CN115536961B - Blow-down pipe with high thermal stability - Google Patents

Blow-down pipe with high thermal stability Download PDF

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CN115536961B
CN115536961B CN202211260881.1A CN202211260881A CN115536961B CN 115536961 B CN115536961 B CN 115536961B CN 202211260881 A CN202211260881 A CN 202211260881A CN 115536961 B CN115536961 B CN 115536961B
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parts
heat stabilizer
migration
calcium carbonate
reaction
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CN115536961A (en
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汪进南
刘俊峰
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Anhui Glant New Material Co Ltd
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a high-thermal-stability sewage pipe, which belongs to the technical field of sewage pipe preparation and comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 15-30 parts of modified nano calcium carbonate, 1.5-3 parts of migration-resistant heat stabilizer, 2-6 parts of impact modifier, 1-3 parts of antioxidant and 1-1.5 parts of lubricant; the self-made migration-resistant heat stabilizer is used for replacing the traditional zinc-calcium heat stabilizer, and the modified calcium carbonate is added to act as reinforcing particles, wherein the migration-resistant heat stabilizer not only has the same characteristics as the traditional calcium-zinc heat stabilizer (neutralizing HCl and replacing unstable chlorine atoms), but also has excellent migration resistance, and the modified calcium carbonate not only has a toughening effect on a pipe substrate, but also can be complexed with metal chloride formed after the migration-resistant heat stabilizer absorbs hydrogen chloride, so that the metal chloride is inhibited from promoting PVC decomposition and inhibiting zinc burning, and the thermal stability of a sewage drain pipe is further improved.

Description

Blow-down pipe with high thermal stability
Technical Field
The invention belongs to the technical field of sewage pipes, and particularly relates to a sewage pipe with high thermal stability.
Background
Polyvinyl chloride (PVC) is prepared from vinyl chloride monomers by free radical polymerization, and hard and soft products meeting different purposes can be prepared by adding appropriate auxiliaries. PVC has the unique properties of high strength, corrosion resistance, flame retardance, insulation, transparency, good compatibility with various plastic additives in a wide range and the like, and is widely applied to pipe fitting products, in particular to drain pipes.
However, PVC is a white powder with an amorphous structure, the degree of branching is small, the glass transition temperature is 77-90 ℃, the decomposition starts at about 170 ℃, the stability to light and heat is poor, hydrogen chloride is generated by decomposition at 100 ℃ or after long-time sunlight exposure, further automatic catalytic decomposition is performed, discoloration is caused, physical and mechanical properties are also rapidly reduced, a stabilizer must be added in practical application to improve the stability to heat and light, the light stability is usually realized by adding an ultraviolet absorber or a light stabilizer, the heat stability is usually enhanced by adding a heat stabilizer, wherein organotin and calcium zinc stabilizers are widely applied (mostly liquid), but in the PVC processing process, the heat stability of PVC cannot be improved for a long time due to the problems of easy migration, volatilization, large consumption and the like.
Therefore, it is necessary to provide a polyvinyl chloride drain pipe with high thermal stability.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a sewage drain pipe with high thermal stability.
The aim of the invention can be achieved by the following technical scheme:
a sewage pipe with high thermal stability comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 15-30 parts of modified nano calcium carbonate, 1.5-3 parts of migration-resistant heat stabilizer, 2-6 parts of impact modifier, 1-3 parts of antioxidant and 1-1.5 parts of lubricant;
the drain pipe with high thermal stability is manufactured by the following steps:
adding polyvinyl chloride, modified nano calcium carbonate, migration-resistant heat stabilizer, impact modifier, antioxidant and lubricant into a high-speed stirrer, mixing at the rotating speed of 1000-1500r/min, setting the initial temperature of a charging barrel to 105 ℃ and heating, when the temperature of the mixture in the charging barrel reaches 120 ℃, putting into a low-speed stirrer for cold mixing and stirring, stirring at the rotating speed of 300-500r/min until the temperature of the mixture is reduced to 45 ℃, discharging, transferring the obtained material into a double-screw extruder for extrusion molding, and obtaining the drain pipe with high thermal stability.
