CN115403878A - Polyvinyl chloride pipe and preparation method thereof - Google Patents
Polyvinyl chloride pipe and preparation method thereof Download PDFInfo
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- CN115403878A CN115403878A CN202210988809.4A CN202210988809A CN115403878A CN 115403878 A CN115403878 A CN 115403878A CN 202210988809 A CN202210988809 A CN 202210988809A CN 115403878 A CN115403878 A CN 115403878A
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- polyvinyl chloride
- chloride pipe
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 74
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 8
- 239000003549 soybean oil Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- -1 monoglyceride fatty acid ester Chemical class 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- 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)
Abstract
The invention discloses a polyvinyl chloride pipe and a preparation method thereof, belonging to the technical field of polyvinyl chloride pipes, wherein the polyvinyl chloride pipe comprises 50-60 parts of polyvinyl chloride particles, 50 parts of modified particles and 18-22 parts of activated nano-fillers; wherein, the emulsifier is added into the epoxidized soybean oil and fully stirred to obtain an emulsion; dispersing nano calcium carbonate with water, adding the hydrophobic modified nano silicon dioxide and the emulsion, stirring and mixing, finally adding a silane coupling agent KH-792, stirring and mixing, drying, and crushing to obtain an activated nano filler; the activation treatment is beneficial to increasing the compatibility of the nano calcium carbonate and the hydrophobic modified nano silicon dioxide with other materials, and improving the tensile strength and the impact strength of the polyvinyl chloride pipe, thereby prolonging the service life of the polyvinyl chloride pipe; the silicon-containing polyacrylate modifier is added into the modified particles, so that the hydrophobic effect and the antibacterial property of the polyvinyl chloride pipe can be improved, and the service life of the polyvinyl chloride pipe is further prolonged.
Description
Technical Field
The invention belongs to the technical field of polyvinyl chloride pipes, and particularly relates to a polyvinyl chloride pipe and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is a polymer obtained by polymerizing vinyl chloride monomers under the action of an initiator or light and heat according to a free radical polymerization reaction mechanism, and vinyl chloride homopolymers and vinyl chloride copolymers are collectively called vinyl chloride resin. The molecular weight of the polyvinyl chloride produced industrially is generally between 5 and 11 ten thousand, the polyvinyl chloride has larger polydispersity, the molecular weight is increased along with the reduction of polymerization temperature, the polyvinyl chloride has no fixed melting point, the polyvinyl chloride begins to soften at 80 to 85 ℃, becomes a viscoelastic body at 130 ℃, and is converted into a viscous state at 160 to 180 ℃; the polyvinyl chloride has better mechanical property and dielectric property, and is widely applied to the fields of building materials, industrial products, daily necessities, bottom plate leather, wires and cables, packaging films, pipes and the like.
The polyvinyl chloride pipe comprises a hard polyvinyl chloride pipe, wherein the hard polyvinyl chloride pipe is produced by taking polyvinyl chloride resin as a main raw material, adding a proper amount of a stabilizer, a lubricant, a filler, a toner and the like, and performing plastic extrusion, injection molding and other steps. The hard polyvinyl chloride pipe has the characteristics of light weight, corrosion resistance, small water flow resistance and the like, and is mainly applied to dust water delivery and supply projects, farmland water conservancy water delivery irrigation projects, aquaculture water supply and drainage projects and the like. However, the hard polyvinyl chloride pipe has poor impact resistance and durability, and is not beneficial to long-term use in drainage projects, so that the service life of the polyvinyl chloride pipe needs to be prolonged.
Disclosure of Invention
The invention aims to provide a polyvinyl chloride pipe and a preparation method thereof, and aims to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
a polyvinyl chloride pipe comprises the following raw materials in parts by mass:
50-60 parts of polyvinyl chloride particles, 50 parts of modified particles and 18-22 parts of activated nano filler.
