CN110746722A - Preparation method of heat-resistant polyvinyl chloride pipeline material - Google Patents
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Abstract
The invention relates to the technical field of pipelines, and discloses a preparation method of a heat-resistant polyvinyl chloride pipeline material. The method comprises the following steps: 1) weighing the following raw materials in parts by weight: 100-120 parts of polyvinyl chloride resin, 5-10 parts of nano calcium carbonate, 2-5 parts of a calcium-zinc stabilizer, 2-5 parts of mesoporous silica composite particles, 1-3 parts of calcium stearate, 0.5-1 part of phosphite ester, 0.5-1 part of phenyl salicylate and 0.5-1 part of silane coupling agent; 2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent into a high-speed stirrer, and heating and stirring to obtain a premix; 3) adding a calcium zinc stabilizer, phosphite ester and phenyl salicylate into the premix, and continuously stirring to obtain a blend; 4) and adding the blend into a screw extruder for extrusion granulation to obtain the product. The polyvinyl chloride pipeline material prepared by the invention has excellent thermal stability.
Description
Technical Field
The invention relates to the technical field of pipelines, in particular to a preparation method of a heat-resistant polyvinyl chloride pipeline material.
Background
The plastic pipe has been developed for more than 60 years since the coming out, has the characteristics of light weight, good chemical stability, convenient use, environmental protection, long service life and the like, is widely applied to the fields of industry, agriculture, construction, daily use and the like, has better economic benefit and social benefit compared with the traditional plastic pipe, and has better and more accepted performance by people. At present, along with the rapid increase of the requirements of buildings, municipal administration, water conservancy and industry and agriculture on plastic pipes, the field of the plastic pipes in China shows a high-speed development state, wherein polyvinyl chloride (PVC) pipes are the main products of the plastic pipes in China at present and account for 55 percent of the total amount of the pipes in China. The polyvinyl chloride pipeline drain pipe has the advantages of light weight, low price, corrosion resistance and the like, and is widely applied to indoor drainage of residential buildings and public buildings. The main disadvantage of polyvinyl chloride pipes is that the thermal stability is poor, and under the excitation of heat, oxygen, light and the like, the active sites such as double bonds in the defects in the structure of the polyvinyl chloride resin can generate free radicals, thereby initiating the chain reaction of removing HCl. The melting point of the polyvinyl chloride resin is about 200 ℃, but the polyvinyl chloride resin begins to decompose and release hydrogen chloride gas at 100 ℃, so that a heat stabilizer needs to be added to improve the heat stability of the polyvinyl chloride resin.
Chinese patent publication No. CN109161127 discloses an antibacterial polyvinyl chloride pipe and a preparation method thereof, and the polyvinyl chloride pipe obtained by using raw materials of polyvinyl chloride, slow-release antibacterial particles, light calcium carbonate, an impact modifier, a stabilizer, a lubricant, a silane coupling agent and the like has good antibacterial performance, but has poor thermal stability, easy pyrolysis and short service life. Chinese patent publication No. CN102850696 discloses a high-toughness polyvinyl chloride pipe material which is prepared by using polyvinyl chloride resin, chlorinated polyvinyl chloride resin and acrylic resin as main components, and organic tin heat stabilizer or calcium zinc stabilizer is added to improve the heat resistance of the pipe material; also for example, chinese patent publication No. CN102863713 discloses a high elongation and high impact polyvinyl chloride pipe composition and a preparation method thereof, the composition comprises polyvinyl chloride resin, a lightly chlorinated HDPE and an interpenetrating network copolymer of acrylate, a heat stabilizer, a lubricant, a filler, and a colorant, and the heat stability of the polyvinyl chloride pipe is improved by adding an organotin heat stabilizer. In the technical scheme, the thermal stability of the polyvinyl chloride is improved by adding the thermal stabilizer, so that the polyvinyl chloride pipeline is prevented from thermal degradation, but the thermal stability of the polyvinyl chloride pipeline is improved by the thermal stabilizer in a limited way.