Further, the migration resistant heat stabilizer is prepared by the steps of
Step S11, adding maleic anhydride into a four-neck flask, melting solid maleic anhydride under heating and mechanical stirring conditions, heating to 100-130 ℃, adding pentaerythritol, and performing mechanical stirring reaction for 4-6 hours to obtain an intermediate product a, wherein the molar ratio of maleic anhydride to pentaerythritol is 1:4.3-4.5, using maleic anhydride and pentaerythritol as substrates, and obtaining an intermediate product a containing ester groups, carbon-carbon double bonds and carboxyl end groups through esterification reaction;
step S12, placing the four-neck flask containing the intermediate product a in an oil bath pot at 120 ℃, slowly dropwise adding a calcium acetate aqueous solution and a zinc acetate aqueous solution while stirring, stirring for 3-4 hours after the dropwise adding is finished, performing rotary evaporation of water after the reaction is finished, and performing reduced pressure distillation to remove acetic acid until no liquid is distilled off to obtain a migration-resistant heat stabilizer, wherein the mass ratio of the intermediate product a to the calcium acetate to the zinc acetate is 15.1-16.3:9.68:12.07, reacting the intermediate product a with calcium acetate and zinc acetate to obtain the migration resistant heat stabilizer containing ester groups, carbon-carbon double bonds and carboxylate structures.
Further, the modified calcium carbonate is prepared by the following steps:
adding deionized water, absolute ethyl alcohol and ethylaluminum acetoacetate diisopropyl ester into a reaction kettle, stirring for 10min, heating to 60 ℃, adding nano calcium carbonate, continuously stirring for 30-60min under the protection of nitrogen, carrying out suction filtration after the reaction is finished, drying a filter cake, placing the filter cake into the reaction kettle, adding tetrahydrofuran, stirring for 10-15min, adding modified ricinoleate and azodiisobutyronitrile, heating to reflux for 3-4h, and carrying out rotary evaporation to remove a solvent after the reaction is finished, thus obtaining modified calcium carbonate;
wherein, the dosage ratio of deionized water, absolute ethyl alcohol, ethylaluminum acetoacetate diisopropyl ester, nano calcium carbonate, modified ricinoleate and azodiisobutyronitrile is 20-30mL:50-60mL:2g:25-30g:6.3-8.4g:0.2g.
According to the invention, the surface of nano calcium carbonate is modified by using ethylaluminum diacetate diisopropyl ester and unsaturated double bonds are introduced, then under the action of an initiator, the modified ricinoleic acid ester enters the surface of the calcium carbonate through the polymerization grafting reaction of the unsaturated double bonds to obtain modified calcium carbonate, the modified calcium carbonate has the toughening effect on a pipe substrate and also plays a role in improving the thermal stability of the substrate, the toughening effect is realized on the one hand by the reinforcing effect of inorganic calcium carbonate, and on the other hand, the ricinoleic acid ester grafted on the surface of the modified calcium carbonate belongs to a plant oil-based plasticizer, and has larger molecular weight than that of a o-benzene plasticizer, small mobility and good plasticizing effect; the improvement of the thermal stability is that firstly inorganic calcium carbonate can absorb HCl generated by PVC heating, secondly the modified ricinoleate molecular chain contains a plurality of epoxy groups and hydroxyl groups, the epoxy groups can absorb HCl generated by PVC thermal decomposition and replace unstable chlorine atoms, the hydroxyl groups can be complexed with metal chloride formed after the migration-resistant heat stabilizer absorbs hydrogen chloride, and the metal chloride is inhibited to promote PVC decomposition and inhibit zinc burning.