The modified particles are prepared by the following steps:
step 1: mixing vinyl trimethoxy silane and butyl methacrylate to obtain a mixed solution; adding 1/3 of the mixed solution into a flask, adding azobisisobutyronitrile as an initiator, and stirring at 75 ℃ for 30-40min; adding the rest 2/3 of the mixed solution and glycidyl methacrylate into the flask, continuously stirring and carrying out reflux reaction for 45-60min, cooling to 70 ℃, carrying out heat preservation polymerization for 20h, and then heating to 110 ℃, carrying out heat preservation for 2-2.5h to obtain a silicon-containing polyacrylate modifier;
step 2: uniformly mixing polyvinyl chloride powder, nitrile rubber, methyl tin mercaptide, a silicon-containing polyacrylate modifier, an ultraviolet absorbent UV531 and an antioxidant 1010 in a high-speed mixer, then transferring the mixture to an open mill, carrying out open milling for 20-30min at the temperature of 165-175 ℃, and carrying out granulation to prepare modified particles.
Furthermore, the using ratio of the vinyltrimethoxysilane, the butyl methacrylate, the azobisisobutyronitrile and the glycidyl methacrylate is 64g:100g:0.33g:30g.
Further, the dosage ratio of the polyvinyl chloride powder, the nitrile rubber, the methyl tin mercaptide, the silicon-containing polyacrylate modifier, the ultraviolet absorbent UV531 and the antioxidant 1010 is 100g:8g:3.5g:8.5g:8g:6g.
The activated nanofiller is prepared by the steps of:
step S1: adding nano silicon dioxide and absolute ethyl alcohol into a flask, stirring for 30min, then adding vinyl trimethoxy silane, adjusting the pH value to 3 by using glacial acetic acid, ultrasonically dispersing for 30min at the temperature of 20-25 ℃, then dropwise adding ammonia water into the flask to adjust the pH value to 10, stirring for 2-3h at the temperature of 60 ℃, cooling, carrying out suction filtration, drying and crushing to obtain hydrophobically modified nano silicon dioxide;
step S2: adding emulsifier into the epoxidized soybean oil, and stirring for 5-10min at 200-300r/min to obtain emulsion; dispersing nano calcium carbonate by using water, adding hydrophobic modified nano silicon dioxide and emulsion, stirring for 30min under the condition of 250-300r/min, finally adding silane coupling agent KH-792, continuously stirring for 30min, drying, and crushing to obtain the activated nano filler.
Further, the weight ratio of nano silicon dioxide, absolute ethyl alcohol and vinyl trimethoxy silane is 4g:120mL of: 15g.
Further, the dosage ratio of the epoxidized soybean oil to the emulsifier is 100g:25-30g.
Further, the dosage ratio of the nano calcium carbonate, water, the hydrophobic modified nano silicon dioxide, the emulsion and the silane coupling agent KH-792 is 30g:48mL of: 20g:20-25g:10g.
Further, the emulsifier is sodium dodecyl sulfate and monoglyceride fatty acid ester according to a ratio of 3:2, and mixing the components in a mass ratio.
The preparation method of the polyvinyl chloride pipe comprises the following steps:
preheating a high-speed stirrer to 105 ℃, adding polyvinyl chloride particles, modified particles and activated nano filler, heating to 120 ℃, uniformly stirring to obtain a mixture, cooling the mixture to 40 ℃, discharging, and putting the mixture into a double-screw extruder for extrusion molding to obtain the polyvinyl chloride pipe.
The invention has the beneficial effects that:
the polyvinyl chloride pipe raw material comprises activated nano filler, wherein nano silicon dioxide is subjected to hydrophobic modification treatment, so that the hydrophobic effect of the polyvinyl chloride pipe is improved; the nano calcium carbonate and the hydrophobic modified nano silicon dioxide are subjected to activation treatment, namely, the emulsified epoxidized soybean oil is used for coating the nano filler, and then the silane coupling agent is used for surface treatment, so that the dispersibility and the adhesive force of the nano filler are favorably increased, the compatibility of the nano calcium carbonate and the hydrophobic modified nano silicon dioxide with other materials is increased, the tensile strength and the impact strength of the polyvinyl chloride pipe are improved, and the service life of the polyvinyl chloride pipe is prolonged.
