CN110541975B - Polyolefin pipe material capable of self-cleaning, preventing scaling and waxing as well as preparation method and application thereof - Google Patents
Polyolefin pipe material capable of self-cleaning, preventing scaling and waxing as well as preparation method and application thereof Download PDFInfo
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- CN110541975B CN110541975B CN201910877319.5A CN201910877319A CN110541975B CN 110541975 B CN110541975 B CN 110541975B CN 201910877319 A CN201910877319 A CN 201910877319A CN 110541975 B CN110541975 B CN 110541975B
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- 239000000463 material Substances 0.000 title claims abstract description 188
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 140
- 238000004140 cleaning Methods 0.000 title claims abstract description 16
- 238000004018 waxing Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 48
- 239000011737 fluorine Substances 0.000 claims abstract description 48
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 11
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- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 5
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 230000008021 deposition Effects 0.000 abstract description 6
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- 230000008018 melting Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000012988 Dithioester Substances 0.000 description 3
- 125000005022 dithioester group Chemical group 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
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- 230000002209 hydrophobic effect Effects 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
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- 239000012991 xanthate Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004595 color masterbatch Substances 0.000 description 2
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- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000012987 RAFT agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- HSNHLHNSJCYPNU-UHFFFAOYSA-N o-propan-2-yl propan-2-ylsulfanylmethanethioate Chemical compound CC(C)OC(=S)SC(C)C HSNHLHNSJCYPNU-UHFFFAOYSA-N 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention relates to a polyolefin pipe material with self-cleaning, anti-scaling and wax-deposition functions and a preparation method and application thereof, wherein the polyolefin pipe material comprises a pipe material inner layer and a pipe material outer layer, the pipe material inner layer is made of a blend material of a polyolefin modified material containing fluorine groups and a matrix polyolefin material, and the pipe material outer layer is made of a polyolefin material; the preparation method of the polyolefin pipe comprises the following steps: 1) blending the polyolefin modified material containing the fluorine group with a matrix polyolefin material to obtain a blended material; 2) co-extruding the blending material and the polyolefin material in a double layer manner to obtain the anti-scaling and anti-waxing polyolefin pipe; the polyolefin pipe can be used for manufacturing an inner pipe of a steel wire winding pipe. Compared with the prior art, the invention reduces the surface energy of the inner wall of the pipeline by introducing the fluorine-containing group chain segment, so that the pipeline has the functions of scale prevention and wax deposition, and in addition, the introduction of the fluorine-containing group is also beneficial to improving the high temperature resistance and the corrosion resistance of the pipeline, so that the polyolefin pipe has wider application prospect.
Description
Technical Field
The invention belongs to the technical field of pipes, and relates to a polyolefin pipe with self-cleaning, anti-scaling and wax-deposition functions, and a preparation method and application thereof.
Background
In the process of oilfield water injection and crude oil transportation, due to the changes of environmental conditions such as pressure, temperature and the like and the adsorption effect of a fluid medium and the surface of a pipe, wax and inorganic salt in a transportation medium can be deposited on the pipe wall to form a wax scaling layer, so that the flow area is reduced, and the transportation resistance is increased. The wax precipitation and the scale formation reduce the circulation area of the pipeline, increase the friction resistance, reduce the conveying capacity of the pipeline, even block the pipeline in serious conditions, and cause great economic loss. In addition, the heating in the north is mainly central heating, and the quality of water in the north is relatively poor, will be at the pipeline inner wall scale deposit after operation a period to can lead to the water resistance to increase and influence the heating effect, generally just need wash once 3-5 years, waste time and energy and cost money, seriously influence user experience and feel.
The solid-liquid interface theory considers that the surface energy of the material is an important factor for initiating wax precipitation and scaling. Reducing the surface energy of the pipe material can reduce the degree of fouling of the inner wall of the pipe. Therefore, in the investigation process, the modification of the inner wall of the pipe is proposed, so that the inner wall of the pipe forms lower surface energy, the hydrophobic-oleophobic performance is realized, and the problems of scaling and wax deposition of the pipe are fundamentally solved.