Further, the modified ricinoleate is prepared by the steps of:
s21, placing pentaerythritol and ricinoleic acid in a reactor, protecting nitrogen, and adding a solid catalyst SO 4 2- /TiO 2 Stirring at 140 ℃ for 3-4 hours, then changing the mixture into a decompression reaction device, vacuumizing at 140 ℃ for 2 hours to obtain an intermediate product b, mixing the intermediate product b, phosphoric acid and formic acid, dropwise adding 30wt% of hydrogen peroxide at 50 ℃, carrying out heat preservation reaction for 3-4 hours after the dropwise adding is finished, washing the product with distilled water for 3 times after the reaction is finished, and carrying out rotary evaporation at 50 ℃ to obtain epoxy ricinoleate;
wherein, pentaerythritol, ricinoleic acid and solid catalyst SO 4 2- /TiO 2 The dosage ratio of (2) is 18.2-23g:298g:2.8-2.9g; the mass ratio of the intermediate product b to phosphoric acid to formic acid to 30wt% hydrogen peroxide is 80:1:15:60-66, esterifying pentaerythritol and ricinoleic acid under the action of a solid catalyst, and then performing epoxidation reaction;
s22, mixing epoxy ricinoleate, 4-vinylaniline and toluene, adding p-benzoquinone, heating to 100-110 ℃, stirring and reacting for 5-6 hours, removing toluene by reduced pressure distillation after the reaction is finished, washing a distillation product with hot water of 50-80 ℃, and drying to obtain modified ricinoleate;
wherein the dosage ratio of the epoxy ricinoleate to the 4-vinylaniline to the toluene is 12.5-13.8g:3.5-4.2g:200-300mL, wherein the dosage of the p-benzoquinone is the mass of the epoxy ricinoleate and the 4-vinylaniline and 0.1-0.2%, so that the epoxy group of the epoxy ricinoleate and the amino group of the 4-vinylaniline undergo a ring-opening reaction to obtain the ricinoleate containing unsaturated double bonds, epoxy groups and hydroxyl groups.
Further, the impact modifier is one or more of CPE (chlorinated polyethylene), ACR (acrylic copolymer) and MBS (methyl methacrylate-butadiene-styrene terpolymer) in any ratio.
Further, the antioxidant is one or more of antioxidants 1010, 1076 and 168, and the antioxidants are combined according to any proportion.
Further, the lubricant is one or more of paraffin wax, polyethylene wax, stearic acid and calcium stearate, which are combined according to any proportion.
The invention has the beneficial effects that:
the invention provides a drain pipe with high thermal stability, which uses a self-made migration-resistant heat stabilizer to replace the traditional zinc-calcium heat stabilizer, and adds modified calcium carbonate to act as reinforcing particles, wherein the migration-resistant heat stabilizer not only has the same characteristics as the traditional calcium-zinc heat stabilizer (neutralizing HCl and replacing unstable chlorine atoms), but also has excellent migration resistance, and the first point is represented by the characteristic of a macromolecular structure of the migration-resistant heat stabilizer and is not easy to migrate; the second point is represented by the existence of a plurality of ester groups in the heat stabilizer, so that the compatibility of the heat stabilizer and the PVC matrix is improved; the third point is that the carbon-carbon double bond in the molecular structure can be added with the conjugated double bond existing in PVC to form a saturated high polymer chain, so that the purpose of preventing the growth of conjugated polyene chain is achieved, the heat stabilizer can be anchored in the PVC matrix through chemical bonds, and the stability of the heat stabilizer in the matrix is improved; the modified calcium carbonate not only has toughening effect on a pipe substrate, but also can complex with metal chloride formed after hydrogen chloride is absorbed by the migration-resistant heat stabilizer, so that the metal chloride is inhibited from promoting PVC decomposition, the phenomenon of zinc burning is inhibited, the thermal stability of a sewage pipe is further improved, and the sewage pipe prepared by the invention has good mechanical property and high thermal stability.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Solid catalyst SO 4 2- /TiO 2 Is obtained by reference (Zhang Qi, chang Jie, wang Tiejun, etc., solid acid catalyst SO) 4 2- /Si 2 -TiO 2 Preparation of (C) and catalytic esterification Properties [ J ]]Catalytic journal, 2006,27 (11): 1033-1038).