The silicon-containing polyacrylate modifier is added into the modified particles, so that the hydrophobic effect of the polyvinyl chloride pipe can be enhanced, the adhesion force of water and the polyvinyl chloride pipe is reduced, the water flow resistance of the polyvinyl chloride pipe is reduced, and the pollution discharge effect and the pollution resistance are increased; and the antibacterial property of the polyvinyl chloride pipe can be improved, so that the corrosion of liquid and microorganisms to the polyvinyl chloride pipe is reduced, and the service life of the polyvinyl chloride pipe is further prolonged.
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.
Example 1
Preparing modified particles comprising the steps of:
step 1: mixing 64g of vinyltrimethoxysilane and 100g of butyl methacrylate to obtain a mixed solution; adding 1/3 of the mixed solution into a flask, adding 0.33g of azobisisobutyronitrile as an initiator, and stirring at 75 ℃ for 30min; then adding the rest 2/3 of the mixed solution and 30g of glycidyl methacrylate into the flask, continuously stirring and carrying out reflux reaction for 45min, cooling to 70 ℃, carrying out heat preservation polymerization for 20h, then heating to 110 ℃, and carrying out heat preservation for 2h to obtain a silicon-containing polyacrylate modifier;
step 2: 100g of polyvinyl chloride powder, 8g of nitrile rubber, 3.5g of methyl tin mercaptide, 8.5g of silicon-containing polyacrylate modifier, 8g of ultraviolet absorbent UV531 and 6g of antioxidant 1010 are mixed uniformly in a high-speed mixer, then the mixture is transferred to an open mill to be milled for 20min at 165 ℃, and modified particles are prepared by dicing.
Example 2
Preparing modified particles comprising the steps of:
step 1: mixing 64g of vinyl trimethoxy silane and 100g of butyl methacrylate to obtain a mixed solution; adding 1/3 of the mixed solution into a flask, adding 0.33g of azobisisobutyronitrile as an initiator, and stirring for 35min at 75 ℃; adding the rest 2/3 of the mixed solution and 30g of glycidyl methacrylate into the flask, continuously stirring and carrying out reflux reaction for 50min, cooling to 70 ℃, carrying out heat preservation polymerization for 20h, and then heating to 110 ℃, and carrying out heat preservation for 2.2h to obtain a silicon-containing polyacrylate modifier;
and 2, step: 100g of polyvinyl chloride powder, 8g of nitrile rubber, 3.5g of methyl tin mercaptide, 8.5g of silicon-containing polyacrylate modifier, 8g of ultraviolet absorbent UV531 and 6g of antioxidant 1010 are mixed uniformly in a high-speed stirrer, then the mixture is transferred to an open mill to be milled for 25min at the temperature of 170 ℃, and the mixture is granulated to prepare modified particles.
Example 3
Preparing modified particles comprising the steps of:
step 1: mixing 64g of vinyltrimethoxysilane and 100g of butyl methacrylate to obtain a mixed solution; adding 1/3 of the mixed solution into a flask, adding 0.33g of azobisisobutyronitrile as an initiator, and stirring for 40min at 75 ℃; adding the rest 2/3 of the mixed solution and 30g of glycidyl methacrylate into the flask, continuously stirring and carrying out reflux reaction for 60min, cooling to 70 ℃, carrying out heat preservation polymerization for 20h, and then heating to 110 ℃, and carrying out heat preservation for 2.5h to obtain a silicon-containing polyacrylate modifier;
step 2: 100g of polyvinyl chloride powder, 8g of nitrile rubber, 3.5g of methyl tin mercaptide, 8.5g of silicon-containing polyacrylate modifier, 8g of ultraviolet absorbent UV531 and 6g of antioxidant 1010 are mixed uniformly in a high-speed stirrer, then the mixture is transferred to an open mill to be milled for 30min at the temperature of 175 ℃, and the mixture is granulated to prepare modified particles.
