CN115122712B - Modified PPR low-temperature-resistant pipeline and preparation method thereof - Google Patents
Modified PPR low-temperature-resistant pipeline and preparation method thereof Download PDFInfo
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- CN115122712B CN115122712B CN202210881076.4A CN202210881076A CN115122712B CN 115122712 B CN115122712 B CN 115122712B CN 202210881076 A CN202210881076 A CN 202210881076A CN 115122712 B CN115122712 B CN 115122712B
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- pipe body
- temperature
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 116
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 67
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 67
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 60
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 229910052788 barium Inorganic materials 0.000 claims abstract description 49
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011521 glass Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000007822 coupling agent Substances 0.000 claims abstract description 35
- 238000001125 extrusion Methods 0.000 claims abstract description 30
- 239000000805 composite resin Substances 0.000 claims abstract description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010457 zeolite Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002667 nucleating agent Substances 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims abstract 7
- 238000002156 mixing Methods 0.000 claims description 80
- 229920001903 high density polyethylene Polymers 0.000 claims description 60
- 239000004700 high-density polyethylene Substances 0.000 claims description 60
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 56
- 239000002131 composite material Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 29
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 28
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 26
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 25
- 239000004917 carbon fiber Substances 0.000 claims description 25
- 230000000694 effects Effects 0.000 claims description 24
- 239000000395 magnesium oxide Substances 0.000 claims description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 23
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 196
- 239000011229 interlayer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
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- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- -1 Polypropylene Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
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- 239000011159 matrix material Substances 0.000 description 3
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 1
Classifications
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- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- C—CHEMISTRY; METALLURGY
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified PPR low-temperature-resistant pipeline, which comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer, wherein the pipe body inner layer, the modified PPR middle layer and the pipe body outer layer are formed by sequentially co-extrusion from inside to outside, the modified PPR middle layer is formed by randomly copolymerizing PPR, nano calcium carbonate, barium glass powder, talcum powder, a coupling agent, a nucleating agent TMB and absolute ethyl alcohol, the pipe body inner layer is made of PEEK resin composite material, and the antibacterial layer is formed by nano silver and zeolite powder; the preparation process comprises the following steps: raw materials of an antibacterial layer, a pipe inner layer, a modified PPR middle layer and a pipe outer layer of the modified PPR low-temperature-resistant pipeline are proportionally fed into respective feeders; quantitatively feeding into different extruders to melt and plasticize; and then forming a pipe blank through coextrusion, and cooling, shaping and drying to obtain the modified PPR low-temperature-resistant pipeline. The invention effectively improves the low-temperature toughness, the dimensional stability and the heat-resistant stability of the random copolymerization PPR pipeline.
Description
Technical Field
The invention relates to the technical field of plastic pipelines, in particular to a modified PPR low-temperature-resistant pipeline and a preparation method thereof.
Background
PPR (Random copolymer Polypropylene: english: polypropylene-Random) water pipe is a polymeric material pipe, commonly called as three-type Polypropylene, PPR pipe is a updated product of UPVC water supply pipe, aluminum plastic pipe, PE-X pipe and PE-RT pipe, has the advantages of energy saving, material saving, environmental protection, low density, light weight, corrosion resistance and the like, is simple and convenient in the installation, construction and maintenance process, can greatly lighten the construction strength of workers, and can be widely applied to the construction fields of building water supply and drainage, urban and rural water supply and drainage, urban fuel gas, electric power and optical cable jackets, industrial fluid transportation, agricultural irrigation and the like, municipal administration, industry and agriculture; because the PPR pipe is formed by extruding random copolymer polypropylene, the strength and high temperature resistance of the polypropylene are well ensured, and the PPR pipe has the comprehensive advantages of safety, sanitation, convenient construction, long service life and the like, and is widely applied to the fields of liquid transportation and gas transportation, thereby becoming the dominant force of water pipe materials. However, the PPR pipe can be embrittled at low temperature under low temperature, and cracks can be formed after the PPR pipe is impacted by external force, so that certain hidden danger can be caused in practical application, and particularly in cold winter, the PPR pipe is extremely easy to cause embrittlement when impacted in the transportation, construction and use processes, so that the service life of the PPR pipe is shortened, the use effect of the PPR pipe is affected, and therefore, the PPR pipe with low temperature resistance and good low temperature toughness is necessary to be researched and developed.
Disclosure of Invention
The invention aims to provide a modified PPR low-temperature-resistant pipeline and a preparation method thereof, wherein the surface modifier is used for carrying out wet surface modification on nano calcium carbonate, and then the modified PPR low-temperature-resistant pipeline is compounded with a random copolymerization PPR material, so that the compatibility of nano particles in a polymer matrix is realized, and the stability of a molecular structure and the capability of bearing stress of molecules in the PPR pipeline to the structure are improved through crosslinking and nano particle compatible polymerization of the PPR pipe; the low-temperature toughness, the dimensional stability and the heat-resistant stability of the random copolymer PPR pipeline are effectively improved. The technical scheme adopted by the invention is as follows:
according to one aspect of the invention, a modified PPR low-temperature-resistant pipeline is provided, the modified PPR low-temperature-resistant pipeline comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer which are formed by sequentially co-extrusion from inside to outside, and the modified PPR middle layer is prepared from the following raw materials in parts by weight: 80-120 parts of random copolymerization PPR, 20-40 parts of nano calcium carbonate, 8-15 parts of barium glass powder, 5-8 parts of talcum powder, 0.2-2 parts of coupling agent, 0.1-1 part of nucleating agent TMB and 25-45 parts of absolute ethyl alcohol; the particle size of the barium glass powder is 0.02-0.5 mu m; the particle size of the nano calcium carbonate is 70nm-120nm, and the coupling agent is any one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent.
