CN116874947A - Seawater corrosion-resistant high-strength PVC-U material, and preparation method and application thereof - Google Patents
Seawater corrosion-resistant high-strength PVC-U material, and preparation method and application thereof Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 80
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- 238000005260 corrosion Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 55
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 48
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 48
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 37
- 230000002441 reversible effect Effects 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 10
- 229920002748 Basalt fiber Polymers 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 3
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009364 mariculture Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention discloses a seawater corrosion-resistant high-strength PVC-U material, and a preparation method and application thereof, and belongs to the technical field of modification of polymer composite materials. The seawater corrosion resistant high-strength PVC-U material comprises the following components in parts by mass: 100 parts of polyvinyl chloride resin; 3-15 parts of a network type toughening agent; 2.5-5 parts of heat stabilizer; 0.1 to 1.5 portions of heat reversible cross-linking agent; 0.0125-0.375 part of crosslinking regulator and 5-25 parts of filler; 0.7 to 12 parts of auxiliary agent, and the mass part ratio of the heat reversible cross-linking agent to the cross-linking regulator is 4 to 8:1. by adjusting the proportion of the thermal reversible cross-linking agent and the cross-linking regulator, the problem of poor thermal stability of the PVC material caused by hydrogen chloride removal in the cross-linking process is solved, and the toughness, strength and seawater corrosion resistance of the PVC-U material are further improved.
Description
Technical Field
The invention relates to the technical field of modification of polymer composite materials, in particular to a seawater corrosion-resistant high-strength PVC-U material, and a preparation method and application thereof.
Background
With the improvement of living standard of people, the demands for marine products are becoming larger, the natural-growth marine products can not meet the demands of people, and industrial mariculture is generated. The industrial mariculture and seedling raising factories are mainly arranged in coastal areas, water is taken from the sea by adopting a water suction pump, a large number of pipelines are required to be used for conveying seawater, due to the fact that seawater is high in corrosiveness, metal pipelines are used for conveying, the service life of the pipelines is short, corrosion resistance and economic adaptability are comprehensively considered, PVC plastic pipelines are mostly adopted for conveying seawater in the market, however, the existing PVC pipelines are usually prepared by adopting calcium carbonate as a filler, the obtained PVC materials can meet the requirements of water supply and drainage for fresh water, the inner surfaces of the PVC pipelines filled with calcium carbonate and contacted with the seawater in the seawater environment are extremely easy to corrode, and therefore the whole or partial thinning of the pipe wall is caused, the strength of the pipeline is reduced or stress concentration occurs, the brittleness of the product is poor, the pipe wall is easy to leak or destroy, and a large amount of manpower and material resources are required to be wasted once the maintenance is damaged.
The prior art CN 109679243A discloses a heat-resistant corrosion-resistant polyvinyl chloride water supply and drainage pipe and a preparation method thereof, and the method uses a thermal crosslinking technology and adopts the following steps: 100 parts of polyvinyl chloride, 10-30 parts of ethylene-vinyl acetate oligomer, 2-5 parts of heat stabilizer, 0.5-2.0 parts of cross-linking agent, 0.4-1.0 parts of lubricant, 10-25 parts of filler and 0.1-0.5 part of pigment. After chemical crosslinking, the prior art loses the thermoplasticity of the original PVC pipe, causes the defects of toughness and strength of the pipe, and influences the corrosion resistance of the PVC pipe.
Disclosure of Invention
The invention aims to solve the technical problems of insufficient toughness, strength and seawater corrosion resistance of the existing PVC material, and provides the seawater corrosion resistant high-strength PVC-U material, and the problems of poor thermal stability of the PVC material caused by hydrogen chloride removal in the crosslinking process are solved by adjusting the proportion of the thermally reversible crosslinking agent and the crosslinking regulator, so that the defects of low toughness, low strength and poor seawater corrosion resistance of the PVC material are overcome.
The invention further aims at providing a preparation method of the seawater corrosion-resistant high-strength PVC-U material.
The invention further aims to provide application of the seawater corrosion resistant high-strength PVC-U material in the field of seawater transportation.
It is a further object of the present invention to provide a PVC-U pipe for transporting seawater.