Example 4
Preparing the activated nanofiller comprising the steps of:
step S1: adding 4g of nano-silica and 120mL of absolute ethyl alcohol into a flask, stirring for 30min, then adding 15g of vinyl trimethoxy silane, adjusting the pH value to 3 by using glacial acetic acid, performing ultrasonic dispersion for 30min at the temperature of 20 ℃, then dropwise adding ammonia water into the flask to adjust the pH value to 10, stirring for 2h at the temperature of 60 ℃, cooling, performing suction filtration, drying, and crushing to obtain hydrophobically modified nano-silica;
step S2: adding 25g of emulsifier into 100g of epoxidized soybean oil, and stirring for 5min at 200r/min to obtain an emulsion; dispersing 30g of nano calcium carbonate in 48mL of water, adding 20g of hydrophobic modified nano silicon dioxide and 20g of emulsion, stirring for 30min under the condition of 250r/min, finally adding 10g of silane coupling agent KH-792, continuing stirring for 30min, drying, and crushing to obtain activated nano filler; wherein, the emulsifier is sodium dodecyl sulfate and monoglyceride fatty acid ester according to the weight ratio of 3:2, and mixing the components in a mass ratio.
Example 5
The preparation of the activated nano filler comprises the following steps:
step S1: adding 4g of nano-silica and 120mL of absolute ethyl alcohol into a flask, stirring for 30min, then adding 15g of vinyl trimethoxy silane, adjusting the pH value to 3 by using glacial acetic acid, ultrasonically dispersing for 30min at 22 ℃, then dropwise adding ammonia water into the flask to adjust the pH value to 10, stirring for 2.5h at 60 ℃, cooling, carrying out suction filtration, drying and crushing to obtain the hydrophobically modified nano-silica;
step S2: adding 28g of emulsifier into 100g of epoxidized soybean oil, and stirring for 8min at the speed of 250r/min to obtain an emulsion; dispersing 30g of nano calcium carbonate in 48mL of water, then adding 20g of hydrophobic modified nano silicon dioxide and 22g of emulsion, stirring for 30min under the condition of 280r/min, finally adding 10g of silane coupling agent KH-792, continuing stirring for 30min, drying, and crushing to obtain activated nano filler; wherein, the emulsifier is sodium dodecyl sulfate and monoglyceride fatty acid ester according to the weight ratio of 3:2, and mixing the components in a mass ratio.
Example 6
The preparation of the activated nano filler comprises the following steps:
step S1: adding 4g of nano-silica and 120mL of absolute ethyl alcohol into a flask, stirring for 30min, then adding 15g of vinyl trimethoxy silane, adjusting the pH value to 3 by using glacial acetic acid, performing ultrasonic dispersion for 30min at 25 ℃, then dropwise adding ammonia water into the flask to adjust the pH value to 10, stirring for 3h at 60 ℃, cooling, performing suction filtration, drying, and crushing to obtain hydrophobically modified nano-silica;
step S2: adding 30g of emulsifier into 100g of epoxidized soybean oil, and stirring for 10min at the speed of 300r/min to obtain an emulsion; dispersing 30g of nano calcium carbonate in 48mL of water, then adding 20g of hydrophobic modified nano silicon dioxide and 25g of emulsion, stirring for 30min under the condition of 300r/min, finally adding 10g of silane coupling agent KH-792, continuing stirring for 30min, drying, and crushing to obtain activated nano filler; wherein the emulsifier is sodium dodecyl sulfate and monoglyceride fatty acid ester according to a ratio of 3:2, and mixing the components in a mass ratio.
Example 7
The preparation method of the polyvinyl chloride pipe comprises the following steps:
preheating a high-speed stirrer to 105 ℃, adding 5kg of polyvinyl chloride particles, 5kg of modified particles prepared in the embodiment 1 and 1.8kg of activated nano filler prepared in the embodiment 4, heating to 120 ℃, uniformly stirring to obtain a mixture, cooling the mixture to 40 ℃, discharging, and putting the mixture into a double-screw extruder for extrusion molding to obtain the polyvinyl chloride pipe.