Disclosure of Invention
The invention provides a preparation method of a heat-resistant polyvinyl chloride pipeline material, aiming at overcoming the problem of poor thermal stability of a polyvinyl chloride pipe in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a heat-resistant polyvinyl chloride pipeline material comprises the following steps:
1) weighing the following raw materials in parts by weight: 100-120 parts of polyvinyl chloride resin, 5-10 parts of nano calcium carbonate, 2-5 parts of a calcium-zinc stabilizer, 2-5 parts of mesoporous silica composite particles, 1-3 parts of calcium stearate, 0.5-1 part of phosphite ester, 0.5-1 part of phenyl salicylate and 0.5-1 part of silane coupling agent;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent into a high-speed stirrer, and stirring for 20-30min at the temperature of 108-;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 10-20min to obtain a blend;
4) and adding the blend into a screw extruder for extrusion granulation to obtain the product.
Preferably, the apparent density of the polyvinyl chloride resin is more than or equal to 0.45g/cm3The viscosity is 85-120mL/g, the degree of polymerization is 800-1200, and the K value is 60-68.
Preferably, the method for preparing the mesoporous silica composite particle comprises the following steps: adding an epoxy silane coupling agent into an ethanol water solution, stirring and dissolving, adjusting the pH to 5-6, heating in a water bath to 40-50 ℃, stirring and hydrolyzing for 1-2h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, stirring and reacting for 20-30min, and then filtering, washing and drying to obtain alkylated silica microspheres; adding 3,3 '-diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution, adding alkylated silica microspheres into the 3,3 '-diaminodipropylamine solution, stirring to form a dispersion, dropwise adding a sodium hydroxide solution into the dispersion, heating to 70-80 ℃, stirring and reacting for 1-2 hours, and then filtering, washing and drying to obtain silica-loaded 3,3' -diaminodipropylamine microspheres; adding the silica-loaded 3,3' -diaminodipropylamine microspheres into an ethanol aqueous solution, then adding ammonia water and hexadecyl trimethyl ammonium bromide, dropwise adding tetraethyl orthosilicate under the stirring condition, reacting for 2-4h after dropwise adding is finished, and then centrifuging, filtering, washing and drying to obtain the mesoporous silica composite particles.
Preferably, the mass ratio of the silica microspheres to the epoxy silane coupling agent is 1: 1-2.
Preferably, the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1: 3-5.
Preferably, the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1: 1-1.6.
Preferably, the preparation method of the silica microspheres comprises the following steps: adding ammonia water into ethanol water solution, mixing uniformly to obtain mixed solution, heating in water bath to 30-35 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, keeping the temperature for reaction for 3-5h after dropwise adding, and then centrifuging, filtering, washing and drying to obtain the silicon dioxide microspheres.
Preferably, the addition amount of the tetraethyl orthosilicate is 5-10% of the mass of the ethanol water solution.
The preparation method comprises the steps of firstly, uniformly mixing polyvinyl chloride resin, nano calcium carbonate filler, mesoporous silica composite particles, calcium stearate lubricant and silane coupling agent by using a high-speed stirrer under the heating condition to obtain a premix, then adding a calcium zinc stabilizer, a phosphite antioxidant and a phenyl salicylate ultraviolet absorbent, further stirring and mixing to obtain a blend, feeding the blend into a screw extruder for melt blending, and performing melt extrusion granulation to obtain the polyvinyl chloride pipeline material.
Firstly, the linear conjugated polyene generates cyclization to generate aromatic hydrocarbon compounds, the more aromatic hydrocarbon compounds are generated, the more the thermal degradation of the polyvinyl chloride resin is serious; secondly, the hydrogen chloride gas released by the polyvinyl chloride resin when heated can catalyze the thermal degradation of the polyvinyl chloride, thereby playing a role in accelerating the negative effect of the polyvinyl chloride degradation. In order to improve the thermal stability of the polyvinyl chloride resin, on one hand, the addition of the calcium-zinc stabilizer prevents the linear conjugated polyene from generating cyclization to generate an aromatic hydrocarbon compound, thereby inhibiting the further thermal degradation of the polyvinyl chloride resin and improving the heat resistance of the polyvinyl chloride resin; on the other hand, the mesoporous silica composite particles are added to remove hydrogen chloride gas generated by polyvinyl chloride when heated, the mesoporous silica composite particles have a porous structure and have extremely strong adsorption performance, and the mesoporous silica composite particles are used for adsorbing the hydrogen chloride gas generated by polyvinyl chloride resin, so that the hydrogen chloride is prevented from generating a catalytic effect on the degradation of polyvinyl chloride, and the thermal stability of the polyvinyl chloride pipeline material is improved.