The preparation of the raw materials of the modified PPR interlayer further preferably comprises the following steps: adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating up and carrying out ultrasonic stirring for 10-30 min to obtain a mixture A;
adding nano calcium carbonate into a kneader for stirring, adding the mixture A for continuous stirring for 10-20 min, and taking out to obtain a mixture B; adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 10-30 min at 160-200 ℃; and then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain the modified PPR intermediate layer raw material master batch.
The above scheme is further preferable that the temperature of melt extrusion granulation in the twin-screw extruder is 80-120 ℃, and the twin-screw rotating speed of the twin-screw extruder is 30-100 rpm.
The above scheme is further preferable that the temperature of stirring in the kneader is 120-180 ℃, the stirring speed is 600-1200rpm, and the stirring time is 5-10 min.
The above scheme is further preferable that an antibacterial layer is arranged on the inner wall of the inner layer of the pipe body at intervals, the thickness ratio of the antibacterial layer to the inner layer of the pipe body to the modified PPR intermediate layer to the outer layer of the pipe body is 0.2-0.5:2:4:0.8-1.5, the antibacterial layer is arranged on the inner wall of the inner layer of the pipe body along the axial direction or the circumferential direction, the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetraol stearate and di-tert-butyl peroxyisopropyl benzene; according to the invention, the nano calcium carbonate particle size is 60-100 nm, each 100 parts by weight of the high-density polyethylene composite material is prepared by mixing 35-65 parts of high-density polyethylene, 5-10 parts of carbon fiber, 15-25 parts of nano calcium carbonate, 6-12 parts of high-activity magnesium oxide, 2-8 parts of pentetanol stearate and 5-10 parts of di-tert-butyl peroxyisopropyl benzene, mixing nano calcium carbonate, high-activity magnesium oxide, pentetanol stearate and di-tert-butyl peroxyisopropyl benzene for 20-30 min at the temperature of 100-120 ℃, mixing the mixing speed of 300-600rpm, adding the high-density polyethylene, pentetanol stearate, di-tert-butyl peroxyisopropyl benzene and carbon fiber, mixing for 3-8 min at the temperature of 160-200 ℃, mixing the speed of 800-1000 rpm, and granulating to obtain the high-density polyethylene composite material.
The scheme is further preferable that the antibacterial layer is prepared from nano silver and zeolite powder, and the mass ratio of the nano silver to the zeolite powder is 1:4-8.
The above scheme is further preferable, the inner layer of the pipe body is made of PEEK resin composite material, the PEEK resin composite material is made by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 3-6:1:0.5, the particle size of the PEEK resin is 1 μm-10 μm, the fiber length of the barium glass is 2-5mm, the average length of the lignocellulose is 0.5mm-2mm, and the preparation process is as follows: firstly, mixing barium glass and lignocellulose at 120-150 ℃, stirring and drying for 20-40min; and adding PEEK resin, stirring and mixing, and carrying out melt extrusion granulation at 300-380 ℃ to obtain a particle material of 20-60 mu m, thereby obtaining the PEEK resin composite material.
The preparation process of the PEEK resin composite material further preferably comprises the following steps: firstly, mixing barium glass and lignocellulose at 120-150 ℃, stirring and drying for 20-40min; and adding PEEK resin, stirring and mixing, melting and extruding at 300-380 ℃, and granulating into 20-60 mu m particle materials to obtain the PEEK resin composite material.
According to another aspect of the invention, the invention provides a preparation method of a modified PPR low-temperature-resistant pipeline, which comprises the following steps:
step 1: feeding, namely feeding raw materials of an antibacterial layer, an inner pipe layer, an intermediate modified PPR layer and an outer pipe layer of the modified PPR low-temperature-resistant pipeline into respective feeders in proportion;
step 2, extrusion molding, namely quantitatively feeding raw materials of the antibacterial layer, the inner layer of the pipe body, the modified PPR middle layer and the outer layer of the pipe body into different extruders from a feeding machine for melting and plasticizing; extruding an antibacterial layer and an inner layer of the pipe body in a double-layer coextrusion mode, and extruding a modified PPR middle layer and an outer layer of the pipe body in a double-layer coextrusion mode so as to form a pipe blank, wherein the pipe blank enters a sizing sleeve to be extruded and formed into a pipe shape under the traction of a tractor, so that a multi-layer sizing composite pipe is formed;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
The above scheme is further preferable that the temperature of the extruded antibacterial layer is 160-190 ℃; the temperature of the inner layer of the extruded tube body is 250-300 ℃; the temperature of the extrusion modified PPR middle layer is 200-250 ℃, and the temperature of the extrusion pipe outer layer is 180-220 ℃.
(1) According to the invention, the nano calcium carbonate is subjected to wet surface modification by the surface modifier, and then is compounded with the random copolymerization PPR material, so that the compatibility of nano particles in a polymer matrix is realized, and the stability of a molecular structure and the capability of bearing stress of molecules in a structure of the PPR pipe are improved by crosslinking and nano particle compatible polymerization of the PPR pipe; effectively improves the rheological property, the dimensional stability and the heat-resistant stability of the random copolymer PPR product.
(2) The invention adopts one-step extrusion molding production, has simple process, less equipment investment and high production efficiency, and prepares the PPR temperature pipeline with excellent low-temperature toughness and mechanical property, thereby maintaining the rigidity, strength and pressure resistance of the PPR; and the PPR pipe with high temperature resistance and freezing resistance and high toughness is formed by co-extrusion inside and outside the PPR middle layer, so that the probability of brittle fracture of the PPR pipe at low temperature or normal temperature is reduced, the problem of insufficient toughness and rigidity of the PPR pipe is solved, the problem of brittle fracture easily caused after external force impact is effectively improved, the service life of the PPR pipe is prolonged, the practical market requirement is met, and the transportation and application reliability of the PPR pipe in a low-temperature environment is improved.