The above object of the present invention is achieved by the following technical scheme:
the seawater corrosion resistant high-strength PVC-U material comprises the following components in parts by mass:
100 parts of polyvinyl chloride resin; 3-15 parts of a network type toughening agent; 2.5-5 parts of heat stabilizer; 0.1 to 1.5 portions of heat reversible cross-linking agent; 0.0125-0.375 parts of crosslinking regulator; 5-25 parts of filler; 0.7-12 parts of auxiliary agent;
the weight portion ratio of the thermally reversible cross-linking agent to the cross-linking regulator is 4-8: 1.
because the alkalinity of the thermal reversible cross-linking agent is too strong, the reaction of removing hydrogen chloride from the PVC can be induced in the PVC preparation process, the thermal stability of the PVC is reduced, and the toughness, the strength and the seawater corrosion resistance of the material are further affected. The cross-linking regulator is added, the mass part ratio of the thermally reversible cross-linking agent to the cross-linking regulator is regulated, free radicals which cause the reduction of the thermal stability of the material are eliminated, the defect of the thermal stability of the material caused by the removal of hydrogen chloride by PVC in the cross-linking process of the thermally reversible cross-linking agent is overcome, and meanwhile, the toughness, the strength and the seawater corrosion resistance of the PVC-U material are improved. When the proportion of the thermal reversible crosslinking agent and the crosslinking regulator is improper, the PVC material has the problems of excessive crosslinking or insufficient crosslinking degree, and the thermal stability of the material is affected, so that the toughness, the strength and the seawater corrosion resistance of the material are affected.
The network type toughening agent is added into the PVC system, and the network type toughening agent and the thermoreversible crosslinking agent can form a bicontinuous phase co-crosslinking network with the PVC resin matrix at room temperature, so that corrosive seawater is more difficult to enter the matrix, and the seawater corrosion resistance of the PVC-U material is improved.
In a specific embodiment of the invention, the auxiliary agent is one or more of a lubricant, a processing aid and a pigment;
the lubricant is preferably a polyethylene wax;
the heat stabilizer is preferably a non-toxic calcium/zinc stabilizer free of heavy metals;
the processing modification auxiliary agent is preferably an acrylic ester compound;
the pigment is preferably one or more of titanium dioxide, carbon black or a colorant.
Preferably, the ratio of the thermoreversible crosslinking agent to the crosslinking regulator is 4.5-6.5: 1.
under the proportion, the PVC-U material has better crosslinking effect, so that the toughness, strength and seawater corrosion resistance of the material are better.
Preferably, the thermally reversible crosslinking agent is one or more of cyclopentadienyl metals, biscyclopentadienyl metal compounds.
Under the strong alkaline action of cyclopentadienyl metal and dicyclopentadienyl metal compound, substitution reaction is carried out with chlorine atoms on a PVC main chain to produce PVC with cyclopentadienyl group or dicyclopentadienyl group side chains, and then PVC with cyclopentadienyl group or dicyclopentadienyl group side chains generates PVC resin with covalent bond crosslinking due to interaction between cyclopentadienyl or dicyclopentadienyl groups, so that the mechanical property of the material can be improved.
Preferably, the crosslinking modifier is a ceria nanoparticle.
The ceria has the function of eliminating free radicals, can improve the thermal stability, toughness, strength and seawater corrosion resistance of the material, has good compatibility with polymers, and can be uniformly dispersed in the polymers.
Preferably, the specific surface area of the cerium oxide nano-particles is 100-120 m 2 /g。
Under the specific surface area, the addition of nano-scale cerium dioxide can not only improve the thermal stability of the material, but also increase the crosslinking point of the heat reversible crosslinking agent, and under the same crosslinking condition, the toughness, the strength and the seawater corrosion resistance of the PVC can be improved.
Preferably, the filler is basalt fiber.
Fillers are likewise one of the indispensable constituents in PVC pipes. PVC, as a polymer, is not strong enough to ensure practical use of the materials prepared from it, and fillers to enhance rigidity are often indispensable in order to ensure that PVC materials have sufficient utility. The traditional filler such as calcium carbonate can reduce the seawater corrosion resistance of PVC materials after being added into PVC, but the filler adopted in the invention is basalt fiber which is oriented and distributed in the surface of the PVC matrix after being added into a PVC system, has stronger binding force with the PVC matrix and can not reduce the seawater corrosion resistance of PVC pipes.
More preferably, the basalt fibers are silane-modified basalt fibers.
After PVC is added into the basalt fiber modified by silane, the binding force between the basalt fiber and a PVC matrix is further enhanced, so that the addition of basalt filler can not reduce the seawater corrosion resistance of the PVC material.
Preferably, the network type toughening agent is any one or more of ethylene-vinyl acetate copolymer (EVA), nitrile Butadiene Rubber (NBR), isocyanate-terminated polyurethane Prepolymer (PUR), styrene block copolymer (SBS) and Chlorinated Polyethylene (CPE).