According to the formula of the polyvinyl chloride pipe material, the mesoporous silica is added to adsorb hydrogen chloride gas generated by polyvinyl chloride when heated, and although the mesoporous silica has excellent adsorption performance on the hydrogen chloride gas, the mesoporous silica has limited adsorption capacity on the hydrogen chloride, and the mesoporous silica is easy to reach an adsorption saturated state. In order to improve the adsorption capacity of the mesoporous silica, the self-made mesoporous silica composite particle solves the problem that the mesoporous silica is easy to saturate in hydrogen chloride adsorption, and improves the adsorption capacity of the mesoporous silica to the hydrogen chloride, and the specific preparation method of the mesoporous silica composite particle comprises the following steps: firstly, preparing silicon dioxide microspheres, adopting a hydrolyzed epoxy silane coupling agent to carry out modification treatment on the silicon dioxide microspheres, attaching hydroxyl groups to the hydrolyzed epoxy silane coupling agent, reacting and dehydrating the hydroxyl groups with the hydroxyl groups on the surfaces of the silicon dioxide microspheres, grafting the epoxy silane coupling agent to the surfaces of the silicon dioxide microspheres, then utilizing the epoxy groups in the epoxy silane coupling agent to carry out ring opening under the action of alkaline sodium hydroxide and react with partial amino groups in 3,3 '-diaminodipropylamine molecules, grafting 3,3' -diaminodipropylamine to the surfaces of the silicon dioxide microspheres, carrying out amination on the surfaces of the silicon dioxide microspheres, utilizing the aminated silicon dioxide microspheres as a template, adopting a sol-gel method to hydrolyze tetraethyl orthosilicate to generate nano silicon dioxide, depositing nano silicon dioxide on the surfaces of the aminated silicon dioxide microspheres, and because the surfaces of the silicon dioxide microspheres are aminated, the surface of the silicon dioxide microsphere is loaded with more amino groups, and the amino groups and tetraethyl orthosilicate are hydrolyzed to generate nano silicon dioxide with hydrogen bond acting force, so that more nano silicon dioxide is deposited on the surface of the aminated silicon dioxide microsphere, and a porous silicon dioxide shell layer is formed on the surface of the aminated silicon dioxide microsphere to obtain the mesoporous silicon dioxide composite particle with the adsorption effect. The specific action mechanism of the mesoporous silica composite particle on hydrogen chloride is as follows: the hydrogen chloride gas is adsorbed by the porous structure of the mesoporous silica composite particle, and the hydrogen chloride enters the mesoporous silica composite particle and then reacts with amino on the surface of the aminated silica microsphere to remove part of adsorbed hydrogen chloride, so that the mesoporous silica can not reach a saturated state in a short time for adsorbing the hydrogen chloride, and more hydrogen chloride gas can be adsorbed in the process of heating polyvinyl chloride, thereby improving the thermal stability of the polyvinyl chloride pipe.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The raw materials, equipment and the like used in the present invention are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
The polyvinyl chloride resins used in specific examples 1 to 4 had apparent densities of not less than 0.45g/cm3The viscosity is 85-120mL/g, the degree of polymerization is 800-1200, and the K value is 60-68. The nano calcium carbonate has an average particle diameter of 20nm and a density of 5.7-5.8g/cm3. The calcium zinc stabilizer is 518B type calcium zinc stabilizer produced in the Shangxi Macro chemical industry. The phosphite used was 8601 nontoxic phosphite produced by Chang and New chemical materials Co.
