CN112831138A - Environment-friendly hard polyvinyl chloride double-wall corrugated pipe and production process thereof - Google Patents
Environment-friendly hard polyvinyl chloride double-wall corrugated pipe and production process thereof Download PDFInfo
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- CN112831138A CN112831138A CN202110127322.2A CN202110127322A CN112831138A CN 112831138 A CN112831138 A CN 112831138A CN 202110127322 A CN202110127322 A CN 202110127322A CN 112831138 A CN112831138 A CN 112831138A
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- Prior art keywords
- corrugated pipe
- environment
- wall corrugated
- polyvinyl chloride
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 61
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 22
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 12
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 230000002528 anti-freeze Effects 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 230000036314 physical performance Effects 0.000 abstract description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 150000004291 polyenes Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 101100004408 Arabidopsis thaliana BIG gene Proteins 0.000 description 2
- 101100206901 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TIR3 gene Proteins 0.000 description 2
- 239000007798 antifreeze agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 101100259716 Arabidopsis thaliana TAA1 gene Proteins 0.000 description 1
- 101100206899 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TIR2 gene Proteins 0.000 description 1
- VJAHJNCIPPOVSB-UHFFFAOYSA-K [6-methylheptyl-bis[(2-sulfanylacetyl)oxy]stannyl] 2-sulfanylacetate Chemical compound [O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS.CC(C)CCCCC[Sn+3] VJAHJNCIPPOVSB-UHFFFAOYSA-K 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 229940083916 aluminum distearate Drugs 0.000 description 1
- RDIVANOKKPKCTO-UHFFFAOYSA-K aluminum;octadecanoate;hydroxide Chemical compound [OH-].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RDIVANOKKPKCTO-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FFGHLLOLFQHABK-UHFFFAOYSA-L dibutyltin(2+);dodecane-1-thiolate Chemical compound CCCCCCCCCCCCS[Sn](CCCC)(CCCC)SCCCCCCCCCCCC FFGHLLOLFQHABK-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- TXSUIVPRHHQNTM-UHFFFAOYSA-N n'-(3-methylanilino)-n-phenyliminobenzenecarboximidamide Chemical compound CC1=CC=CC(NN=C(N=NC=2C=CC=CC=2)C=2C=CC=CC=2)=C1 TXSUIVPRHHQNTM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention relates to an environment-friendly hard polyvinyl chloride double-wall corrugated pipe and a production process thereof, wherein the environment-friendly hard polyvinyl chloride double-wall corrugated pipe is environment-friendly, improves the performance and the impact resistance of the pipe, and improves the ageing resistance and the toughness of the pipe, and the production process comprises the following raw materials: PVC resin 1, a heat stabilizer, an impact modifier, a processing aid, a lubricant and a filler, wherein the impact modifier comprises a mixture of nano particle-g-MBS particles and acrylic resin. The invention solves the problems of easy scorching and more shrivelled ribs when the lead salt stabilizer is replaced by the environment-friendly stabilizer in the production of the PVC-U double-wall corrugated pipe, obtains the sanitary performance and the physical performance which meet the requirements of GB/T17219-1998 and GB/T18477.1-2007 standards, and makes a technical response for processing the PVC double-wall corrugated pipe without lead salt and international rail connection as early as possible.
Description
Technical Field
The invention belongs to the field of polyvinyl chloride, relates to a hard polyvinyl chloride double-wall corrugated pipe, and particularly relates to an environment-friendly hard polyvinyl chloride double-wall corrugated pipe which is environment-friendly, improves the performance and the impact resistance of the pipe, and improves the ageing resistance and the toughness of the pipe, and a production process thereof.
Background
Polyvinyl chloride (PVC) is one of thermoplastic plastics which are the earliest to realize industrial production in the world, and has the advantages of wear resistance, chemical corrosion resistance, good electrical insulation performance and the like due to low price and wide raw material sources, so that the polyvinyl chloride (PVC) is widely applied to the aspects of industry, agriculture, daily necessities and the like. However, PVC also has the disadvantages of low impact strength, insufficient heat resistance and the like, and the further development of PVC is limited by the disadvantages. Therefore, the modification of PVC by adding different modifiers is the key point of industrial research.