The invention also provides a preparation method of the seawater corrosion-resistant high-strength PVC-U material, which comprises the following steps:
s1, uniformly mixing all the components (except the filler) to obtain a mixture;
s2, plasticizing the mixture obtained in the step S1 and the filler together, and extruding to obtain the seawater corrosion resistant high-strength PVC-U material.
In the specific embodiment of the invention, in the step S1, a high-speed mixer is used for mixing, and a low-speed cold mixer is used for mixing; the mixing temperature of the high-speed mixer can be 100-115 ℃, and the mixing time can be 5-8 min; the mixing temperature of the low-speed cold mixer can be 45-50 ℃, and the mixing time can be 3-5 min; in the step S2, the plasticizing temperature can be 160-220 ℃, the die temperature can be 170-220 ℃, and the prepared material can be PVC pipe with nominal diameter of dn50 x 2.0 mm.
The invention also protects the application of the seawater corrosion resistant high-strength PVC-U material in the field of seawater transportation.
The invention also provides a PVC-U pipe for transporting seawater, which is prepared from the seawater corrosion-resistant high-strength PVC-U material.
Compared with the prior art, the invention has the following beneficial effects:
the seawater corrosion resistant high-strength PVC-U material provided by the invention improves the thermal stability, toughness, strength and seawater corrosion resistance of PVC-U, after 112 days of seawater soaking, the mass change percentage can be only 0.05%, the yield stress change percentage is up to 98.2%, the thermal stability time is up to 38min, the Vicat softening temperature is up to 100.2 ℃, the tensile yield stress is up to 78Mpa, and no rupture exists in a drop impact test.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified. Wherein:
polyvinyl chloride resin: SG5 resin with viscosity of 112mL/g purchased from Xinjiang Zhongtai;
heat stabilizer: a calcium zinc heat stabilizer purchased from Guangdong Xinda QY-2021A1;
and (3) a lubricant: polyethylene wax purchased from Luan group LA-W110;
processing aid: acrylic ester (ACR), purchased from shandong ruifeng LP-90;
and (3) pigment: titanium dioxide purchased from Bai Li Bib BLR-688;
thermoreversible crosslinking agent: cyclopentadienyl sodium purchased from wuhan Kang Qiong;
crosslinking regulator-a: cerium oxide nanoparticles having a specific surface area of 110m 2 G, purchasing from gold mine technology;
crosslinking regulator-b: cerium oxide nanoparticles having a specific surface area of 30m 2 G, purchasing from gold mine technology;
and (3) filling: silane modified basalt fiber, chopped fiber BFCS 611-10-3, fiber diameter 10 μm purchased from Sichuan-scale;
network type toughening agent: chlorinated Polyethylene (CPE) purchased from eastern family 135A;
core-shell toughening agent: methyl methacrylate-butadiene-styrene (MBS), purchased from Shandong Ruifeng LB-564;
example 1
The seawater corrosion resistant high-strength PVC-U material comprises the following components in parts by mass:
100 parts of polyvinyl chloride resin; 3 parts of a network type toughening agent; 2.5 parts of a heat stabilizer; 0.5 parts of a thermoreversible crosslinking agent; 0.1 part of crosslinking regulator-a; 5 parts of filler; 0.5 parts of lubricant; 0.1 part of processing aid; 0.1 part of pigment;
the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator-a is 5:1.
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the embodiment 1 comprises the following steps:
s1, 100 parts of polyvinyl chloride resin, 0.1 part of processing aid, 0.5 part of lubricant and 2.5 parts of heat stabilizer; adding 0.5 part of a thermal reversible crosslinking agent, 0.1 part of a crosslinking regulator-a, 3 parts of a network type toughening agent and 0.1 part of pigment into a high-speed mixer, mixing at a high speed for 5min at a temperature of 110 ℃, then transferring into a low-speed cold mixer, stirring and cooling, and mixing at a low speed for 3min when the temperature is reduced to 50 ℃;
s2, conveying the mixed product of the S1 to a feeding port of a double-screw extruder through a pipe chain, simultaneously, metering and discharging 20 parts of filler through a hopper parallel to a discharging pipe chain of the S1 mixture, feeding the filler and the S1 mixture into the double-screw extruder for plasticizing, and extruding at a barrel temperature of 210 ℃ and a die temperature of 200 ℃ to obtain the PVC-U pipe with the nominal diameter dn50 x 2.0 mm.