Example 1
The preparation method of the silicon dioxide microspheres comprises the following steps:
adding ammonia water with the mass concentration of 15% into ethanol water with the mass concentration of 50% according to the volume ratio of the ammonia water to the ethanol water of 1:8, uniformly mixing to obtain a mixed solution, heating the mixed solution in a water bath to 35 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, wherein the addition amount of the tetraethyl orthosilicate is 8% of the mass of the ethanol water solution, carrying out heat preservation reaction for 3 hours after the dropwise adding is finished, centrifuging, filtering, washing, and transferring the obtained product into an oven to be dried for 2 hours at the temperature of 50 ℃ to obtain the silicon dioxide microspheres.
The preparation method of the mesoporous silica composite particle comprises the following steps:
adding an epoxy silane coupling agent KH560 into an ethanol aqueous solution with the mass concentration of 80%, stirring and dissolving, adjusting the pH to 5.5, heating in a water bath to 40 ℃, stirring and hydrolyzing for 1.5h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, wherein the mass ratio of the silica microspheres to the epoxy silane coupling agent KH560 is 1:1.8, stirring and reacting for 30min, filtering, washing, and drying in an oven at 45 ℃ for 3h to obtain alkylated silica microspheres;
adding 3,3' -diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution with the mass concentration of 5%, adding alkylated silica microspheres into the 3,3' -diaminodipropylamine solution, stirring to form a dispersion liquid, wherein the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1:4, dropwise adding a sodium hydroxide aqueous solution with the mass concentration of 1% into the dispersion liquid, wherein the dropwise adding amount of the sodium hydroxide aqueous solution is 10 wt% of the alkylated silica microspheres, heating to 70 ℃, stirring and reacting for 1.5h, filtering, washing, and drying in an oven at 50 ℃ for 2h to obtain silica-loaded 3,3' -diaminodipropylamine microspheres;
adding silica-supported 3,3' -diaminodipropylamine microspheres into 50% ethanol aqueous solution according to the mass-volume ratio of 1g/60mL, then adding 15% ammonia water and hexadecyl trimethyl ammonium bromide according to the mass-volume ratio of 1:8, dropwise adding tetraethyl orthosilicate under the stirring condition, wherein the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:1.2, the mass ratio of the hexadecyl trimethyl ammonium bromide to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:4, reacting for 3 hours after the dropwise addition is finished, centrifuging, filtering, washing, and drying for 1 hour in an oven at 60 ℃ to obtain the mesoporous silica composite particles.
The preparation method of the heat-resistant polyvinyl chloride pipeline material comprises the following steps:
1) weighing the following raw materials in parts by weight: 120 parts of polyvinyl chloride resin, 10 parts of nano calcium carbonate, 4 parts of calcium zinc stabilizer, 4 parts of mesoporous silica composite particles, 3 parts of calcium stearate, 0.8 part of phosphite ester, 0.5 part of phenyl salicylate and KH5500.6 parts of silane coupling agent;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent KH550 into a high-speed stirrer, and stirring at 110 ℃ for 25min to obtain a premix;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 15min to obtain a blend;
4) adding the blend into a screw extruder for extrusion granulation, wherein the setting parameters of the screw extruder are as follows: temperature in the first zone: 185 ℃, a second zone temperature of 175 ℃, a third zone temperature of 172 ℃, a fourth zone temperature of 170 ℃, a confluence core temperature of 168 ℃, a first head zone temperature of 185 ℃ and a second head zone temperature of 192 ℃.
Example 2
The preparation method of the silicon dioxide microspheres comprises the following steps:
adding ammonia water with the mass concentration of 15% into ethanol water with the mass concentration of 50% according to the volume ratio of the ammonia water to the ethanol water of 1:8, uniformly mixing to obtain a mixed solution, heating the mixed solution in a water bath to 30 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, keeping the temperature for reacting for 5 hours after the addition of the tetraethyl orthosilicate is completed, centrifuging, filtering, washing, and drying in an oven at 50 ℃ for 2 hours to obtain the silicon dioxide microspheres.