The buried double-wall corrugated pipe for drainage and pollution discharge has been produced in China for more than 10 years, and the production technology is relatively mature. However, the heat stabilizer for processing is lead salt, and is a long and narrow flow channel corresponding to the lead salt, and the consumption of the lead salt is not less. Lead salt is the most effective and cheap heat stabilizer for processing hard polyvinyl chloride, but it is also well known that it causes serious pollution to human and environment. Since the 80 th of the 20 th century, the world countries have put forward the need of prohibiting the use of lead and cadmium heat stabilizers. At present, cadmium salt is eliminated, lead salt is eliminated in 2015-2020, so that the processing of PVC plastics without lead salt and international connection rails is a great trend, and technical response should be made as soon as possible. The development of domestic environment-friendly PVC heat stabilizers has not kept pace in the early years, and the imported price is high, so that the use of composite lead salt is advocated. Although the composite lead salt can reduce the pollution to the processing environment, the lead salt is lead in nature, and the existing conditions are updated to the production process of the double-wall corrugated pipe for buried drainage and pollution discharge at present, which has great breakthrough in the service performance, variety and price of the environment-friendly PVC heat stabilizer, so that the double-wall corrugated pipe can be technically used for processing plastics without using lead salt and international connecting rails.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide an environment-friendly hard polyvinyl chloride double-wall corrugated pipe which is environment-friendly, improves the performance and the impact resistance of the pipe, and improves the ageing resistance and the toughness of the pipe.
Another aspect of the invention is to provide a production process of the environment-friendly rigid polyvinyl chloride double-wall corrugated pipe.
In order to achieve the purpose, the invention adopts the following technical scheme:
the environment-friendly hard polyvinyl chloride double-wall corrugated pipe comprises the following raw materials in parts by weight: 150 portions of PVC resin, 9.5 to 10 portions of heat stabilizer, 6 to 8 portions of impact modifier, 1.8 to 2.2 portions of processing aid, 1.1 to 1.5 portions of lubricant and 20 to 25 portions of filler.
In a preferred embodiment of the present invention, the heat stabilizer includes one or more of organotin compounds and metal soaps.
In the technical scheme, the organic tin heat stabilizer can be: dibutyltin dilaurate, di-n-octyltin maleate, dibutyltin bis (monobutylaleate), dibutyltin bis (lauryl mercaptide), dibutyltin S, S' -bis (isooctyltin thioglycolate), di-n-octyltin dilaurate, and the like; the metal soap heat stabilizer may be: calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminum distearate, calcium laurate, zinc laurate, calcium ricinoleate, zinc 2-ethylhexanoate, and the like.
As a preferred embodiment of the present invention, the impact modifier comprises a mixture of nanoparticle-g-MBS particles with an acrylic resin.
In the technical scheme, hydrogen chloride is generated in the thermal degradation process of a PVC material, and a double bond structure is generated on a PVC chain, in addition, the generated hydrogen chloride can be used as a brittle catalyst to further catalyze the thermal degradation process of PVC, so that a conjugated polyene structure is generated, the impact resistance modifier disclosed by the invention has a structure which is subjected to conjugated addition with conjugated polyene, the generation of the conjugated polyene structure can be effectively inhibited, the occurrence of a discoloration phenomenon is obviously reduced, and through the addition of nano particles-g-MBS particles, the impact resistance modifier can perform a coupling effect with free radicals produced in the thermal degradation process of PVC to a certain extent, so that the removal of hydrogen chloride in PVC can be inhibited to a certain extent, and the production of a conjugated polyene sequence is hindered; the impact resistance of the pipe is improved by adopting the nano particle-g-MBS particles, the toughness of the pipe can be improved together with the filler, when the pipe is subjected to external acting force, the acrylic resin in the impact modifier can absorb a large amount of external energy through self deformation, and the nano particle-g-MBS particles can serve as a stress concentrator and force a matrix to generate plastic deformation to absorb the external energy; when the nano particle-g-MBS particles dispersed in the pipe are impacted by external energy, the stress is transferred to the nano particle-g-MBS particles, so that the effect of hindering the development of cracks is achieved, and the fatigue and the adhesion of the pipe are reduced.
As a preferable scheme of the invention, the processing aid comprises one or more of a flame retardant, a coupling agent, an antioxidant or an antifreeze.
In a preferred embodiment of the present invention, the lubricant is polyethylene wax and ethylene bisricinoleic acid amide at a mass ratio of 1: 2-3.
In a preferred embodiment of the present invention, the filler is activated nano calcium carbonate.
As a preferred embodiment of the present invention, the nanoparticles include nano calcium phosphate, nano silicon carbide or nano boron nitride.
As a preferred scheme of the invention, the preparation method of the nanoparticle-g-MBS particle comprises the following steps: adding the nano particles, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain the nano-particle-g-MBS particle.