Example 2
A seawater corrosion resistant high strength PVC-U material, differing from example 1 in 0.5 parts of a thermoreversible crosslinking agent; 0.062 parts of a crosslinking regulator;
the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator-a is 8:1.
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the embodiment 2 is different from that in the embodiment 1 in that:
the thermoreversible crosslinking agent in step S1 was 0.5 part and the crosslinking regulator-a was 0.062 part.
Example 3
A seawater corrosion resistant high strength PVC-U material, differing from example 1 in 0.5 parts of a thermoreversible crosslinking agent; 0.125 parts of crosslinking regulator-a;
the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator-a is 4:1.
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the embodiment 3 is different from that in the embodiment 1 in that:
the amount of the thermally reversible crosslinking agent in step S1 was 0.5 part and the amount of the crosslinking regulator-a was 0.125 part.
Example 4
A seawater corrosion resistant high strength PVC-U material is different from example 1 in that the crosslinking regulator is 0.1 part of crosslinking regulator-b.
The preparation method of the seawater corrosion resistant high-strength PVC-U material in the embodiment 4 is different from that in the embodiment 1 in that:
the crosslinking regulator in the step S1 is a crosslinking regulator-b.
Comparative example 1
A seawater corrosion resistant high strength PVC-U material, differing from example 1 in 0.5 parts of a thermoreversible crosslinking agent; 0.05 parts of a crosslinking regulator-a;
the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator-a is 10:1.
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the comparative example 1 is different from that in the example 1 in that:
0.5 part of a thermoreversible crosslinking agent in the step S1; 0.05 part of crosslinking regulator-a.
Comparative example 2
A seawater corrosion resistant high strength PVC-U material, differing from example 1 in 0.5 parts of a thermoreversible crosslinking agent; 0.5 parts of a crosslinking regulator-a;
the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator-a is 1:1.
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the comparative example 2 is different from that in the example 1 in that:
0.5 part of a thermoreversible crosslinking agent in the step S1; 0.5 part of crosslinking regulator-a.
Comparative example 3
A seawater corrosion resistant high strength PVC-U material, differing from example 1 in that no crosslinking modifier was added;
the preparation method of the seawater corrosion resistant high-strength PVC-U material in the comparative example 3 is different from that of the example 1 in that:
in step S1, no crosslinking regulator is added.
Comparative example 4
A seawater corrosion resistant high strength PVC-U material differs from example 1 in that the toughening agent used is a non-network type toughening agent MBS.
The preparation method of the seawater corrosion resistant high-strength PVC-U material in the comparative example 4 is different from that of the example 1 in that:
in the step S1, the toughening agent is MBS.
Test example Performance measurement
(1) Thermal stability test
Heat stabilization time: and (3) carrying out dynamic thermal stability test on the formula system in the step S1 by using a torque rheometer, and sampling every 2 minutes to carry out color test until the color changes.
The length of the thermal stability time represents the quality of the thermal stability of the material system.
(2) Toughness testing
Drop hammer impact test: the test method is measured according to GB/T14152 2001, the drop weight is 0.5kg, and the drop height is 1.0m at 0 ℃.
The requirements are:indicating that the toughness of the material is good.
(3) Intensity test
Tensile yield stress: the detection method is determined according to GB/T8804.2-2003.
The higher the tensile yield stress, the better the material strength.
Hydrostatic test: the detection method is measured according to GB/T6111-2018, the test pressure is 10MPa, and the test time is 1 hour.
The requirements are: 1h, no leakage and no rupture, which indicates that the material strength is good.
(4) Seawater corrosion resistance test
Seawater corrosion resistance: testing the tubing according to ISO 4433-3; soaking in seawater for 112 days. Percent mass change = (initial mass of sample before soak-mass of sample after soak)/initial mass of sample before soak x 100%. Percentage change in tensile yield stress = (tensile yield stress after soak/tensile yield stress before soak) ×100%.
The requirements are: the lower the mass change percentage is <5%, the better. The greater the tensile yield stress change percentage >80%, the better.
(5) Heat resistance
Vicat softening temperature test: the detection method is determined according to GB/T8802-2001.
The higher the Vicat softening temperature is, the better the heat resistance of the material is.
Table 1 test example performance test results
As can be seen from the test results of the table, the PVC-U material prepared in each embodiment of the invention has long thermal stability time, enhanced toughness, high strength, excellent heat resistance and seawater corrosion resistance, and maintains the original thermoplasticity of the pipe.