The preparation method of the mesoporous silica composite particle comprises the following steps:
adding an epoxy silane coupling agent KH560 into an ethanol aqueous solution with the mass concentration of 80%, stirring and dissolving, adjusting the pH to 5.5, heating in a water bath to 50 ℃, stirring and hydrolyzing for 1.5h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, wherein the mass ratio of the silica microspheres to the epoxy silane coupling agent KH560 is 1:1.8, stirring and reacting for 20min, filtering, washing, and drying in an oven at 45 ℃ for 3h to obtain alkylated silica microspheres;
adding 3,3' -diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution with the mass concentration of 5%, adding alkylated silica microspheres into the 3,3' -diaminodipropylamine solution, stirring to form a dispersion liquid, wherein the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1:4, dropwise adding a sodium hydroxide aqueous solution with the mass concentration of 1% into the dispersion liquid, wherein the dropwise adding amount of the sodium hydroxide aqueous solution is 10 wt% of the alkylated silica microspheres, heating to 80 ℃, stirring and reacting for 1.5h, filtering, washing, and drying in an oven at 50 ℃ for 2h to obtain silica-loaded 3,3' -diaminodipropylamine microspheres;
adding silica-supported 3,3' -diaminodipropylamine microspheres into 50% ethanol aqueous solution according to the mass-volume ratio of 1g/60mL, then adding 15% ammonia water and hexadecyl trimethyl ammonium bromide according to the mass-volume ratio of 1:8, dropwise adding tetraethyl orthosilicate under the stirring condition, wherein the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:1.2, the mass ratio of the hexadecyl trimethyl ammonium bromide to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:4, reacting for 3 hours after the dropwise addition is finished, centrifuging, filtering, washing, and drying for 1 hour in an oven at 60 ℃ to obtain the mesoporous silica composite particles.
The preparation method of the heat-resistant polyvinyl chloride pipeline material comprises the following steps:
1) weighing the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 5 parts of nano calcium carbonate, 3 parts of a calcium-zinc stabilizer, 3 parts of mesoporous silica composite particles, 1 part of calcium stearate, 0.6 part of phosphite ester, 1 part of phenyl salicylate and KH5500.6 parts of a silane coupling agent;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent KH550 into a high-speed stirrer, and stirring at 110 ℃ for 25min to obtain a premix;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 15min to obtain a blend;
4) adding the blend into a screw extruder for extrusion granulation, wherein the setting parameters of the screw extruder are as follows: temperature in the first zone: 185 ℃, a second zone temperature of 175 ℃, a third zone temperature of 172 ℃, a fourth zone temperature of 170 ℃, a confluence core temperature of 168 ℃, a first head zone temperature of 185 ℃ and a second head zone temperature of 192 ℃.
Example 3
The preparation method of the silicon dioxide microspheres comprises the following steps:
adding ammonia water with the mass concentration of 15% into ethanol water with the mass concentration of 50% according to the volume ratio of the ammonia water to the ethanol water of 1:8, uniformly mixing to obtain a mixed solution, heating the mixed solution in a water bath to 32 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, keeping the temperature for reacting for 4 hours after the addition of the tetraethyl orthosilicate is completed, centrifuging, filtering, washing, and drying in an oven at 50 ℃ for 2 hours to obtain the silicon dioxide microspheres.
The preparation method of the mesoporous silica composite particle comprises the following steps:
adding an epoxy silane coupling agent KH560 into an ethanol aqueous solution with the mass concentration of 80%, stirring and dissolving, adjusting the pH value to 6, heating in a water bath to 43 ℃, stirring and hydrolyzing for 2h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, wherein the mass ratio of the silica microspheres to the epoxy silane coupling agent KH560 is 1:2, stirring and reacting for 25min, filtering, washing, and drying in an oven at 45 ℃ for 3h to obtain alkylated silica microspheres;
adding 3,3' -diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution with the mass concentration of 5%, adding alkylated silica microspheres into the 3,3' -diaminodipropylamine solution, stirring to form a dispersion liquid, wherein the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1:5, dropwise adding a sodium hydroxide aqueous solution with the mass concentration of 1% into the dispersion liquid, wherein the dropwise adding amount of the sodium hydroxide aqueous solution is 10 wt% of the alkylated silica microspheres, heating to 75 ℃, stirring and reacting for 2 hours, filtering, washing, and drying in an oven at 50 ℃ for 2 hours to obtain silica-loaded 3,3' -diaminodipropylamine microspheres;
adding the silica-supported 3,3' -diaminodipropylamine microspheres into 50% ethanol aqueous solution according to the mass-volume ratio of 1g/60mL, then adding 15% ammonia water and hexadecyl trimethyl ammonium bromide according to the mass-volume ratio of 1:8, dropwise adding tetraethyl orthosilicate under the stirring condition, wherein the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:1, the mass ratio of the hexadecyl trimethyl ammonium bromide to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:4, reacting for 4 hours after the dropwise addition is finished, centrifuging, filtering, washing, and drying for 1 hour in an oven at 60 ℃ to obtain the mesoporous silica composite particles.