High molecular materials with low surface energy are the primary consideration, while the surface energy of fluorine-containing materials is the lowest among the polymeric materials. However, the conventional fluorine-containing modifier has low molecular weight and poor compatibility with polyolefin matrix. Although it can migrate to the surface, to some extent, reduce the surface energy. But because the bonding force between the polyolefin and the polyolefin is weak, the polyolefin can be gradually taken away along with the liquid conveying in the pipeline and the scraping of impurities in the liquid, and the continuous action effect of the polyolefin is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a polyolefin pipe with self-cleaning, anti-scaling and anti-waxing functions, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the polyolefin pipe comprises an inner layer and an outer layer, wherein the inner layer is made of a blend material of a polyolefin modified material containing fluorine groups and a matrix polyolefin material, and the outer layer is made of a polyolefin material.
Further, the polyolefin modified material containing the fluorine group comprises a polyolefin main chain segment and a fluorine-containing group chain segment grafted on the polyolefin main chain segment.
The main chain segment is a polyolefin chain segment, has good compatibility with a matrix polyolefin material in the blending material, and is favorable for the entanglement of the main chain segment and the chain segment in the matrix polyolefin material due to the long chain length of the main chain segment, so that the binding force of the two materials in the blending material is improved; the fluorine-containing group chain segment is grafted on the polyolefin main chain segment as a functional chain segment, and the fluorine-containing group chain segment with smaller surface energy can be gathered to the surface of the blending material, namely to the surface of the inner layer of the pipe, so that the surface energy of the inner wall of the pipe is reduced; in addition, the fluorine-containing group chain segment which cannot be migrated to the surface in the blending material can be anchored between the main chain segment and the matrix polyolefin material chain segment in the matrix polyolefin material, so that the entanglement between the two chain segments is enhanced, and the bonding force between the fluorine-containing group polyolefin modified material and the matrix polyolefin material is further improved.
Further, the polyolefin main chain segment comprises one of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), heat-resistant Polyethylene (PERT) or ultrahigh molecular weight polyethylene (UHMWPE);
the fluorine-containing group chain segment comprises one of functional groups generated by graft polymerization of fluorine-containing and double-bond reaction monomers such as poly (trifluoroethyl acrylate), poly (hexafluorobutyl acrylate), poly (dodecafluoro heptyl methacrylate), poly (perfluorodecyl ethylene) and the like.
Further, the base polyolefin material in the blended material and the polyolefin material in the outer layer of the pipe are the same polyolefin material, and the polyolefin material comprises one of high-density polyethylene, heat-resistant polyethylene and ultrahigh molecular weight polyethylene.
Further, the mass percentage of the polyolefin modified material containing fluorine groups in the blending material is 5-100 wt%.
Further, the thickness ratio of the inner layer of the pipe to the outer layer of the pipe is 1 (0-10), wherein the preferable thickness ratio is 1 (3-6), the thickness ratio can be properly adjusted according to application requirements, and a core die used for extruding the inner layer is subjected to mirror polishing and coated with a polytetrafluoroethylene coating to ensure sufficient low roughness.
The preparation method of the self-cleaning anti-scaling wax polyolefin pipe comprises the following steps:
1) blending the polyolefin modified material containing the fluorine group with a matrix polyolefin material to obtain a blended material;
2) and carrying out double-layer co-extrusion molding on the blending material and the polyolefin material to obtain the anti-scaling and anti-waxing polyolefin pipe.
Wherein, the matrix polyolefin material is a conventional commercial material, and the polyolefin modified material containing fluorine groups is a commercial material, or is prepared by adopting a method reported by a currently published literature, or is prepared by adopting the following steps:
1) placing the powder of the polyolefin main chain segment (such as LDPE powder, MDPE powder and the like) in a plasma device, performing vacuum treatment under the vacuum degree of 200mTorr, introducing helium or argon with the pressure of 250 and 1250mTorr as protective gas, then performing glow discharge with the treatment power of 10-250W (preferably 50-250W), namely plasma treatment, adjusting the plasma treatment condition to generate a large amount of free radicals on the surface of the polyolefin powder, and obtaining the powder of the polyolefin main chain segment with the surface containing the free radicals after treating for 10-600 s;
2) placing the polyolefin main chain segment powder with the surface containing the free radicals in the air for 5-1440min, and converting the surface free radicals into surface peroxides by oxygen in the air so as to obtain the polyolefin main chain segment powder with the surface containing the peroxides;
3) adding polyolefin main chain segment powder with surface containing peroxide as a free radical initiator into a solution of a polymerization monomer of a fluorine-containing group segment (such as poly (trifluoroethyl acrylate), poly (hexafluorobutyl acrylate) and the like), carrying out free radical polymerization of the polymerization monomer at 50-100 ℃ under the protection of nitrogen or argon, and reacting for 2-24h to obtain polymer powder, wherein the addition amount of the polyolefin main chain segment powder with surface containing peroxide is 5-95% of the mass of the polymerization monomer, the concentration of the polymerization monomer solution is 0.1-1g/mL, and the solvent is one of 1, 4-dioxane, toluene, xylene, N-methylpyrrolidone, N-methylacetamide, N-dimethylformamide or N, N-dimethylacetamide;
4) and washing and drying the polymer powder in sequence to obtain the polyolefin modified material with the surface grafted with the fluorine-containing group chain segment.
