw is 150-210° C., the temperature of the second zone is 160-220° C., the temperature of the third zone is 150-210° C., and the die temperature is 160-200° C., and a tube is prepared by melt extrusion;

[0018] (3) The tube guided out from the die in step (2) is pulled at a pulling speed of 2-10 rpm, a vacuum sizing pressure of 0.005-0.05 MPa, and a shaping temperature of -15°C-60°C to obtain a shape memory liner tube with high heat-resistant creep.

[0019] In the preparation method of the present invention, the screw extruder used is a single-screw extruder or a twin-screw extruder, and the length-to-diameter ratio of the extruder is 30-50:1.

[0020] The feature of the present invention is that the high heat-resistant creep shape memory pipe material can be used in a high temperature environment of 90-100°C, and has both outstanding high temperature heat-resistant creep performance and oil resistance; at the same time, it has a shape memory function and is used for trenchless lining repair of oilfield pipelines and trenchless lining repair of civil water pipes. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be further described below in conjunction with specific embodiments, which will help to understand the present invention. The scope of rights of the present invention shall be based on the description in the claims.

[0022] raw materials

[0023] High isotactic polybutene-1 (PB), melt index 0.65 (190℃, 2.16MPa); high isotactic polybutene kettle alloy (PBA), melt index 1.0 (190℃, 2.16MPa); polyethylene pipe special material PERT, melt index 0.8 (190℃, 2.16MPa); copolymer polypropylene pipe special material PPR, melt index 1.2 (210℃, 2.16MPa); other additives, all commercially available industrial products

[0024] Example 1

[0025] Weigh 50 parts of PB, 50 parts of PBA, 1.5 parts of antioxidant 1010, 3 parts of dye TiO2, 0.05 parts of initiator diisopropylbenzene peroxide, and 0.10 parts of co-initiator EDMA according to weight. Add the weighed materials into a high-speed mixer, the speed of the high-speed mixer is 700rpm, the temperature of the high-speed mixer is 110℃, the mixing time is 10 minutes, and the material is discharged after the mixing is completed. Put the mixed materials into a single-screw extruder, the temperature of the first zone of the screw is 185℃, the temperature of the second zone is 190℃, the temperature of the third zone is 175℃, the die temperature is 180℃, the rotation frequency of the single-screw extruder is 10Hz, the traction speed of the traction machine is 5rpm, the vacuum sizing pressure is 0.01MPa, the shaping temperature is 15℃, and the tube with an outer diameter of about 20mm and a wall thickness of about 1mm is extruded.

[0026] Example 2

[0027] According to weight, weigh 100 parts of PBA, 2 parts of antioxidant 264, 10 parts of carbon black N330, 0.15 parts of initiator azobisisobutylnitrile, and 0.3 parts of auxiliary initiator triallyl isocyanurate. Add the weighed materials to a high-speed mixer, the speed of the high-speed mixer is 1200rpm, the temperature of the high-speed mixer is 120℃, the mixing time is 5 minutes, and the material is discharged after the mixing is completed. Put the mixed materials into a single-screw extruder, the temperature of the first zone is 190℃, the temperature of the second zone is 200℃, the temperature of the third zone is 190℃, the die temperature is 190℃, the rotation frequency of the single-screw extruder is 7Hz, the traction speed of the traction machine is 4rpm, the vacuum sizing pressure is 0.02MPa, the shaping temperature is 25℃, and the tube with an outer diameter of about 20mm and a wall thickness of about 1mm is extruded.

[0028] Example 3

[0029] Weigh 30 parts of PB, 70 parts of PBA, 0.5 parts of antioxidant 2264, 3 parts of silicon dioxide, 0.2 parts of initiator di-tert-butyl peroxide isopropylbenzene, and 0.4 parts of auxiliary initiator trimethylolpropane trimethacrylate according to weight. Add the weighed materials into a high-speed mixer, the speed of the high-speed mixer is 700rpm, the temperature of the high-speed mixer is 110℃, the mixing time is 15 minutes, and the material is discharged after the mixing is completed. Put the mixed materials into a single-screw extruder, the temperature of the first zone of the screw is 185℃, the temperature of the second zone is 190℃, the temperature of the third zone is 200℃, the temperature of the die is 190℃, the rotation frequency of the single-screw extruder is 10Hz, the traction speed of the traction machine is 5rpm, the vacuum sizing pressure is 0.01MPa, the shaping temperature is -10℃, and the tube with an outer diameter of about 20mm and a wall thickness of about 1mm is extruded.

[0030] Comparative Example 1

[0031] According to weight, 100 parts of PERT, 2 parts of antioxidant 264, 10 parts of carbon black N330, 0.15 parts of initiator azobisisobutylnitrile, and 0.3 parts of co-initiator triallyl isocyanurate are weighed. The weighed materials are added to a high-speed mixer, the speed of the high-speed mixer is 1200rpm, the temperature of the high-speed mixer is 120℃, the mixing time is 5 minutes, and the material is discharged after the mixing is completed. The mixed materials are put into a single-screw extruder, the temperature of the first zone is 190℃, the temperature of the second zone is 200℃, the temperature of the third zone is 190℃, the die temperature is 190℃, the rotation frequency of the single-screw extruder is 7Hz, the traction speed of the traction machine is 4rpm, the vacuum sizing pressure is 0.02MPa, the shaping temperature is 25℃, and the tube with an outer diameter of about 20mm and a wall thickness of about 1mm is extruded.