Drawings
FIG. 1 is a schematic view showing the internal structure of a modified PPR low temperature resistant pipeline according to embodiments 1 to 3 of the present invention;
FIG. 2 is a schematic cross-sectional structure of FIG. 1;
FIG. 3 is a schematic view showing the internal structure of a modified PPR low temperature resistant pipeline according to embodiment 4 of the present invention
FIG. 4 is a schematic cross-sectional structure of FIG. 3;
in the drawing, a pipe body inner layer 1, a modified PPR middle 2, a pipe body outer layer 3 and an antibacterial layer 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below by referring to the accompanying drawings and by illustrating preferred embodiments. It should be noted, however, that many of the details set forth in the description are merely provided to provide a thorough understanding of one or more aspects of the invention, and that these aspects of the invention may be practiced without these specific details.
Example 1:
referring to fig. 1 and 2, according to the modified PPR low temperature resistant pipeline provided by the invention, the modified PPR low temperature resistant pipeline comprises a pipe body inner layer 1, a modified PPR middle layer 2 and a pipe body outer layer 3 which are formed by coextrusion in sequence from inside to outside, wherein the pipe body inner layer is made of a PEEK resin composite material; an antibacterial layer 4 is arranged on the inner wall of the inner layer of the pipe body at intervals, and the thickness ratio of the antibacterial layer 4 to the inner layer 1 of the pipe body to the modified PPR middle layer 2 to the outer layer 3 of the pipe body is 0.2:2:4:0.8; the antibacterial layer is arranged on the inner wall of the inner layer of the pipe body along the axial direction.
The PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 2:1:0.5, and firstly mixing, stirring and drying the barium glass and the lignocellulose at 120 ℃ for 20min; adding PEEK resin, stirring and mixing, melting and extruding at 300 ℃, and granulating to obtain a 20 mu m granular material, so as to obtain a PEEK resin composite material; the particle size of PEEK resin is 1 mu m, the fiber length of barium glass is 2mm, and the average length of lignocellulose is 0.5mm; polyether ether ketone (PEEK) is a linear aromatic high molecular compound containing chain links in a molecular main chain, and is a high-temperature-resistant and high-performance thermoplastic special engineering plastic. PEEK has good mechanical properties, chemical resistance, abrasion resistance, hydrolysis resistance and other properties; PEEK resin, barium glass and lignocellulose are loaded on fibers to be mutually fused, so that the mechanical bonding capability of the PEEK resin is enhanced, and the mechanical properties of the composite material such as stretching, impact and bending are effectively improved. Simultaneously, the thermal expansion coefficient and the cold contraction coefficient of the material are reduced, the lignocellulose has a capillary structure, the raw material mixing is effectively promoted to be more uniform, the cracking or the pulling crack and the like caused by the displacement generated in the material are prevented, the stability and the thermal stability of the inner layer of the pipe body can be ensured by the lignocellulose, and the pipeline has a good cracking resistance in the use process.
The outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing. In the embodiment, the particle size of the nano calcium carbonate is 60nm, each 100 parts by weight of the high-density polyethylene composite material is prepared by mixing 65 parts of high-density polyethylene, 5 parts of carbon fiber, 15 parts of nano calcium carbonate, 8 parts of high-activity magnesium oxide, 2 parts of pentatetrol stearate and 5 parts of bis-tert-butyl peroxyisopropyl benzene, mixing the nano calcium carbonate, the high-activity magnesium oxide, the pentatetrol stearate and the bis-tert-butyl peroxyisopropyl benzene for 20min at 100 ℃, mixing the mixture at 300rpm, adding the high-density polyethylene, the pentatetrol stearate, the bis-tert-butyl peroxyisopropyl benzene and the carbon fiber, mixing the mixture at 800rpm at 160 ℃, and granulating to obtain the high-density polyethylene composite material; after mixing, the raw materials are promoted to be mixed more uniformly, the obtained composite material can resist low temperature, and the outer layer of the pipe body can be effectively prevented from being cracked or pulled and the like. High Density Polyethylene (HDPE) is nontoxic, odorless, has crystallinity of 80% -90%, softening point of 125-135 ℃, and service temperature of 100 ℃; has excellent hardness, tensile strength and creep property; the wear resistance toughness and the cold resistance are good; the chemical stability is good, and the water-soluble polyurethane resin is insoluble in any organic solvent, and is resistant to corrosion by acid, alkali and various salts under the condition of room temperature; the nano calcium carbonate is also called ultrafine calcium carbonate, can improve rheological property in the preparation process of the plastic master batch, improves formability of the plastic master batch, has the functions of toughening and reinforcing, and can effectively improve bending strength, bending elastic modulus, heat distortion temperature and dimensional stability of the PPR pipe; the special fiber formed by carbon elements has the characteristics of good high temperature resistance, friction resistance, corrosion resistance and the like, is fibrous in shape, soft, can be processed into various fabrics, is widely applied to reinforced epoxy resin composite materials, has extremely high specific strength and specific modulus, and has low density, so that the specific strength and specific modulus are high. Carbon fibers are widely used in the fields of reinforcing materials, resins, metals, ceramics, carbon, and the like.