As a preferable scheme of the invention, the mass ratio of the nanoparticle-g-MBS particles to the acrylic resin is as follows: 2-3:1.
The invention also provides a production process of the environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing the raw materials according to the proportion;
2) mixing materials: mixing materials at a high speed to 85-95 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 45-50 ℃;
3) and (3) low-temperature plasticizing extrusion process: and extruding the environment-friendly hard polyvinyl chloride double-wall corrugated pipe material on PVC-U double-wall corrugated pipe production equipment and a mould by using standby materials at the temperature of an extruder barrel of 155-175 ℃ and the temperature of a neck mold of not more than 200 ℃, and cutting and flaring the environment-friendly hard polyvinyl chloride double-wall corrugated pipe material.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention solves the problems of easy scorching and more shrivelled ribs when the lead salt stabilizer is replaced by the environment-friendly stabilizer in the production of the PVC-U double-wall corrugated pipe, obtains the sanitary performance and the physical performance which both accord with the requirements of GB/T17219-1998 and GB/T18477.1-2007 standards, and makes technical response for processing the PVC double-wall corrugated pipe without lead salt and international rail connection as early as possible;
2) the invention adopts the nano particle-g-MBS particles to improve the shock resistance of the pipe, and can improve the toughness of the pipe together with the filler, when the pipe is subjected to external acting force, the acrylic resin in the shock resistance modifier can absorb a large amount of external energy through self deformation, and the nano particle-g-MBS particles can act as a stress concentrator and force a matrix to generate plastic deformation to absorb the external energy; when the nano particle-g-MBS particles dispersed in the pipe are impacted by external energy, the stress is transferred to the nano particle-g-MBS particles, so that the effect of hindering the development of cracks is achieved, and the fatigue and the adhesion of the pipe are reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the present invention are all commercially available.
Example 1
The embodiment provides a production process of an environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing materials according to the following proportion; the weight portion of the material is as follows: 120 parts of PVC resin, 9.5 parts of heat stabilizer, 6 parts of impact modifier, 1.8 parts of processing aid, 1.1 parts of lubricant and 20 parts of filler;
wherein the heat stabilizer is dibutyltin dilaurate and calcium laurate in a mass ratio of 1: 1;
the impact modifier comprises the following components in percentage by mass: 2:1 of nano silicon carbide-g-MBS particles and acrylic resin; the preparation method of the nano silicon carbide-g-MBS particles comprises the following steps: adding nano silicon carbide, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding a methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain nano silicon carbide-g-MBS particles;
the processing aid is a flame retardant and an antioxidant in a mass ratio of 1:2, and the flame retardant and the antioxidant are commonly used in the field;
the lubricant is polyethylene wax and ethylene bis-ricinoleic acid amide in a mass ratio of 1:2, and the filler is active nano calcium carbonate;
2) mixing materials: mixing materials at a high speed until the temperature is 85 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 45 ℃;
3) and (3) low-temperature plasticizing extrusion process: under the condition that the temperature of an extruder barrel is 155 ℃ and the temperature of a neck ring mold is not more than 200 ℃, the prepared material is extruded on PVC-U double-wall corrugated pipe production equipment and a mold to form the environment-friendly hard polyvinyl chloride double-wall corrugated pipe, and the environment-friendly hard polyvinyl chloride double-wall corrugated pipe is obtained by cutting and flaring.
Example 2
The embodiment provides a production process of an environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing materials according to the following proportion; the weight portion of the material is as follows: 125 parts of PVC resin, 9.8 parts of heat stabilizer, 6.5 parts of impact modifier, 2 parts of processing aid, 1.2 parts of lubricant and 22 parts of filler;
wherein the heat stabilizer is dibutyltin dilaurate and calcium laurate in a mass ratio of 1: 1;
the impact modifier comprises the following components in percentage by mass: 2.5:1 of nano boron nitride-g-MBS particles and acrylic resin; the preparation method of the nanometer boron nitride-g-MBS particles comprises the following steps: adding nano boron nitride, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding a methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain the nano boron nitride-g-MBS particles;
the processing aid is a flame retardant and an antifreeze agent with the mass ratio of 1:1.5, and the flame retardant and the antifreeze agent are commonly used in the field;
the lubricant is polyethylene wax and ethylene bis-ricinoleic acid amide in a mass ratio of 1:2.2, and the filler is active nano calcium carbonate;
2) mixing materials: mixing materials at a high speed to 90 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 48 ℃;
3) and (3) low-temperature plasticizing extrusion process: under the conditions that the temperature of an extruder barrel is 165 ℃ and the temperature of a neck ring mold is not more than 200 ℃, the prepared material is extruded on PVC-U double-wall corrugated pipe production equipment and a mold to form an environment-friendly hard polyvinyl chloride double-wall corrugated pipe, and the pipe is cut and flared.