[0032] Comparative Example 2

[0033] According to weight, weigh 100 parts of PPR, 2 parts of antioxidant 264, 10 parts of dye carbon black N330, 0.15 parts of initiator azobisisobutylnitrile, and 0.3 parts of auxiliary initiator triallyl isocyanurate. Add the weighed materials to a high-speed mixer, the speed of the high-speed mixer is 1200rpm, the temperature of the high-speed mixer is 120℃, the mixing time is 5 minutes, and the material is discharged after the mixing is completed. Put the mixed materials into a single-screw extruder, the temperature of the first zone is 190℃, the temperature of the second zone is 200℃, the temperature of the third zone is 190℃, the die temperature is 190℃, the rotation frequency of the single-screw extruder is 7Hz, the traction speed of the traction machine is 4rpm, the vacuum sizing pressure is 0.02MPa, the shaping temperature is 25℃, and the tube with an outer diameter of about 20mm and a wall thickness of about 1mm is extruded.

[0034] The pipes produced by Examples 1-3 and Comparative Examples 1 and 2 were tested, and the results are listed in Table 1. From the data in Table 1, it can be seen that the pipes produced by Examples 1-3 have excellent heat-resistant creep performance, and the creep deformation variable at 70 degrees is much lower than that of PPR and significantly lower than that of PERT; the pipes of the examples have good oil resistance at 65 degrees, and the tensile strength does not change much after being soaked in 65-degree light oil, and the oil resistance is significantly better than that of PERT; the pipes of the examples also have good shape memory function, and the shape recovery rate after stimulation at 130°C-170°C reaches 96%, which is higher than 92% and 90% of PPR and PERT.

[0035] Table 1 Pipe properties of the embodiments and comparative examples

[0036]

Claims

1. A method for preparing a shape memory pipe material with high heat-resistant creep, characterized in that: The following steps are involved: (1) 100 parts of a polybutene-based resin, 0.1-5 parts of an antioxidant, 0-15 parts of a dye, 0-15 parts of a filler, 0.01-5 parts of an initiator, and 0.02-10 parts of a co-initiator are mixed in a high-speed mixer at a mixing temperature of 60-120° C., a rotating speed of 500-1500 r / min, and a mixing time of 2-30 minutes to obtain a uniformly dispersed mixed material; (2) adding the mixed material prepared in step (1) into a screw extruder, wherein the screw rotation frequency is 5-15 Hz, the temperature of the first zone of the screw is 150-210° C., the temperature of the second zone is 160-220° C., the temperature of the third zone is 150-210° C., and the die temperature is 160-200° C., and a tube is prepared by melt extrusion; (3) pulling the tube guided out from the die in step (2) at a pulling speed of 2-10 rpm, a vacuum sizing pressure of 0.005-0.05 MPa, and a shaping temperature of -15°C-60°C to obtain a shape memory liner tube with high heat-resistant creep; The polybutene-based resin is high isotactic polybutene-1 and high isotactic polybutene in-kettle alloy, wherein the weight ratio of high isotactic polybutene-1 and high isotactic polybutene in-kettle alloy is 0-50:100-50, and the weight average molecular weight of the polybutene-based resin is 500,000-1,000,000.

2. The preparation method according to claim 1, characterized in that: The screw extruder is a single-screw extruder or a twin-screw extruder, and the length-to-diameter ratio of the extruder is 30-50:

1.

3. The preparation method according to claim 1, characterized in that: The high heat-resistant creep shape memory liner pipe contains the following components in parts by weight: 100 parts of polybutene-based resin, 0.1-5 parts of antioxidant, 0-15 parts of dye, 0-15 parts of filler, 0.01-5 parts of initiator, and 0.02-10 parts of co-initiator. The pipe material changes shape under the action of external force and can restore its original shape at a stimulation temperature of 100-190°C. It has high-temperature heat-resistant creep performance, oil resistance, and shape memory function.

4. The preparation method according to claim 1, characterized in that: The antioxidant is selected from one or more of antioxidant 1010, antioxidant 264, antioxidant 2264, antioxidant 2264S, antioxidant MB, antioxidant D, antioxidant H, antioxidant RD, antioxidant AW, antioxidant DOD, antioxidant NBC, antioxidant 4010, and antioxidant 4-1-NA.

5. The preparation method according to claim 1, characterized in that: The dye is selected from one or two or more of titanium dioxide, zinc oxide, cadmium red, zinc yellow and carbon black; the filler is selected from one or two or more of titanium dioxide, carbon black, white carbon black, calcium carbonate, magnesium hydroxide, calcium hydroxide, graphene, kaolin, talc and montmorillonite.

6. The preparation method according to claim 1, characterized in that: The initiator is selected from one or more of peroxide ketal, dibenzoyl peroxide BPO, dicumyl peroxide DCP, di-tert-butyl peroxide isopropylbenzene, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, di(2,4-dichlorobenzoyl) peroxide, azo initiators, and tert-butyl perbenzoate TPB.

7. The preparation method according to claim 1, characterized in that: The auxiliary initiator is selected from one or more of triallyl isocyanurate TIAC, triallyl cyanurate TAC, ethylene glycol dimethacrylate EDMA, divinylbenzene DVB, trimethylolpropane trimethacrylate TMPTMA, trimethylolpropane triacrylate TMPTA, styrene, maleic anhydride, pentaerythritol tetraacrylate, and 1,2-polybutadiene.

8. The preparation method according to claim 1, characterized in that: The high heat-resistant creep shape memory liner tube has a shape memory function after melt extrusion molding, changes shape under the action of external force, and can restore the original shape at a stimulation temperature of 100-190°C.

9. The preparation method according to claim 1, characterized in that: The high heat-resistant creep shape memory liner pipe is used in a high temperature environment of 90-100°C. It has both high temperature heat-resistant creep performance and oil resistance. It also has a shape memory function and is used for trenchless lining repair of oilfield pipelines and trenchless lining repair of civil water pipes.

Images