In the embodiment of the invention, the antibacterial layer is prepared from nano silver and zeolite powder, the mass ratio of the nano silver to the zeolite powder is 1:4, the nano silver of the antibacterial layer can reduce the possibility of bacteria breeding on the inner wall of the PPR pipe and the possibility of bacteria pollution of water, the zeolite powder in the antibacterial layer can not only play a role in reinforcing the inner wall of the pipe, but also promote the slow release of the nano silver, so that the nano silver can perform long-acting antibacterial and bacteriostatic effects on the water in the pipe, and the zeolite and the nano silver can play a role in bacteriostasis together.
In the embodiment of the invention, the modified PPR interlayer is prepared from the following raw materials in parts by weight: 120 parts of random copolymerization PPR, 20 parts of nano calcium carbonate, 8 parts of barium glass powder, 5 parts of talcum powder, 0.2 part of coupling agent, 0.1 part of nucleating agent TMB and 25 parts of absolute ethyl alcohol; the particle size of the barium glass powder is 0.02 mu m, and the particle size of the nano calcium carbonate is 70nm; the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent and a zirconate coupling agent, and the raw material preparation of the modified PPR intermediate layer comprises the following steps:
adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating and carrying out ultrasonic stirring for 10min to obtain a mixture A; adding nano calcium carbonate into a kneader for stirring, wherein the stirring temperature in the kneader is 120 ℃, the stirring speed is 600rpm, the stirring time is 5min, and then adding the mixture A for continuous stirring for 10min, and then taking out to obtain a mixture B; adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 10min at 160 ℃; and then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain the modified PPR intermediate layer raw material master batch, wherein the temperature of the melt extrusion granulation in the double-screw extruder is 120 ℃, and the double-screw rotating speed of the double-screw extruder is 30rpm.
The preparation method of the modified PPR low-temperature-resistant pipeline comprises the following steps:
step 1: feeding, namely feeding raw materials of an antibacterial layer, an inner pipe layer, an intermediate modified PPR layer and an outer pipe layer of the modified PPR low-temperature-resistant pipeline into respective feeders in proportion; the antibacterial layer is prepared from nano silver and zeolite powder in a mass ratio of 1:4, the inner layer of the pipe body is prepared from a PEEK resin composite material, and the PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a mass ratio of 2:1:0.5;
the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing; the modified PPR interlayer is prepared from the following raw materials in parts by weight: 120 parts of random copolymerization PPR, 20 parts of nano calcium carbonate, 8 parts of barium glass powder, 5 parts of talcum powder, 0.2 part of coupling agent, 0.1 part of nucleating agent TMB and 25 parts of absolute ethyl alcohol;
step 2, extrusion molding, namely quantitatively feeding the antibacterial layer raw material, the pipe inner layer raw material, the modified PPR middle layer raw material and the pipe outer layer raw material into different extruders from a feeder for melting and plasticizing; extruding the antibacterial layer and the inner layer of the pipe body in a double-layer coextrusion mode, wherein the temperature of the extruded antibacterial layer is 160 ℃; the temperature of the inner layer of the extruded tube body is 250 ℃; extruding the modified PPR middle layer and the outer tube layer in a double-layer coextrusion mode so as to form a tube blank, wherein the temperature of the extruded modified PPR middle layer is 200 ℃, the temperature of the extruded outer tube layer is 180 ℃, and the tube blank enters a sizing sleeve to be extruded and formed into a tube shape under the traction of a tractor to form a multi-layer sizing composite tube;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
Example 2:
referring to fig. 1 and 2, according to the modified PPR low temperature resistant pipeline provided by the invention, the modified PPR low temperature resistant pipeline comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer which are formed by coextrusion in sequence from inside to outside, wherein the pipe body inner layer is made of a PEEK resin composite material; an antibacterial layer is arranged on the inner wall of the inner layer of the pipe body at intervals, and the thickness ratio of the antibacterial layer to the inner layer of the pipe body to the modified PPR intermediate layer to the outer layer of the pipe body is 0.5:2:4:1.5; the antibacterial layer is arranged on the inner wall of the inner layer of the pipe body along the axial direction.
The PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 3:1:0.5, and firstly mixing, stirring and drying the barium glass and the lignocellulose at 150 ℃ for 40min; adding PEEK resin, stirring and mixing, melting and extruding at 380 ℃, and granulating to obtain 60 mu m particle materials, thus obtaining PEEK resin composite materials; the particle size of PEEK resin is 10 mu m, the fiber length of barium glass is 5mm, and the average length of lignocellulose is 2mm; polyether ether ketone (PEEK) is a linear aromatic high molecular compound containing chain links in a molecular main chain, and is a high-temperature-resistant and high-performance thermoplastic special engineering plastic. PEEK has good mechanical properties, chemical resistance, abrasion resistance, hydrolysis resistance and other properties; PEEK resin, barium glass and lignocellulose are loaded on fibers to be mutually fused, so that the mechanical bonding capability of the PEEK resin is enhanced, and the mechanical properties of the composite material such as stretching, impact and bending are effectively improved. Simultaneously, the thermal expansion and cold contraction coefficients of the material are reduced;
the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing. In the embodiment, the particle size of the nano calcium carbonate is 100nm, each 100 parts by weight of the high-density polyethylene composite material is prepared by mixing 35 parts of high-density polyethylene, 10 parts of carbon fiber, 25 parts of nano calcium carbonate, 12 parts of high-activity magnesium oxide, 8 parts of pentatetrol stearate and 10 parts of bis-tert-butyl peroxyisopropyl benzene, mixing the nano calcium carbonate, the high-activity magnesium oxide, the pentatetrol stearate and the bis-tert-butyl peroxyisopropyl benzene for 30min at 120 ℃, mixing the high-density polyethylene, the pentatetrol stearate, the bis-tert-butyl peroxyisopropyl benzene and the carbon fiber for 8min at 200 ℃, mixing the high-density polyethylene composite material is obtained by granulating.