Example 3
The embodiment provides a production process of an environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing materials according to the following proportion; the weight portion of the material is as follows: 130 parts of PVC resin, 9.7 parts of heat stabilizer, 7.5 parts of impact modifier, 1.95 parts of processing aid, 1.3 parts of lubricant and 24 parts of filler;
wherein the heat stabilizer is dibutyltin dilaurate and calcium laurate in a mass ratio of 1: 1;
the impact modifier comprises the following components in percentage by mass: 3:1 of nano boron nitride-g-MBS particles and acrylic resin; the preparation method of the nanometer boron nitride-g-MBS particles comprises the following steps: adding nano boron nitride, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding a methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain the nano boron nitride-g-MBS particles;
the processing aid comprises a flame retardant, a coupling agent and an antioxidant in a mass ratio of 1:1:0.5, wherein the flame retardant, the coupling agent and the antioxidant are commonly used in the field;
the lubricant is polyethylene wax and ethylene bis-ricinoleic acid amide in a mass ratio of 1:2.7, and the filler is active nano calcium carbonate;
2) mixing materials: mixing materials at a high speed until the temperature reaches 95 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 50 ℃;
3) and (3) low-temperature plasticizing extrusion process: under the conditions that the temperature of an extruder barrel is 175 ℃ and the temperature of a neck ring mold is not more than 200 ℃, the prepared material is extruded on PVC-U double-wall corrugated pipe production equipment and a mold to form an environment-friendly hard polyvinyl chloride double-wall corrugated pipe, and the pipe is cut and flared.
Example 4
The embodiment provides a production process of an environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing materials according to the following proportion; the weight portion of the material is as follows: 150 parts of PVC resin, 10 parts of heat stabilizer, 8 parts of impact modifier, 2.2 parts of processing aid, 1.5 parts of lubricant and 25 parts of filler;
wherein the heat stabilizer is dibutyltin dilaurate and calcium laurate in a mass ratio of 1: 1;
the impact modifier comprises the following components in percentage by mass: 3:1 of nano boron nitride-g-MBS particles and acrylic resin; the preparation method of the nanometer boron nitride-g-MBS particles comprises the following steps: adding nano boron nitride, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding a methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain the nano boron nitride-g-MBS particles;
the processing aid is a coupling agent and an antioxidant in a mass ratio of 2:1, and the coupling agent and the antioxidant are commonly used in the field;
the lubricant is polyethylene wax and ethylene bis-ricinoleic acid amide in a mass ratio of 1:3, and the filler is active nano calcium carbonate;
2) mixing materials: mixing materials at a high speed until the temperature is 95 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 45-50 ℃;
3) and (3) low-temperature plasticizing extrusion process: under the conditions that the temperature of an extruder barrel is 175 ℃ and the temperature of a neck ring mold is not more than 200 ℃, the prepared material is extruded on PVC-U double-wall corrugated pipe production equipment and a mold to form an environment-friendly hard polyvinyl chloride double-wall corrugated pipe, and the pipe is cut and flared.
Example 5
The embodiment provides a production process of an environment-friendly rigid polyvinyl chloride double-wall corrugated pipe, which comprises the following steps:
1) preparing materials according to the following proportion; the weight portion of the material is as follows: 145 parts of PVC resin, 10 parts of heat stabilizer, 8 parts of impact modifier, 1.8 parts of processing aid, 1.5 parts of lubricant and 25 parts of filler;
wherein the heat stabilizer is dibutyltin dilaurate and calcium laurate in a mass ratio of 1: 1;
the impact modifier comprises the following components in percentage by mass: 2:1 of nano calcium phosphate-g-MBS particles and acrylic resin; the preparation method of the nano calcium phosphate-g-MBS particle comprises the following steps: adding nano calcium phosphate, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; adding a methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain nano calcium phosphate-g-MBS particles;
the processing aid is prepared from the following components in a mass ratio of 2: 3:1, the flame retardant, the antioxidant and the antifreeze are commonly used in the field;
the lubricant is polyethylene wax and ethylene bis-ricinoleic acid amide in a mass ratio of 1:2, and the filler is active nano calcium carbonate;
2) mixing materials: mixing materials at a high speed until the temperature is 85 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 50 ℃;
3) and (3) low-temperature plasticizing extrusion process: under the conditions that the temperature of an extruder barrel is 175 ℃ and the temperature of a neck ring mold is not more than 200 ℃, the prepared material is extruded on PVC-U double-wall corrugated pipe production equipment and a mold to form an environment-friendly hard polyvinyl chloride double-wall corrugated pipe, and the pipe is cut and flared.