Example 1
The migration-resistant heat stabilizer is prepared by the following steps of
Step S11, adding 9.8g of maleic anhydride into a four-neck flask, melting solid maleic anhydride under heating and mechanical stirring conditions, heating to 100 ℃, adding 58.54g of pentaerythritol, and performing mechanical stirring reaction for 4 hours to obtain an intermediate product a;
and S12, placing a four-neck flask containing 15.1g of the intermediate product a in an oil bath pot at 120 ℃, slowly dropwise adding 50mL of calcium acetate aqueous solution containing 9.68g of calcium acetate and 50mL of zinc acetate aqueous solution containing 12.07g of zinc acetate while stirring, stirring for reaction for 3 hours after the dropwise adding is finished, distilling water in a rotary mode, and distilling acetic acid under reduced pressure until no liquid is distilled out to obtain the migration resistant heat stabilizer.
Example 2
The migration-resistant heat stabilizer is prepared by the following steps of
Step S11, adding 9.8g of maleic anhydride into a four-neck flask, melting solid maleic anhydride under heating and mechanical stirring conditions, then heating to 130 ℃, adding 61.2g of pentaerythritol, and performing mechanical stirring reaction for 6 hours to obtain an intermediate product a;
and S12, placing the four-neck flask containing 16.3g of the intermediate product a in an oil bath pot at 120 ℃, slowly dropwise adding 50mL of calcium acetate aqueous solution containing 9.68g of calcium acetate and 50mL of zinc acetate aqueous solution containing 12.07g of zinc acetate while stirring, stirring for reaction for 4 hours after the dropwise adding is finished, distilling water in a rotary mode, and distilling acetic acid under reduced pressure until no liquid is distilled out to obtain the migration resistant heat stabilizer.
Example 3
The modified calcium carbonate is prepared by the following steps:
adding 20mL of deionized water, 50mL of absolute ethyl alcohol and 2g of ethylaluminum acetoacetate diisopropyl ester into a reaction kettle, stirring for 10min, heating to 60 ℃, adding 25g of nano calcium carbonate, continuously stirring for 30min under the protection of nitrogen, carrying out suction filtration, drying a filter cake, placing the filter cake into the reaction kettle, adding 250mL of tetrahydrofuran, stirring for 10min, adding 6.3g of modified ricinoleate and 0.2g of azobisisobutyronitrile, heating to reflux, reacting for 3h, and removing the solvent by rotary evaporation to obtain the modified calcium carbonate.
The modified ricinoleic acid ester is prepared by the following steps:
step S21, 18.2g of pentaerythritol and 298g of ricinoleic acid are placed in a reactor, and 2.8g of solid catalyst SO is added under the protection of nitrogen 4 2- /TiO 2 Stirring at 140 ℃ for reaction for 3 hours, changing the reaction mixture into a decompression reaction device, vacuumizing at 140 ℃ for 2 hours to obtain an intermediate product b, mixing 80g of the intermediate product b, 1g of phosphoric acid and 15g of formic acid, dropwise adding 60g of 30wt% hydrogen peroxide at 50 ℃, after the dropwise adding is finished, carrying out heat preservation reaction for 3 hours, washing the product with distilled water for 3 times, and carrying out rotary evaporation at 50 ℃ to obtain epoxy ricinoleate;
step S22, mixing 12.5g of epoxy ricinoleate, 3.5g of 4-vinylaniline and 200mL of toluene, adding p-benzoquinone, heating to 100 ℃, stirring for reaction for 5 hours, removing toluene by reduced pressure distillation after the reaction is finished, washing a distillation product with hot water at 50 ℃, and drying to obtain modified ricinoleate, wherein the dosage of the p-benzoquinone is 0.1% of the mass of the epoxy ricinoleate and the 4-vinylaniline.