In the embodiment of the invention, the antibacterial layer is prepared from nano silver and zeolite powder, and the mass ratio of the nano silver to the zeolite powder is 1:4-8.
In the embodiment of the invention, the modified PPR interlayer is prepared from the following raw materials in parts by weight: 80 parts of random copolymerization PPR, 60 parts of nano calcium carbonate, 15 parts of barium glass powder, 8 parts of talcum powder, 2 parts of coupling agent, 1 part of nucleating agent TMB and 45 parts of absolute ethyl alcohol; the particle size of the nano calcium carbonate is 120nm, and the particle size of the barium glass powder is 0.5 mu m; the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent and a zirconate coupling agent, and the preparation of the PPR intermediate layer raw material comprises the following steps:
adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating and carrying out ultrasonic stirring for 30min to obtain a mixture A; adding nano calcium carbonate into a kneader for stirring, wherein the stirring temperature in the kneader is 150 ℃, the stirring speed is 1200rpm, the stirring time is 10min, and then adding the mixture A for continuous stirring for 20min, and then taking out to obtain a mixture B; adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 30min at 200 ℃; and then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain PPR intermediate layer raw material master batch, wherein the temperature of the melt extrusion granulation in the double-screw extruder is 120 ℃, and the double-screw rotating speed of the double-screw extruder is 100rpm.
The preparation method of the modified PPR low-temperature-resistant pipeline comprises the following steps:
step 1: feeding, namely feeding raw materials of an antibacterial layer, an inner pipe layer, an intermediate modified PPR layer and an outer pipe layer of the modified PPR low-temperature-resistant pipeline into respective feeders in proportion; the antibacterial layer is prepared from nano silver and zeolite powder in a mass ratio of 1:8, the inner layer of the pipe body is prepared from a PEEK resin composite material, and the PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a mass ratio of 6:1:0.5; the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing; wherein, every 100 weight parts of the high-density polyethylene composite material is prepared by mixing 30 parts of high-density polyethylene, 10 parts of carbon fiber, 30 parts of nano calcium carbonate, 12 parts of high-activity magnesium oxide, 8 parts of pentyl tetrastearate and 10 parts of di-tert-butyl peroxyisopropyl benzene; the modified PPR interlayer is prepared from the following raw materials in parts by weight: 80 parts of random copolymerization PPR, 60 parts of nano calcium carbonate, 15 parts of barium glass powder, 8 parts of talcum powder, 2 parts of coupling agent, 0.1-1 part of nucleating agent TMB and 45 parts of absolute ethyl alcohol;
step 2, extrusion molding, namely quantitatively feeding the antibacterial layer raw material, the pipe inner layer raw material, the modified PPR middle layer raw material and the pipe outer layer raw material into different extruders from a feeder for melting and plasticizing; extruding the antibacterial layer and the inner layer of the pipe body in a double-layer coextrusion mode, wherein the temperature of the extruded antibacterial layer is 190 ℃; the temperature of the inner layer of the extruded tube body is 300 ℃; extruding the modified PPR middle layer and the outer tube layer in a double-layer coextrusion mode so as to form a tube blank, wherein the temperature of the extruded modified PPR middle layer is 250 ℃, the temperature of the extruded outer tube layer is 220 ℃, and the tube blank enters a sizing sleeve to be extruded and formed into a tube shape under the traction of a tractor to form a multi-layer sizing composite tube;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
Example 3
Referring to fig. 1 and 2, according to the modified PPR low temperature resistant pipeline provided by the invention, the modified PPR low temperature resistant pipeline comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer which are formed by coextrusion in sequence from inside to outside, wherein the pipe body inner layer is made of a PEEK resin composite material; an antibacterial layer is arranged on the inner wall of the inner layer of the pipe body at intervals, and the thickness ratio of the antibacterial layer to the inner layer of the pipe body to the modified PPR intermediate layer to the outer layer of the pipe body is 0.3:2:4:1.2; the antibacterial layer is arranged on the inner wall of the inner layer of the pipe body along the axial direction.
The PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 5:1:0.5, and firstly mixing, stirring and drying the barium glass and the lignocellulose at 140 ℃ for 30min; adding PEEK resin, stirring and mixing, and carrying out melt extrusion at 360 ℃ to granulate into 40 mu m particle materials, thus obtaining PEEK resin composite materials; the particle size of PEEK resin is 6-8 mu m, the fiber length of barium glass is 3-4 mm, and the average length of lignocellulose is 1-1.5 mm; polyether ether ketone (PEEK) is a linear aromatic high molecular compound containing chain links in a molecular main chain, and is a high-temperature-resistant and high-performance thermoplastic special engineering plastic. PEEK has good mechanical properties, chemical resistance, abrasion resistance, hydrolysis resistance and other properties; PEEK resin, barium glass and lignocellulose are loaded on fibers to be mutually fused, so that the mechanical bonding capability of the PEEK resin is enhanced, and the mechanical properties of the composite material such as stretching, impact and bending are effectively improved. Simultaneously, the thermal expansion and cold contraction coefficients of the material are reduced;
the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing. In the embodiment, the particle size of the nano calcium carbonate is 80nm, each 100 parts by weight of the high-density polyethylene composite material is prepared by mixing 51 parts of high-density polyethylene, 8 parts of carbon fiber, 18 parts of nano calcium carbonate, 10 parts of high-activity magnesium oxide, 5 parts of pentatetrol stearate and 8 parts of bis-tert-butyl peroxyisopropyl benzene, mixing the nano calcium carbonate, the high-activity magnesium oxide, the pentatetrol stearate and the bis-tert-butyl peroxyisopropyl benzene for 25min at 110 ℃, mixing the mixture at 500rpm, adding the high-density polyethylene, the pentatetrol stearate, the bis-tert-butyl peroxyisopropyl benzene and the carbon fiber, mixing the mixture at 180 ℃ for 6min, mixing the mixture at 900rpm, and granulating to obtain the high-density polyethylene composite material; after mixing, the raw materials are promoted to be mixed more uniformly, the obtained composite material can resist low temperature, and the outer layer of the pipe body can be effectively prevented from being cracked or pulled and the like. High Density Polyethylene (HDPE) is nontoxic, odorless, has crystallinity of 80% -90%, softening point of 125-135 ℃, and service temperature of 100 ℃; has excellent hardness, tensile strength and creep property; the wear resistance toughness and the cold resistance are good; the chemical stability is good, and the water-soluble polyurethane resin is insoluble in any organic solvent, and is resistant to corrosion by acid, alkali and various salts under the condition of room temperature; the nano calcium carbonate is also called ultrafine calcium carbonate, can improve rheological property in the preparation process of the plastic master batch, improves formability of the plastic master batch, has the functions of toughening and reinforcing, and can effectively improve bending strength, bending elastic modulus, heat distortion temperature and dimensional stability of the PPR pipe; the special fiber formed by carbon elements has the characteristics of good high temperature resistance, friction resistance, corrosion resistance and the like, is fibrous in shape, soft, can be processed into various fabrics, is widely applied to reinforced epoxy resin composite materials, has extremely high specific strength and specific modulus, and has low density, so that the specific strength and specific modulus are high. Carbon fibers are widely used in the fields of reinforcing materials, resins, metals, ceramics, carbon, and the like.
In the embodiment of the invention, the antibacterial layer is prepared from nano silver and zeolite powder, the mass ratio of the nano silver to the zeolite powder is 1:6, the nano silver of the antibacterial layer can reduce the possibility of bacteria breeding on the inner wall of the PPR pipe and the possibility of bacteria pollution of water, the zeolite powder in the antibacterial layer can not only play a role in reinforcing the inner wall of the pipe, but also promote the slow release of the nano silver, so that the nano silver can perform long-acting antibacterial and bacteriostatic effects on the water in the pipe, and the zeolite and the nano silver can play a role in bacteriostasis together. In the embodiment of the invention, the modified PPR interlayer is prepared from the following raw materials in parts by weight: 100 parts of random copolymerization PPR, 30 parts of nano calcium carbonate, 12 parts of barium glass powder, 6 parts of talcum powder, 1 part of coupling agent, 0.6 part of nucleating agent TMB and 40 parts of absolute ethyl alcohol; the particle size of the nano calcium carbonate is 100nm, and the particle size of the barium glass powder is 0.05-0.2 mu m; the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent and a zirconate coupling agent, and the raw material preparation of the modified PPR intermediate layer comprises the following steps:
adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating and carrying out ultrasonic stirring for 25min to obtain a mixture A; adding nano calcium carbonate into a kneader for stirring, wherein the stirring temperature in the kneader is 140 ℃, the stirring speed is 1000rpm, the stirring time is 8min, and then adding the mixture A for continuous stirring for 15min, and then taking out to obtain a mixture B; adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 20min at 180 ℃; and then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain the modified PPR intermediate layer raw material master batch, wherein the temperature of the melt extrusion granulation in the double-screw extruder is 100 ℃, and the double-screw rotating speed of the double-screw extruder is 80rpm.
The preparation method of the modified PPR low-temperature-resistant pipeline comprises the following steps:
step 1: feeding, namely proportionally feeding raw materials of a pipe inner layer, a modified PPR middle layer and a pipe outer layer of the modified PPR low-temperature-resistant pipeline into respective feeders;
the antibacterial layer is prepared from nano silver and zeolite powder in a mass ratio of 1:6, the inner layer of the pipe body is prepared from a PEEK resin composite material, and the PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a mass ratio of 5:1:0.5; the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing; wherein, every 100 weight parts of the high-density polyethylene composite material is prepared by mixing 51 parts of high-density polyethylene, 8 parts of carbon fiber, 18 parts of nano calcium carbonate, 10 parts of high-activity magnesium oxide, 5 parts of pentyl tetraol stearate and 8 parts of di-tert-butyl peroxyisopropyl benzene; the modified PPR interlayer is prepared from the following raw materials in parts by weight: 100 parts of random copolymerization PPR, 30 parts of nano calcium carbonate, 12 parts of barium glass powder, 6 parts of talcum powder, 1 part of coupling agent, 0.6 part of nucleating agent TMB and 40 parts of absolute ethyl alcohol;