In addition, in the step 3), the free radical polymerization reaction comprises a common free radical polymerization reaction or a living free radical polymerization reaction;
when the free radical polymerization reaction is common free radical polymerization reaction, polyolefin powder with surface containing peroxide is directly added into a solvent containing a polymerization monomer as a free radical initiator;
when the free radical polymerization reaction is a living free radical polymerization reaction, the polyolefin powder with the surface containing peroxide is firstly reacted with diisopropyl xanthate or dithiobenzoic anhydride to form xanthate or dithioester on the surface of the polyolefin powder, and then the xanthate or dithioester is added into a solvent containing a polymerization monomer. The polyolefin powder containing xanthate or dithioester on the surface can be used as a chain transfer agent of living radical polymerization, namely a RAFT agent, so that the acrylic polymer can be grafted by means of RAFT polymerization.
The inner layer blending material can be directly extruded by an extruder with a high-dispersion screw, and in order to improve the dispersion effect, the double-screw granulation can be firstly carried out, and then the double-layer extrusion of the pipe extruder is carried out.
As a preferable technical scheme, in the blending process of the step 1) and the double-layer co-extrusion molding process of the step 2), conventional modified materials such as color master batches, antioxidants, extrusion modifiers and the like can be added according to needs.
The polyolefin pipe material with the self-cleaning function and the anti-scaling and anti-waxing function can be used for manufacturing an inner pipe of a steel wire winding pipe.
The invention introduces the long-chain polyethylene modified material with fluorine-containing graft, ensures the full combination with the matrix resin, endows the matrix material with lower surface energy, realizes the hydrophobic and oleophobic effects, and is finally applied to the fields needing scale prevention and wax deposition, such as crude oil transportation, heating, bittern transportation, inorganic and organic raw material transportation, and the like. In addition, the melting point of the fluorine-containing graft modified polyethylene material is slightly higher than that of the polyethylene material, so that the high temperature resistance can be improved to a certain extent; the fluorine-containing material can also block H to a certain extent2S、O2And the like, further enhancing the corrosion resistance of the equipment.
Compared with the prior art, the invention has the following characteristics:
1) the invention introduces the low surface energy modified layer as the inner wall of the pipeline, improves the surface performance of the inner wall of the pipeline (in the hydrophobic performance test, the contact angle is increased from 87.7 degrees to 98.4 degrees, so that the pipeline has the functions of self-cleaning, anti-scaling and wax deposition;
2) the modified material is a polyolefin material grafted and modified by a fluorine-containing group chain segment, and the fluorine-containing group chain segment can be migrated and concentrated on the surface of the inner wall of the pipeline, so that the surface energy of the inner wall of the pipeline is reduced; the fluorine-containing group chain segment which is not transferred to the surface can be anchored between the polyolefin main chain segment and the matrix polyolefin material chain segment, so that the bonding force of the two materials in the blending material is improved;
3) the introduction of the fluorine-containing group is beneficial to improving the melting point of the material, and the melting point of the HDPE subjected to grafting modification can be increased from 136.4 ℃ to 141.0 ℃ in a performance test. Therefore, the temperature resistance of the inner layer material of the pipe can be improved to a certain extent. Due to the introduction of the fluorine-containing group, the gas barrier effect is achieved to a certain extent, and the corrosion resistance of the equipment is improved.