Example 4
The modified calcium carbonate is prepared by the following steps:
adding 30mL of deionized water, 60mL of absolute ethyl alcohol and 2g of ethylaluminum acetoacetate diisopropyl ester into a reaction kettle, stirring for 10min, heating to 60 ℃, adding 30g of nano calcium carbonate, continuously stirring for 60min under the protection of nitrogen, carrying out suction filtration after the reaction is finished, drying a filter cake, placing the filter cake into the reaction kettle, adding 300mL of tetrahydrofuran, stirring for 15min, adding 8.4g of modified ricinoleate and 0.2g of azobisisobutyronitrile, heating to reflux, reacting for 4h, and removing the solvent by rotary evaporation to obtain the modified calcium carbonate.
The modified ricinoleic acid ester is prepared by the following steps:
step S21, 23g of pentaerythritol and 298g of ricinoleic acid are placed in a reactor, and 2.9g of solid catalyst SO is added under the protection of nitrogen 4 2- /TiO 2 Stirring at 140 ℃ for reaction for 4 hours, changing the reaction mixture into a decompression reaction device, vacuumizing at 140 ℃ for 2 hours to obtain an intermediate product b, mixing 80g of the intermediate product b, 1g of phosphoric acid and 15g of formic acid, dropwise adding 66g of 30wt% hydrogen peroxide at 50 ℃, after the dropwise adding is finished, carrying out heat preservation for reaction for 4 hours, washing the product with distilled water for 3 times, and carrying out rotary evaporation at 50 ℃ to obtain epoxy ricinoleate;
step S22, mixing 13.8g of epoxy ricinoleate, 4.2g of 4-vinylaniline and 300mL of toluene, adding p-benzoquinone, heating to 110 ℃, stirring for reaction for 6 hours, removing toluene by reduced pressure distillation after the reaction is finished, washing a distillation product with hot water at 80 ℃, and drying to obtain modified ricinoleate, wherein the dosage of the p-benzoquinone is 0.2% of the mass of the epoxy ricinoleate and the 4-vinylaniline.
Comparative example 1
The modified calcium carbonate is prepared by the following steps:
adding 30mL of deionized water, 60mL of absolute ethyl alcohol and 2g of ethylaluminum acetoacetate diisopropyl ester into a reaction kettle, stirring for 10min, heating to 60 ℃, adding 30g of nano calcium carbonate, continuously stirring for 60min under the protection of nitrogen, and after the reaction is finished, carrying out suction filtration, and drying a filter cake to obtain the modified calcium carbonate.
Example 5
A sewage pipe with high thermal stability comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 15 parts of modified nano calcium carbonate of example 3, 1.5 parts of migration-resistant heat stabilizer of example 1, 2 parts of impact modifier, 1 part of antioxidant 1010 and 1 part of stearic acid;
the drain pipe with high thermal stability is manufactured by the following steps:
adding polyvinyl chloride, modified nano calcium carbonate, migration-resistant heat stabilizer, impact modifier, antioxidant and lubricant into a high-speed stirrer, mixing at a rotating speed of 1000r/min, setting the initial temperature of a charging barrel to 105 ℃ and heating, when the temperature of the mixture in the charging barrel reaches 120 ℃, putting the mixture into a low-speed stirrer for cold mixing and stirring, stirring at a rotating speed of 300r/min until the temperature of the mixture is reduced to 45 ℃, discharging, transferring the obtained material into a double-screw extruder for extrusion molding, and obtaining a drain pipe with high thermal stability, wherein the rotating speed of a screw of the screw extruder is 45r/min, the three-stage temperature of the screw is 150 ℃, 175 ℃, 185 ℃ and the temperature of a die is 190 ℃.
Wherein the impact modifier is CPE.