step 2, extrusion molding, namely quantitatively feeding the antibacterial layer raw material, the pipe inner layer raw material, the modified PPR middle layer raw material and the pipe outer layer raw material into different extruders from a feeder for melting and plasticizing; extruding the antibacterial layer and the inner layer of the pipe body in a double-layer coextrusion mode, wherein the temperature of the extruded antibacterial layer is 180 ℃; the temperature of the inner layer of the extruded tube body is 280 ℃; extruding the modified PPR middle layer and the outer tube layer in a double-layer coextrusion mode so as to form a tube blank, wherein the temperature of the extruded modified PPR middle layer is 240 ℃, the temperature of the extruded outer tube layer is 200 ℃, and the tube blank enters a sizing sleeve to be extruded and formed into a tube shape under the traction of a tractor to form a multi-layer sizing composite tube;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
Example 4
Referring to fig. 3 and 4, according to the modified PPR low temperature resistant pipeline provided by the invention, the modified PPR low temperature resistant pipeline comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer which are formed by coextrusion in sequence from inside to outside, wherein the pipe body inner layer is made of a PEEK resin composite material; an antibacterial layer is arranged on the inner wall of the inner layer of the pipe body at intervals, and the thickness ratio of the antibacterial layer to the inner layer of the pipe body to the modified PPR intermediate layer to the outer layer of the pipe body is 0.4:2:4:1; the antibacterial layer is arranged in the circumferential direction of the inner layer of the pipe body. The PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 4:1:0.5, and firstly mixing, stirring and drying the barium glass and the lignocellulose at 150 ℃ for 20min; adding PEEK resin, stirring and mixing, melting and extruding at 370 ℃, and granulating to obtain 50 mu m particle materials, thus obtaining PEEK resin composite materials; the particle size of PEEK resin is 5 mu m, the fiber length of barium glass is 3mm, and the average length of lignocellulose is 1.6mm-1.8mm;
the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing. In the embodiment, the particle size of the nano calcium carbonate is 90nm, each 100 parts by weight of the high-density polyethylene composite material is prepared by mixing 55 parts of high-density polyethylene, 7 parts of carbon fiber, 21 parts of nano calcium carbonate, 6 parts of high-activity magnesium oxide, 4 parts of pentatetrol stearate and 7 parts of bis-tert-butyl peroxyisopropyl benzene, mixing the nano calcium carbonate, the high-activity magnesium oxide, the pentatetrol stearate and the bis-tert-butyl peroxyisopropyl benzene for 25min at 120 ℃, mixing the mixture at 500rpm, adding the high-density polyethylene, the pentatetrol stearate, the bis-tert-butyl peroxyisopropyl benzene and the carbon fiber, mixing the mixture at 190 ℃ for 6min, mixing the mixture at 900rpm, and granulating to obtain the high-density polyethylene composite material.
In the embodiment of the invention, the antibacterial layer is prepared from nano silver and zeolite powder, wherein the mass ratio of the nano silver to the zeolite powder is 1:7; the modified PPR interlayer is prepared from the following raw materials in parts by weight: 90 parts of random copolymerization PPR, 25 parts of nano calcium carbonate, 10 parts of barium glass powder, 5 parts of talcum powder, 0.5 part of coupling agent, 0.8 part of nucleating agent TMB and 45 parts of absolute ethyl alcohol; the particle size of the nano calcium carbonate is 110nm, and the particle size of the barium glass powder is 0.2-0.3 mu m; the coupling agent is any one or more of a silane coupling agent, a titanate coupling agent and a zirconate coupling agent, and the raw material preparation of the modified PPR intermediate layer comprises the following steps:
adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating and carrying out ultrasonic stirring for 15min to obtain a mixture A; adding nano calcium carbonate into a kneader for stirring, wherein the stirring temperature in the kneader is 180 ℃, the stirring speed is 1000rpm, the stirring time is 10min, and then adding the mixture A for continuous stirring for 15min, and then taking out to obtain a mixture B; adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 20min at 190 ℃; and then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain the modified PPR intermediate layer raw material master batch, wherein the temperature of the melt extrusion granulation in the double-screw extruder is 110 ℃, and the double-screw rotating speed of the double-screw extruder is 90rpm.
The preparation method of the modified PPR low-temperature-resistant pipeline comprises the following steps:
step 1: feeding, namely proportionally feeding raw materials of a pipe inner layer, a modified PPR middle layer and a pipe outer layer of the modified PPR low-temperature-resistant pipeline into respective feeders;
the antibacterial layer is prepared from nano silver and zeolite powder in a mass ratio of 1:7, the inner layer of the pipe body is prepared from a PEEK resin composite material, and the PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a mass ratio of 4:1:0.5; the outer layer of the pipe body is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene by mixing; wherein, every 100 weight parts of the high-density polyethylene composite material is prepared by mixing 55 parts of high-density polyethylene, 7 parts of carbon fiber, 21 parts of nano calcium carbonate, 6 parts of high-activity magnesium oxide, 4 parts of pentyl tetrastearate and 7 parts of di-tert-butyl peroxyisopropyl benzene; the modified PPR interlayer is prepared from the following raw materials in parts by weight: 90 parts of random copolymerization PPR, 25 parts of nano calcium carbonate, 10 parts of barium glass powder, 5 parts of talcum powder, 0.5 part of coupling agent, 0.8 part of nucleating agent TMB and 45 parts of absolute ethyl alcohol;
step 2, extrusion molding, namely quantitatively feeding the antibacterial layer raw material, the pipe inner layer raw material, the modified PPR middle layer raw material and the pipe outer layer raw material into different extruders from a feeder for melting and plasticizing; extruding the antibacterial layer and the inner layer of the pipe body in a double-layer coextrusion mode, wherein the temperature of the extruded antibacterial layer is 180 ℃; the temperature of the inner layer of the extruded tube body is 280 ℃; extruding the modified PPR middle layer and the outer tube layer in a double-layer coextrusion mode so as to form a tube blank, wherein the temperature of the extruded modified PPR middle layer is 240 ℃, the temperature of the extruded outer tube layer is 200 ℃, and the tube blank enters a sizing sleeve to be extruded and formed into a tube shape under the traction of a tractor to form a multi-layer sizing composite tube;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
The PPR low temperature resistant pipeline prepared by the example is compared with a pipeline made of unmodified pure PPR material by a related performance test, and the related performance test is specifically shown in the following table 1.