Example 8
The preparation method of the polyvinyl chloride pipe comprises the following steps:
preheating a high-speed stirrer to 105 ℃, adding 5.5kg of polyvinyl chloride particles, 5kg of modified particles prepared in the embodiment 2 and 2kg of activated nano filler prepared in the embodiment 5, heating to 120 ℃, uniformly stirring to obtain a mixture, cooling the mixture to 40 ℃, discharging, and putting the mixture into a double-screw extruder for extrusion molding to obtain the polyvinyl chloride pipe.
Example 9
The preparation method of the polyvinyl chloride pipe comprises the following steps:
preheating a high-speed stirrer to 105 ℃, adding 6kg of polyvinyl chloride particles, 5kg of modified particles prepared in the embodiment 3 and 2.2kg of activated nano filler prepared in the embodiment 6, heating to 120 ℃, uniformly stirring to obtain a mixture, cooling the mixture to 40 ℃, discharging, and putting the mixture into a double-screw extruder for extrusion molding to obtain the polyvinyl chloride pipe.
Comparative example 1: on the basis of example 3, no silicon-containing polyacrylate modifier is added, and the rest steps are kept unchanged to prepare modified particles, and then the polyvinyl chloride pipe is prepared according to the method of example 9.
Comparative example 2: on the basis of the example 6, the nano-silica and the nano-calcium carbonate are directly mixed to be used as the filler, and the polyvinyl chloride pipe is prepared according to the method of the example 9.
Comparative example 3: on the basis of example 3, a silicon-containing polyacrylate modifier is not added, the other steps are kept unchanged, modified particles are prepared, on the basis of example 6, nano silica and nano calcium carbonate are directly mixed to be used as a filler, and a polyvinyl chloride pipe is prepared according to the method of example 9.
The performance tests of examples 7 to 9 and comparative examples 1 to 3 were carried out by taking the above-mentioned mixed materials for preparing polyvinyl chloride pipes as samples, processing the samples into corresponding dumbbell-type tensile bars and notched bars (specification: 80 mm. Times.10 mm. Times.7 mm), placing the bars in an ultraviolet aging test chamber, keeping the bars at a distance of 10cm from an ultraviolet lamp, carrying out ultraviolet aging at 60 ℃ according to GB/T14522, and then periodically sampling for performance tests (including tensile strength test and notched impact test). Referring to GB/T1010.2-2006, respectively testing the tensile strength of the sample strip under the conditions that the temperature is 20-23 ℃ and the tensile speed is 20 mm/min; referring to GB/T1043-2008, the specimens are subjected to notched impact strength tests at 20-23 ℃ and a 2J pendulum, respectively. The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the tensile strength is less affected with the increase of the ultraviolet aging time, and the tensile strength of the dumbbell-shaped sample strip can be increased in a small range after the surface of the dumbbell-shaped sample strip is aged; the range of variation of the impact strength of the notch pattern gradually decreased with increasing uv aging time, and the bars of examples 7-9 had better tensile and impact strengths.
The contact angle and the surface energy of the polyvinyl chloride pipes in examples 7 to 9 and comparative examples 1 to 2 were measured, respectively, and then the different pipes were left under the same environment for 24 hours, wiped with a cotton swab to the same area, and then spread on different plates, respectively, and the colony count was observed after culturing for 18 hours under the same conditions. The results are shown in table 2:
TABLE 2
| Item | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Contact angle/° | 108.3 | 108.5 | 108.9 | 89.3 | 101.7 | 88.4 |
| Surface energy/mJ.m -2 | 25.1 | 25.2 | 25.2 | 38.2 | 27.5 | 38.8 |
| Number of colonies/number | 6 | 5 | 5 | 32 | 8 | 30 |
As can be seen from table 2, the polyvinyl chloride pipes prepared in examples 7 to 9 have larger contact angles and smaller surface energies, have better hydrophobicity, and generate fewer colonies, and the surfaces have certain antibacterial properties.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The polyvinyl chloride pipe is characterized by comprising the following raw materials in parts by mass:
50-60 parts of polyvinyl chloride particles, 50 parts of modified particles and 18-22 parts of activated nano filler;
the activated nanofiller is prepared by the steps of:
step S1: adding nano silicon dioxide and absolute ethyl alcohol into a flask, stirring for 30min, then adding vinyl trimethoxy silane, adjusting the pH value to 3 by using glacial acetic acid, ultrasonically dispersing for 30min at the temperature of 20-25 ℃, then dropwise adding ammonia water into the flask to adjust the pH value to 10, stirring for 2-3h at the temperature of 60 ℃, cooling, filtering, drying and crushing to obtain hydrophobically modified nano silicon dioxide;
step S2: adding emulsifier into the epoxidized soybean oil and stirring for 5-10min at 200-300r/min to obtain emulsion; dispersing nano calcium carbonate by using water, adding hydrophobic modified nano silicon dioxide and emulsion, stirring for 30min under the condition of 250-300r/min, finally adding silane coupling agent KH-792, continuously stirring for 30min, drying, and crushing to obtain the activated nano filler.