Comparative example 1, same as example 1, except that no nano calcium phosphate-g-MBS particles were added.
Comparative example 2, polyvinyl chloride was directly injection molded into a pipe to be tested.
The pipes of examples 1-5 and comparative examples 1-2 were subjected to the relevant performance tests according to the GB/T14152-2001 standard.
Further, 0 ℃ drop hammer impact TIR2) indicates that the 0 ℃ drop hammer impact test conditions are: the hammer head of the drop hammer is d90 type, the mass of the drop hammer is 2Kg, and the drop height is 2 m;
0 ℃ drop hammer impact TIR3) indicates that the 0 ℃ drop hammer impact test conditions are: the hammer head of the drop hammer is d90 type, the mass of the drop hammer is 5.5Kg, and the drop height is 2 m;
-10 ℃ drop impact TIR3) indicates that-10 ℃ drop impact test conditions are: the hammer head of the drop hammer is d90 type, the mass of the drop hammer is 10Kg, and the drop height is 0.5 m. The results of the relevant tests are shown in table 1.
TABLE 1 test results
The pipes of examples 1-5 and comparative examples 1-2 were tested for flexural strength, tensile strength, surface shore hardness (type D), and environmental protection according to the national requirements standards, and the results are shown in table 2.
TABLE 2 test results
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The environment-friendly hard polyvinyl chloride double-wall corrugated pipe is characterized by comprising the following raw materials in parts by weight: 150 portions of PVC resin, 9.5 to 10 portions of heat stabilizer, 6 to 8 portions of impact modifier, 1.8 to 2.2 portions of processing aid, 1.1 to 1.5 portions of lubricant and 20 to 25 portions of filler.
2. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe as claimed in claim 1, wherein the heat stabilizer comprises one or more of organic tin and metal soap.
3. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe as claimed in claim 1, wherein the impact modifier comprises a mixture of nanoparticle-g-MBS particles and acrylic resin.
4. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe as claimed in claim 1, wherein the processing aid comprises one or more of a flame retardant, a coupling agent, an antioxidant or an antifreeze.
5. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe material as claimed in claim 1, wherein the lubricant is polyethylene wax and ethylene bisricinoleic acid amide in a mass ratio of 1: 2-3.
6. The environment-friendly rigid polyvinyl chloride double-walled corrugated pipe as claimed in claim 1, wherein the filler is activated nano calcium carbonate.
7. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe as claimed in claim 3, wherein the nano particles comprise nano calcium phosphate, nano silicon carbide or nano boron nitride.
8. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe material as claimed in claim 3 or 7, wherein the preparation method of the nanoparticle-g-MBS particles comprises the following steps: adding the nano particles, methanesulfonic acid and tetrahydrofuran into a sealed tube according to the molar ratio of 1:1:1, and performing ultrasonic dispersion while magnetically stirring; then adding methacrylic acid methyl ester-butadiene-styrene copolymer, reacting in an oil bath at 50-60 ℃ for 2-3h, taking out, filtering, washing with tetrahydrofuran, centrifuging, and drying to obtain the nano-particle-g-MBS particle.
9. The environment-friendly rigid polyvinyl chloride double-wall corrugated pipe as claimed in claim 3, wherein the mass ratio of the nanoparticle-g-MBS particles to the acrylic resin is as follows: 2-3:1.
10. A process for producing an environmentally friendly rigid polyvinyl chloride double wall corrugated pipe material as claimed in claim 1, wherein the process comprises the steps of:
1) preparing the raw materials according to the proportion;
2) mixing materials: mixing materials at a high speed to 85-95 ℃, discharging the materials into a low-speed cold mixer, stirring the materials, and discharging the materials for later use when the temperature reaches 45-50 ℃;
3) and (3) low-temperature plasticizing extrusion process: and extruding the environment-friendly hard polyvinyl chloride double-wall corrugated pipe material on PVC-U double-wall corrugated pipe production equipment and a mould by using standby materials at the temperature of an extruder barrel of 155-175 ℃ and the temperature of a neck mold of not more than 200 ℃, and cutting and flaring the environment-friendly hard polyvinyl chloride double-wall corrugated pipe material.
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