Table 1: performance test comparison
As can be seen from the table 1, the nano calcium carbonate is subjected to wet surface modification by the surface modifier, and then is compounded with the random copolymerization PPR material, so that the compatibility of nano particles in a polymer matrix is realized, the toughness of the prepared PPR pipeline is obviously enhanced compared with that of a PPR pipeline prepared from the modified PPR material, and the PPR pipeline has the advantages of better low temperature resistance, toughness and high temperature resistance, greatly improves the low temperature brittleness and has good application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The utility model provides a modified PPR low temperature resistant pipeline which characterized in that: the modified PPR low-temperature-resistant pipeline comprises a pipe body inner layer, a modified PPR middle layer and a pipe body outer layer which are formed by sequentially co-extrusion from inside to outside, wherein the modified PPR middle layer is prepared from the following raw materials in parts by weight: 80-120 parts of random copolymerization PPR, 20-40 parts of nano calcium carbonate, 8-15 parts of barium glass powder, 5-8 parts of talcum powder, 0.2-2 parts of coupling agent, 0.1-1 part of nucleating agent TMB and 25-45 parts of absolute ethyl alcohol; the particle size of the barium glass powder is 0.02-0.5 mu m; the particle size of the nano calcium carbonate is 70nm-120nm, and the coupling agent is any one or more of silane coupling agents, titanate coupling agents and zirconate coupling agents;
the preparation of the raw materials of the modified PPR intermediate layer comprises the following steps: adding barium glass powder into absolute ethyl alcohol, mixing and stirring to obtain a mixed solution, adding a coupling agent into the mixed solution, and placing the mixed solution into an ultrasonic stirrer, gradually heating up and carrying out ultrasonic stirring for 10-30 min to obtain a mixture A; adding nano calcium carbonate into a kneader for stirring, adding the mixture A for continuous stirring for 10-20 min, and taking out to obtain a mixture B;
adding the mixture B and the random copolymer PPR into a mixer for mixing, then sequentially adding talcum powder and nucleating agent TMB, and mixing for 10-30 min at 160-200 ℃; then transferring the mixture into a double-screw extruder for melt extrusion granulation, and then drying to obtain modified PPR intermediate layer raw material master batch;
the inner layer of the pipe body is made of a PEEK resin composite material, the PEEK resin composite material is prepared by mixing PEEK resin, barium glass and lignocellulose according to a ratio of 3-6:1:0.5, the particle size of the PEEK resin is 1 mu m-10 mu m, the fiber length of the barium glass is 2mm-5mm, the average length of the lignocellulose is 0.5mm-2mm, and the preparation process comprises the following steps: firstly, mixing barium glass and lignocellulose at 120-150 ℃, stirring and drying for 20-40min; and adding PEEK resin, stirring and mixing, and carrying out melt extrusion at 300-380 ℃ to granulate into particle materials of 20-60 mu m, thereby obtaining the PEEK resin composite material.
2. The modified PPR low temperature resistant pipe according to claim 1, wherein: the temperature of melt extrusion granulation in the twin-screw extruder is 80-120 ℃, and the twin-screw rotating speed of the twin-screw extruder is 30-100 rpm.
3. The modified PPR low temperature resistant pipe according to claim 1, wherein: the temperature of stirring in the kneader is 120-180 ℃, the stirring speed is 600-1200rpm, and the stirring time is 5-10 min.
4. The modified PPR low temperature resistant pipe according to claim 1, wherein: the antibacterial pipe comprises a pipe body inner layer, wherein an antibacterial layer is arranged on the inner wall of the pipe body inner layer at intervals, the thickness ratio of the antibacterial layer to the pipe body inner layer to the modified PPR middle layer to the pipe body outer layer is 0.2-0.5:2:4:0.8-1.5, the antibacterial layer is arranged on the inner wall of the pipe body inner layer along the axial direction or the circumferential direction, the pipe body outer layer is made of a high-density polyethylene composite material, and the high-density polyethylene composite material is made of high-density polyethylene, carbon fiber, nano calcium carbonate, high-activity magnesium oxide, pentatetrol stearate and di-tert-butyl peroxyisopropyl benzene.
5. The modified PPR low temperature resistant pipe according to claim 4, wherein: the antibacterial layer is prepared from nano silver and zeolite powder, wherein the mass ratio of the nano silver to the zeolite powder is 1:4-8.
6. A method for preparing a modified PPR low temperature resistant pipeline according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
step 1: feeding, namely feeding raw materials of an antibacterial layer, an inner pipe layer, an intermediate modified PPR layer and an outer pipe layer of the modified PPR low-temperature-resistant pipeline into respective feeders in proportion;
step 2, extrusion molding, namely quantitatively feeding raw materials of the antibacterial layer, the inner layer of the pipe body, the modified PPR middle layer and the outer layer of the pipe body into different extruders from a feeding machine for melting and plasticizing; extruding an antibacterial layer and an inner layer of the pipe body in a double-layer coextrusion mode, and extruding a modified PPR middle layer and an outer layer of the pipe body in a double-layer coextrusion mode so as to form a pipe blank, wherein the pipe blank enters a sizing sleeve to be extruded and formed into a pipe shape under the traction of a tractor, so that a multi-layer sizing composite pipe is formed;
and 3, cooling and molding, namely cooling and shaping the sized composite structural pipe, and drying to obtain the modified PPR low-temperature-resistant pipeline.
7. The method for preparing the modified PPR low-temperature-resistant pipeline according to claim 6, which is characterized in that: the temperature of the extruded antibacterial layer is 160-190 ℃; the temperature of the inner layer of the extruded tube body is 250-300 ℃; the temperature of the extrusion modified PPR middle layer is 200-250 ℃, and the temperature of the extrusion pipe outer layer is 180-220 ℃.
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