2. The polyvinyl chloride pipe according to claim 1, wherein the nano silica, the absolute ethyl alcohol and the vinyltrimethoxysilane are mixed in a proportion of 4g:120mL of: 15g.
3. The polyvinyl chloride pipe material according to claim 1, wherein the nano calcium carbonate, the water, the hydrophobically modified nano silica, the emulsion and the silane coupling agent KH-792 are used in a ratio of 30g:48mL of: 20g:20-25g:10g.
4. The polyvinyl chloride pipe according to claim 1, wherein the emulsifier is sodium dodecyl sulfate and monoglyceride, and the ratio of the emulsifier to the emulsifier is 3:2, and mixing the components in a mass ratio.
5. The polyvinyl chloride pipe material according to claim 1, wherein the modified particles are prepared by the following steps:
step 1: mixing vinyl trimethoxy silane and butyl methacrylate to obtain a mixed solution; adding 1/3 of the mixed solution into a flask, adding azodiisobutyronitrile as an initiator, and stirring at 75 ℃ for 30-40min; adding the rest 2/3 of the mixed solution and glycidyl methacrylate into the flask, continuously stirring and carrying out reflux reaction for 45-60min, cooling to 70 ℃, carrying out heat preservation polymerization for 20h, and then heating to 110 ℃, carrying out heat preservation for 2-2.5h to obtain a silicon-containing polyacrylate modifier;
step 2: uniformly mixing polyvinyl chloride powder, nitrile rubber, methyl tin mercaptide, a silicon-containing polyacrylate modifier, an ultraviolet absorbent UV531 and an antioxidant 1010 in a high-speed mixer, then transferring the mixture to an open mill, carrying out open milling for 20-30min at the temperature of 165-175 ℃, and carrying out granulation to prepare modified particles.
6. The polyvinyl chloride pipe material according to claim 5, wherein the vinyl trimethoxy silane, the butyl methacrylate, the azobisisobutyronitrile and the glycidyl methacrylate are used in a ratio of 64g:100g:0.33g:30g.
7. The polyvinyl chloride pipe material of claim 5, wherein the ratio of the polyvinyl chloride powder, the nitrile rubber, the methyl tin mercaptide, the silicon-containing polyacrylate modifier, the ultraviolet absorbent UV531 and the antioxidant 1010 is 100g:8g:3.5g:8.5g:8g:6g.
8. The method for preparing polyvinyl chloride pipes according to claim 1, comprising the following steps: and uniformly stirring and mixing the polyvinyl chloride particles, the modified particles and the activated nano filler to obtain a mixture, discharging, and extruding and molding the mixture to obtain the polyvinyl chloride pipe.
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Denomination of invention: A polyvinyl chloride pipe and its preparation method Granted publication date: 20231121 Pledgee: Anhui Hexian Rural Commercial Bank Co.,Ltd. Liyang Branch Pledgor: ANHUI RUIFENG PIPE INDUSTRY Co.,Ltd. Registration number: Y2024980014655 |
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