Example 6
A sewage pipe with high thermal stability comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 25 parts of modified nano calcium carbonate of example 4, 1.9 parts of migration-resistant heat stabilizer of example 1, 4 parts of impact modifier, 2 parts of antioxidant 1010 and 1.3 parts of stearic acid;
the drain pipe with high thermal stability is manufactured by the following steps:
adding polyvinyl chloride, modified nano calcium carbonate, migration-resistant heat stabilizer, impact modifier, antioxidant and lubricant into a high-speed stirrer, mixing at the rotation speed of 1200r/min, setting the initial temperature of a charging barrel to 105 ℃ and heating, when the temperature of the mixture in the charging barrel reaches 120 ℃, putting the mixture into a low-speed stirrer for cold mixing and stirring, stirring at the rotation speed of 400r/min until the temperature of the mixture is reduced to 45 ℃, discharging, transferring the obtained material into a double-screw extruder for extrusion molding, and obtaining a drain pipe with high thermal stability, wherein the screw rotation speed of the screw extruder is 45r/min, the three-section temperature of the screw is 150 ℃, 175 ℃, 185 ℃ and the die temperature is 190 ℃.
Wherein the impact modifier is CPE.
Example 7
A sewage pipe with high thermal stability comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 30 parts of modified nano calcium carbonate of example 3, 3 parts of migration-resistant heat stabilizer of example 2, 6 parts of impact modifier, 3 parts of antioxidant 1010 and 1.5 parts of stearic acid;
the drain pipe with high thermal stability is manufactured by the following steps:
adding polyvinyl chloride, modified nano calcium carbonate, migration-resistant heat stabilizer, impact modifier, antioxidant and lubricant into a high-speed stirrer, mixing at a rotating speed of 1500r/min, setting the initial temperature of a charging barrel to 105 ℃ and heating, when the temperature of the mixture in the charging barrel reaches 120 ℃, putting the mixture into a low-speed stirrer for cold mixing and stirring, stirring at a rotating speed of 500r/min until the temperature of the mixture is reduced to 45 ℃, discharging, transferring the obtained material into a double-screw extruder for extrusion molding, and obtaining a drain pipe with high thermal stability, wherein the rotating speed of a screw of the screw extruder is 45r/min, the three-stage temperature of the screw is 150 ℃, 175 ℃, 185 ℃ and the temperature of a die is 190 ℃.
Wherein the impact modifier is CPE.
Comparative example 2
The migration resistant heat stabilizer in example 5 was replaced with a calcium zinc composite stabilizer sold by Changzhou, city, send chemical Co., ltd. And the rest of the raw materials and the preparation process were the same as those in example 5.
Comparative example 3
The modified calcium carbonate of example 6 was replaced with the material of comparative example 1, and the remaining raw materials and the preparation process were the same as in example 6.
The drain pipes prepared in examples 5 to 7 and comparative examples 2 to 3 were tested for migration resistance: taking the equal-mass sheet of the sewage pipe, respectively placing the equal-mass sheet in 30% acetic acid solution and n-hexane in volume fraction, soaking for 24 hours at 30 ℃, taking out, drying, calculating the mass loss rate (%) of the sheet, and ensuring that the lower the mass loss rate is, the better the migration resistance is, and the tensile strength is: the tensile rate was 10mm/min and the heat aging resistance was measured according to GB/T1040.1-2006: the tensile strength change rate is tested by heat preservation treatment 168 in a heat aging oven at 135 ℃, and the lower the tensile strength change is, the better the thermal stability is, and the Vicat softening point temperature is: according to GB/T1633-2000, the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the drain pipes prepared in examples 5 to 7 were not only good in mechanical properties but also high in thermal stability, compared with comparative examples 2 to 3.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (6)

1. The blow-down pipe with high thermal stability is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 15-30 parts of modified nano calcium carbonate, 1.5-3 parts of migration-resistant heat stabilizer, 2-6 parts of impact modifier, 1-3 parts of antioxidant and 1-1.5 parts of lubricant;