Drawings
FIG. 1 is a schematic structural diagram of a self-cleaning anti-fouling and wax-deposition polyolefin pipe in example 1;
FIG. 2 is an enlarged view of a portion of FIG. 1 at A;
FIG. 3 is a graph showing the results of a contact angle test of a water drop on the surface of an HDPE pellet of the polyethylene modified material without the addition of fluorine-containing groups in example 1;
FIG. 4 is a graph showing the contact angle test results of water drops on the surface of a pressed sheet of the fluorine group-containing polyethylene modified material and the HDPE blend material in example 1;
FIG. 5 is a graph showing the results of a first water drop rolling test performed on the surface of an HDPE pellet of example 1 to which a fluorine group-containing polyethylene modified material is not added;
FIG. 6 is a graph showing the results of a second water drop rolling test performed on the surface of an HDPE pellet of example 1 without a fluorine-containing group-containing polyethylene modified material;
FIG. 7 is a graph showing the results of a first water drop rolling test performed on the surface of a pellet of a fluorine-containing group-containing polyethylene modified material and HDPE blend material in example 1;
FIG. 8 is a graph showing the results of a second water drop rolling test performed on the surface of a pellet of the fluorine-containing group-containing polyethylene modified material and HDPE blend material of example 1;
FIG. 9 is a graph showing the results of melting point and enthalpy of fusion tests for HDPE of example 1 in FIG. 8.
FIG. 10 is a graph showing the melting point and enthalpy of fusion test results for the fluorinated grafted HDPE of example 1.
The notation in the figure is:
1-inner layer of pipe, 2-outer layer of pipe, 3-segment containing fluorine group, and 4-main segment of polyolefin.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The outer layer material of the polyolefin pipe in each of the following examples was a commercially available polyethylene material. The inner layer material is prepared by the following steps:
1) placing the powder of the polyolefin main chain segment (such as LDPE powder, MDPE powder and the like) in a plasma device, performing vacuum treatment under the vacuum degree of 200mTorr, introducing helium or argon with the pressure of 250 and 1250mTorr as protective gas, then performing glow discharge with the treatment power of 10-250W (preferably 50-250W), namely plasma treatment, adjusting the plasma treatment condition to generate a large amount of free radicals on the surface of the polyolefin powder, and obtaining the powder of the polyolefin main chain segment with the surface containing the free radicals after treating for 10-600 s;
2) placing the polyolefin main chain segment powder with the surface containing the free radicals in the air for 5-1440min, and converting the surface free radicals into surface peroxides by oxygen in the air so as to obtain the polyolefin main chain segment powder with the surface containing the peroxides;
3) adding polyolefin main chain segment powder with surface containing peroxide as a free radical initiator into a solution of a polymerization monomer of a fluorine-containing group segment (such as poly (trifluoroethyl acrylate), poly (hexafluorobutyl acrylate) and the like), carrying out free radical polymerization of the polymerization monomer at 50-100 ℃ under the protection of nitrogen or argon, and reacting for 2-24h to obtain polymer powder, wherein the addition amount of the polyolefin main chain segment powder with surface containing peroxide is 5-95% of the mass of the polymerization monomer, the concentration of the polymerization monomer solution is 0.1-1g/mL, and the solvent is one of 1, 4-dioxane, toluene, xylene, N-methylpyrrolidone, N-methylacetamide, N-dimethylformamide or N, N-dimethylacetamide;
4) and washing and drying the polymer powder in sequence to obtain the polyolefin modified material with the surface grafted with the fluorine-containing group chain segment.
Example 1:
as shown in figure 1, the inner layer 1 of the polyolefin pipe material is a blended material of a polyethylene modified material containing fluorine groups and a matrix polyethylene material; the pipe is extruded by a double-layer co-extrusion extruder, and the material of the outer layer 2 of the pipe is polyethylene material.
As shown in fig. 2, the polyethylene modified material containing a fluorine group in the inner layer 1 of the pipe is a modified polyethylene material containing a polyethylene segment as a polyolefin main segment 4 and a fluorine-containing group segment 3 as a graft segment, wherein the polyethylene segment is HDPE, and the fluorine-containing group segment 3 is hexafluorobutyl acrylate.
The polyethylene modified material containing the fluorine groups can migrate to a certain extent, and most of the fluorine-containing group chain segments 3 can gather on the inner wall of the pipeline, so that the aim of reducing the surface energy is fulfilled; the main chain end of the modified material is a polyethylene long chain segment which can be well fused with a matrix polyethylene material; and part of the fluorine-containing groups which do not migrate to the surface can further anchor the acting force between the polyethylene modified material containing the fluorine groups and the matrix polyethylene material.
The inner layer 1 of the pipe is a blending material of polyolefin modified material containing fluorine groups and matrix polyolefin material, wherein the addition amount of the polyolefin modified material containing fluorine groups is 7.5 wt%.
The matrix polyolefin material and the outer layer material of the pipe are both HDPE.
The thickness ratio of the inner layer to the outer layer of the pipe is as follows: 1:5.
The outer diameter of the pipe is 25mm, and the wall thickness is 2.8 mm.