As can be seen from the data of examples 1 to 3 and comparative examples 1 to 2 in Table 1, when the weight part ratio of the thermally reversible crosslinking agent to the crosslinking regulator in the seawater corrosion resistant high strength PVC-U material provided by the invention is 4 to 8:1, the prepared PVC-U pipe has the mass change percentage of seawater corrosion resistance of only 0.05-0.22%, the yield stress change percentage of over 96.2%, the tensile yield stress of over 73Mpa, the Vicat softening temperature of over 96.2 ℃, the pipe is not broken in a drop hammer impact test, and the dynamic thermal stability time of the pipe is over 35min, which indicates that the mass fraction ratio of the thermal reversible cross-linking agent and the cross-linking regulator can improve the thermal stability, toughness, strength, heat resistance and seawater corrosion resistance of the PVC-U material, and can meet the requirement of long thermal mechanical process in the production of large-caliber PVC materials.
In example 4, a specific surface area of 30m was used 2 As a crosslinking regulator, per gram of cerium oxide nanoparticles, it was demonstrated that the crosslinking regulator cerium oxide had a preferred specific surface area of 100 to 120m compared to example 1 2 The PVC-U material prepared outside the specific surface area has a certain seawater corrosion resistance effect, but the effect is inferior to that of the example 1. In comparative example 3, the PVC material cannot meet the thermal stability requirement of material production in the preparation process and cannot extrude the pipe in the thermo-mechanical production process because the crosslinking regulator is not added, which indicates that the crosslinking regulator can improve the thermal stability of the material in the preparation process of the PVC material. In comparative example 4, the core-shell type toughening agent is adopted, the prepared PVC material has certain thermal stability, but the mass change percentage of seawater corrosion resistance of the PVC material reaches 15%, which is far greater than 0.05% in example 1, and the yield stress change percentage is smaller than that of example 1, so that the corrosion resistance of seawater can be improved in the preparation process of the PVC-U material by the network type toughening agent.
In addition, the content of other components is not in the protection range of the invention, the comprehensive performance of the PVC-U material cannot meet the requirements of the invention, the raw material components have a synergistic effect, and the seawater corrosion resistant high-strength PVC-U material can be prepared only by the components in a proper dosage range.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The seawater corrosion resistant high-strength PVC-U material is characterized by comprising the following components in parts by mass:
100 parts of polyvinyl chloride resin; 3-15 parts of a network type toughening agent; 2.5-5 parts of heat stabilizer; 0.1 to 1.5 portions of heat reversible cross-linking agent; 0.0125-0.375 parts of crosslinking regulator; 5-25 parts of filler; 0.7 to 12 parts of auxiliary agent,
the weight portion ratio of the thermally reversible cross-linking agent to the cross-linking regulator is 4-8: 1.
2. the seawater corrosion resistant high strength PVC-U material according to claim 1, wherein the weight portion ratio of the thermally reversible crosslinking agent to the crosslinking regulator is 4.5-6.5: 1.
3. the seawater corrosion resistant high strength PVC-U material of claim 1, wherein the thermally reversible cross-linking agent is one or more of a cyclopentadienyl metal, a biscyclopentadienyl metal compound.
4. The seawater corrosion resistant high strength PVC-U material of claim 1, wherein the cross-linking regulator is ceria nanoparticles.
5. The seawater corrosion resistant high strength PVC-U material according to claim 4, wherein the specific surface area of the cerium oxide nanoparticles is 100-120 m 2 /g。
6. The seawater corrosion resistant high strength PVC-U material of claim 1, wherein the filler is basalt fiber.
7. The seawater corrosion resistant high strength PVC-U material of claim 1, wherein the network toughening agent is any one or more of ethylene-vinyl acetate copolymer, nitrile rubber, isocyanate terminated polyurethane prepolymer, styrenic block copolymer, chlorinated polyethylene.
8. A method for preparing the seawater corrosion resistant high strength PVC-U material according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly mixing all components except the filler to obtain a mixture;
s2, plasticizing the mixture obtained in the step S1 and the filler together, and extruding to obtain the seawater corrosion resistant high-strength PVC-U material.
9. Use of the seawater corrosion resistant high strength PVC-U material according to any one of claims 1 to 7 in the field of seawater transportation.
10. A PVC-U pipe for transporting seawater, wherein the PVC-U pipe for transporting seawater is prepared from the seawater corrosion resistant high strength PVC-U material according to any one of claims 1 to 7.
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