wherein, the migration-resistant heat stabilizer is prepared by the following steps:
step S11, adding maleic anhydride into a four-neck flask, heating to melt the maleic anhydride, heating to 100-130 ℃, adding pentaerythritol, and mechanically stirring for reaction for 4-6 hours to obtain an intermediate product a;
step S12, placing the four-neck flask containing the intermediate product a in an oil bath pot at 120 ℃, slowly dropwise adding a calcium acetate aqueous solution and a zinc acetate aqueous solution while stirring, and stirring for reaction for 3-4 hours after the dropwise adding is finished to obtain a migration-resistant heat stabilizer;
the modified nano calcium carbonate is prepared by the following steps:
mixing deionized water, absolute ethyl alcohol and ethylaluminum acetoacetate diisopropyl ester, heating to 60 ℃, adding nano calcium carbonate, continuously stirring under the protection of nitrogen, carrying out suction filtration after the reaction is finished, drying a filter cake, placing the filter cake in a reaction kettle, adding tetrahydrofuran, stirring, adding modified ricinoleate and azodiisobutyronitrile, and carrying out reflux reaction for 3-4 hours to obtain modified nano calcium carbonate;
the modified ricinoleic acid ester is prepared by the following steps:
s21, placing pentaerythritol and ricinoleic acid in a reactor, protecting nitrogen, and adding a solid catalyst SO 4 2- /TiO 2 Stirring at 140 ℃ for 3-4 hours, then changing the mixture into a decompression reaction device, vacuumizing at 140 ℃ for 2 hours to obtain an intermediate product b, mixing the intermediate product b, phosphoric acid and formic acid, dropwise adding 30wt% of hydrogen peroxide at 50 ℃, carrying out heat preservation reaction for 3-4 hours after the dropwise adding is finished, washing the product with distilled water for 3 times after the reaction is finished, and carrying out rotary evaporation at 50 ℃ to obtain epoxy ricinoleate;
and S22, mixing epoxy ricinoleate, 4-vinylaniline and toluene, adding p-benzoquinone, heating to 100-110 ℃, and stirring for reacting for 5-6h to obtain modified ricinoleate.
2. The high thermal stability drain pipe of claim 1, wherein the molar ratio of maleic anhydride to pentaerythritol in step S11 is 1:4.3-4.5.
3. A highly thermally stable drain pipe as defined in claim 1 wherein the mass ratio of intermediate product a, calcium acetate and zinc acetate in step S12 is 15.1-16.3:9.68:12.07.
4. the high-heat-stability sewage drain pipe according to claim 1, wherein the dosage ratio of deionized water, absolute ethyl alcohol, ethylaluminum acetoacetate diisopropyl ester, nano calcium carbonate, modified ricinoleate and azodiisobutyronitrile is 20-30mL:50-60mL:2g:25-30g:6.3-8.4g:0.2g.
5. The high thermal stability drain pipe according to claim 1, wherein in step S21 pentaerythritol, ricinoleic acid, solid catalyst SO 4 2- /TiO 2 The dosage ratio of (2) is 18.2-23g:298g:2.8-2.9g; the mass ratio of the intermediate product b to phosphoric acid to formic acid to 30wt% hydrogen peroxide is 80:1:15:60-66.
6. A highly thermally stable drain pipe as defined in claim 1 wherein the ratio of epoxy ricinoleate, 4-vinylaniline and toluene used in step S22 is 12.5-13.8g:3.5-4.2g:200-300mL, and the dosage of the p-benzoquinone is 0.1-0.2% of the mass of the epoxy ricinoleate and the 4-vinylaniline.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567669A (en) * 1967-08-04 1971-03-02 Diamond Shamrock Corp Preparation of rigid polyvinyl chloride particles having a high bulk density
CN1807519A (en) * 2006-01-27 2006-07-26 华南理工大学 Modified nanometer calcium carbonate and method for making same and uses
CN115073861A (en) * 2022-07-15 2022-09-20 安徽瑞丰管业有限公司 Anti-tensile polyvinyl chloride communication pipe and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567669A (en) * 1967-08-04 1971-03-02 Diamond Shamrock Corp Preparation of rigid polyvinyl chloride particles having a high bulk density
CN1807519A (en) * 2006-01-27 2006-07-26 华南理工大学 Modified nanometer calcium carbonate and method for making same and uses
CN115073861A (en) * 2022-07-15 2022-09-20 安徽瑞丰管业有限公司 Anti-tensile polyvinyl chloride communication pipe and preparation method thereof

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