The preparation method of the heat-resistant polyvinyl chloride pipeline material comprises the following steps:
1) weighing the following raw materials in parts by weight: 110 parts of polyvinyl chloride resin, 8 parts of nano calcium carbonate, 5 parts of a calcium-zinc stabilizer, 5 parts of mesoporous silica composite particles, 2 parts of calcium stearate, 1 part of phosphite ester, 0.8 part of phenyl salicylate and 1 part of silane coupling agent KH 5501;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent KH550 into a high-speed stirrer, and stirring for 30min at 108 ℃ to obtain a premix;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 20min to obtain a blend;
4) adding the blend into a screw extruder for extrusion granulation, wherein the setting parameters of the screw extruder are as follows: temperature in the first zone: 185 ℃, a second zone temperature of 175 ℃, a third zone temperature of 172 ℃, a fourth zone temperature of 170 ℃, a confluence core temperature of 168 ℃, a first head zone temperature of 185 ℃ and a second head zone temperature of 192 ℃.
Example 4
The preparation method of the silicon dioxide microspheres comprises the following steps:
adding ammonia water with the mass concentration of 15% into ethanol water with the mass concentration of 50% according to the volume ratio of the ammonia water to the ethanol water of 1:8, uniformly mixing to obtain a mixed solution, heating the mixed solution in a water bath to 32 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, keeping the temperature for reacting for 4 hours after the addition of the tetraethyl orthosilicate is finished, centrifuging, filtering, washing, and drying in an oven at 50 ℃ for 2 hours to obtain the silicon dioxide microspheres.
The preparation method of the mesoporous silica composite particle comprises the following steps:
adding an epoxy silane coupling agent KH560 into an ethanol aqueous solution with the mass concentration of 80%, stirring and dissolving, adjusting the pH value to 5, heating in a water bath to 43 ℃, stirring and hydrolyzing for 1h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, wherein the mass ratio of the silica microspheres to the epoxy silane coupling agent KH560 is 1:1, stirring and reacting for 25min, filtering, washing, and drying in an oven at 45 ℃ for 3h to obtain alkylated silica microspheres;
adding 3,3' -diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution with the mass concentration of 5%, adding alkylated silica microspheres into the 3,3' -diaminodipropylamine solution, stirring to form a dispersion liquid, wherein the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1:3, dropwise adding a sodium hydroxide aqueous solution with the mass concentration of 1% into the dispersion liquid, wherein the dropwise adding amount of the sodium hydroxide aqueous solution is 10 wt% of the alkylated silica microspheres, heating to 75 ℃, stirring and reacting for 1h, filtering, washing, and drying in an oven at 50 ℃ for 2h to obtain silica-loaded 3,3' -diaminodipropylamine microspheres;
adding the silica-supported 3,3' -diaminodipropylamine microspheres into 50% ethanol aqueous solution according to the mass-volume ratio of 1g/60mL, then adding 15% ammonia water and hexadecyl trimethyl ammonium bromide according to the mass-volume ratio of 1:8, dropwise adding tetraethyl orthosilicate under the stirring condition, wherein the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:1.6, the mass ratio of the hexadecyl trimethyl ammonium bromide to the silica-supported 3,3' -diaminodipropylamine microspheres is 1:4, reacting for 2 hours after the dropwise addition is finished, centrifuging, filtering, washing, and drying for 1 hour in an oven at 60 ℃ to obtain the mesoporous silica composite particles.