The pipe is formed by double-layer co-extrusion and one-step forming. Wherein, the core mould used for inner layer extrusion is mirror polished and coated with a polytetrafluoroethylene coating to ensure enough low roughness.
As shown in FIGS. 3 and 4, the contact angle of the inner layer material HDPE added with the modified material is increased from 87.7 degrees to 98.4 degrees, and the surface hydrophobic property is obviously improved. The rolling behaviors of water drops before and after modification of the inner layer material are respectively tested, as shown in fig. 5 and 6, the water drops on the surface of the HDPE material roll to have an obvious trailing phenomenon, as shown in fig. 7 and 8, the modified water drops roll on the surface of the material more easily, and the trailing phenomenon does not occur. The results all show that the addition of the modified material is beneficial to improving the surface hydrophobicity of the inner layer material of the pipe. In addition, as shown in fig. 9 and 10, the melting point of HDPE is 136.4 ℃, the melting point of the fluorine-containing graft modification material is 141.0 ℃, and the melting temperature of the added fluorine-containing graft modification material is obviously higher than that of HDPE, so that the temperature resistance of the pipe can be improved to a certain extent.
Example 2:
the polyolefin pipe material has inner layer and outer layer of both the inner layer and the outer layer of the pipe material of modified polyethylene material containing fluoric group and mixed UHMWPE material.
The polyethylene modified material containing the fluorine-containing group is a modified polyethylene material which takes a polyethylene chain segment as a polyolefin main chain segment 4 and takes a fluorine-containing group chain segment 3 as a grafting chain segment, wherein the polyethylene chain segment is LDPE, and the fluorine-containing group chain segment 3 is polyacrylic acid dodecafluoroheptyl ester.
The amount of the fluorine group-containing polyethylene modified material added was 10 wt%.
The core die used is mirror polished and coated with a polytetrafluoroethylene coating to ensure sufficiently low roughness.
The outer diameter of the pipe is 65mm, and the inner diameter is 55 mm. The prepared pipe can be subsequently used as an inner pipe of a steel wire winding pipe.
Example 3:
an anti-scaling and anti-waxing polyolefin pipe is shown in figure 1, and has a two-layer structure, wherein the inner layer 1 of the pipe is a blend material of a polyethylene modified material containing fluorine groups and PERT, and the outer layer 2 of the pipe is made of PERT.
The polyethylene modified material containing the fluorine-containing group is a modified polyethylene material which takes a polyethylene chain segment as a polyolefin main chain segment 4 and takes a fluorine-containing group chain segment 3 as a grafting chain segment, wherein the polyethylene chain segment is PERT, and the fluorine-containing group chain segment 3 is poly (trifluoroethyl acrylate).
The amount of the fluorine group-containing polyethylene modified material added to the blend material was 7.5 wt%.
The proportion of the inner layer 1 of the pipe and the outer layer 2 of the pipe is as follows: 1:5.
The outer diameter of the pipe is 25mm, and the wall thickness is 2.8mm
The pipe is formed by double-layer co-extrusion and one-step forming. Wherein, the core mould used for inner layer extrusion is mirror polished and coated with a polytetrafluoroethylene coating to ensure enough low roughness.
Example 4:
a polyolefin pipe material capable of automatically cleaning and preventing scaling and wax deposition comprises a pipe material inner layer 1 and a pipe material outer layer 2, wherein the pipe material inner layer 1 is made of a blend material of a polyolefin modified material containing fluorine groups and a matrix polyolefin material, and the pipe material outer layer 2 is made of a polyolefin material.
The polyolefin modified material containing the fluorine-containing group comprises a polyolefin main chain segment 4 and a fluorine-containing group chain segment 3 grafted on the polyolefin main chain segment 4, wherein the polyolefin main chain segment 4 is LDPE, and the fluorine-containing group chain segment 1 is poly (decafluoroheptyl methacrylate).
The matrix polyolefin material in the blending material and the polyolefin material in the outer layer 2 of the pipe are both high-density polyethylene. The mass percentage of the polyolefin modified material containing fluorine groups in the blending material is 5 wt%.
The thickness ratio of the inner layer 1 to the outer layer 2 of the pipe is 1: 10. Wherein, the core mould used for inner layer extrusion is mirror polished and coated with a polytetrafluoroethylene coating to ensure enough low roughness.
The anti-scaling and anti-waxing polyolefin pipe material in the embodiment is prepared by the following method:
1) blending the polyolefin modified material containing the fluorine group with a matrix polyolefin material to obtain a blended material;
2) and carrying out double-layer co-extrusion molding on the blending material and the polyolefin material to obtain the anti-scaling and anti-waxing polyolefin pipe.
Adding conventional modified materials such as color master batches, antioxidants, extrusion modifiers and the like in the blending process of the step 1) and the double-layer co-extrusion molding process of the step 2).
Example 5:
a polyolefin pipe material capable of automatically cleaning and preventing scaling and wax deposition comprises a pipe material inner layer 1 and a pipe material outer layer 2, wherein the pipe material inner layer 1 is made of a blend material of a polyolefin modified material containing fluorine groups and a matrix polyolefin material, and the pipe material outer layer 2 is made of a polyolefin material.
The polyolefin modified material containing the fluorine-containing group comprises a polyolefin main chain segment 4 and a fluorine-containing group chain segment 3 grafted on the polyolefin main chain segment 4, wherein the polyolefin main chain segment 4 is MDPE, and the fluorine-containing group chain segment 1 is one of poly (perfluorodecyl ethylene).
The matrix polyolefin material in the blending material and the polyolefin material in the outer layer of the pipe are both high-density polyethylene, and the mass percentage of the polyolefin modified material containing fluorine groups in the blending material is 20 wt%.
The thickness ratio of the inner layer 1 to the outer layer 2 of the pipe is 1: 10. Wherein, the core mould used for inner layer extrusion is mirror polished and coated with a polytetrafluoroethylene coating to ensure enough low roughness.
The anti-scaling and anti-waxing polyolefin pipe material in the embodiment is prepared by the following method:
1) blending the polyolefin modified material containing the fluorine group with a matrix polyolefin material to obtain a blended material;
2) and carrying out double-layer co-extrusion molding on the blending material and the polyolefin material to obtain the anti-scaling and anti-waxing polyolefin pipe.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. The polyolefin pipe material is characterized by comprising a pipe material inner layer and a pipe material outer layer, wherein the pipe material inner layer is made of a blend material of a polyolefin modified material containing fluorine groups and a matrix polyolefin material, and the pipe material outer layer is made of a polyolefin material;
the polyolefin modified material containing the fluorine group comprises a polyolefin main chain segment and a fluorine-containing group chain segment grafted on the polyolefin main chain segment;
the polyolefin main chain section comprises one of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, heat-resistant polyethylene or ultrahigh molecular weight polyethylene;
the fluorine-containing group chain segment is one of functional groups generated by graft polymerization of fluorine-containing and double-bond reaction monomers, and comprises poly (trifluoroethyl acrylate), poly (hexafluorobutyl acrylate), poly (dodecafluoro heptyl methacrylate) and poly (perfluorodecyl ethylene).
2. The self-cleaning anti-scaling polyolefin pipe as claimed in claim 1, wherein the base polyolefin material in the blend material and the polyolefin material in the outer layer of the pipe are the same polyolefin material, and the polyolefin material comprises one of high density polyethylene, heat resistant polyethylene and ultra high molecular weight polyethylene.
3. The self-cleaning anti-scaling polyolefin pipe as claimed in claim 1, wherein the polyolefin modified material containing fluorine groups in the blended material is 5-100 wt%.
4. The self-cleaning anti-scaling polyolefin pipe material as claimed in claim 1, wherein the thickness ratio of the inner layer to the outer layer is 1 (0-10).
5. A process for the preparation of a self-cleaning antifouling waxed polyolefin pipe, as claimed in any one of claims 1 to 4, comprising:
1) blending the polyolefin modified material containing the fluorine group with a matrix polyolefin material to obtain a blended material;
2) and co-extruding the blending material and the polyolefin material in a double layer manner to obtain the anti-scaling and anti-waxing polyolefin pipe.
6. Use of a self-cleaning anti-fouling and wax-depositing polyolefin pipe material as claimed in any one of claims 1 to 4 for making an inner pipe of a wire-wound pipe.
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| CN111421932A (en) * | 2020-04-21 | 2020-07-17 | 天津市伟星新型建材有限公司 | Anti-scaling plastic pipe with far infrared radiation function and preparation method thereof |
| CN113357446B (en) * | 2021-06-01 | 2023-09-29 | 天津市伟星新型建材有限公司 | Self-cleaning floor heating pipeline and preparation method thereof |
| CN113308034A (en) * | 2021-07-16 | 2021-08-27 | 山东科力新材料有限公司 | Anti-scaling mining pipe and preparation method thereof |
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