The preparation method of the heat-resistant polyvinyl chloride pipeline material comprises the following steps:
1) weighing the following raw materials in parts by weight: 110 parts of polyvinyl chloride resin, 8 parts of nano calcium carbonate, 2 parts of a calcium-zinc stabilizer, 2 parts of mesoporous silica composite particles, 2 parts of calcium stearate, 0.5 part of phosphite ester, 0.8 part of phenyl salicylate and KH5500.5 parts of a silane coupling agent;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent KH550 into a high-speed stirrer, and stirring at 115 ℃ for 20min to obtain a premix;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 10min to obtain a blend;
4) adding the blend into a screw extruder for extrusion granulation, wherein the setting parameters of the screw extruder are as follows: temperature in the first zone: 185 ℃, a second zone temperature of 175 ℃, a third zone temperature of 172 ℃, a fourth zone temperature of 170 ℃, a confluence core temperature of 168 ℃, a first head zone temperature of 185 ℃ and a second head zone temperature of 192 ℃.
Comparative example 1: comparative example 1 is different from example 1 in that the mesoporous silica composite particles are not added to the polyvinyl chloride pipe material component.
Comparative example 2: comparative example 2 is different from example 1 in that the mesoporous silica composite particle is replaced with a general mesoporous silica commercially available.
Thermal stability test
1. And (3) hot baking test: the polyvinyl chloride pipe plastic particles prepared in the examples 1-4 and the comparative examples 1-2 are placed in a double-roller open mill to be plasticated into sheets, the roller temperature of the double-roller open mill is set to be 170 ℃, the roller distance is 1mm, the sheets are cut into sample sheets with the thickness of 10mm multiplied by 10mm after being discharged, the sample sheets are placed in an oven with the temperature of 180 ℃ to be heated and baked, and the color change condition of the sample sheets is observed every 20 min. The test results are shown in the following table:
| 20min | 40min | 60min | 80min | 100min | |
| example 1 | Light yellow | Light yellow | Yellow colour | Yellow brown | Black color |
| Example 2 | Light yellow | Light yellow | Yellow colour | Yellow brown | Black color |
| Example 3 | Light yellow | Light yellow | Yellow colour | Yellow brown | Black color |
| Example 4 | Light yellow | Light yellow | Yellow colour | Yellow brown | Black color |
| Comparative example 1 | Yellow brown | Black color | Black color | Black color | Black color |
| Comparative example 2 | Yellow colour | Yellow brown | Black color | Black color | Black color |
2. Thermal stability time: thermal stability time test of polyvinyl chloride pipe plastic pellets prepared in examples 1 to 4 and comparative examples 1 to 2 test was conducted in accordance with GB/T2917-1982. polyvinyl chloride pipe plastic pellets of 2 mm. times.2 mm were put into a test tube and gently shaken 20 times, the temperature of the test specimen was maintained in a glycerin bath (200. + -. 1 ℃ C.), and the time (static thermal stability time) at which the decomposed hydrogen chloride caused the congo red test paper above the test specimen to start to turn blue was measured. The test results are shown in the following table:
the longer the blackening time and the Congo red color change time are, the better the thermal stability of the material is proved, and the test results can obtain that the polyvinyl chloride blackening time of the examples 1-4 is 80-100min, the Congo red color change time is more than 65min, the polyvinyl chloride blackening time of the comparative examples 1-2 is less than 60min, and the Congo red color change time is 30-40min, so that the thermal stability of the polyvinyl chloride material of the examples 1-4 is proved to be higher than that of the comparative examples 1 and 2. The thermal stability of the polyvinyl chloride material in the examples 1 to 4 is higher than that in the comparative example 1, because the hydrogen chloride gas released by the polyvinyl chloride resin when heated can catalyze the thermal degradation of polyvinyl chloride, which has the negative effect of accelerating the degradation of polyvinyl chloride, the mesoporous silica composite particles with porous structures are added in the examples 1 to 4, and the hydrogen chloride gas generated by the polyvinyl chloride resin is adsorbed by the mesoporous silica composite particles, so that the catalytic effect of the hydrogen chloride on the degradation of polyvinyl chloride is avoided, and the thermal stability of the polyvinyl chloride pipeline material is improved. The thermal stability of the polyvinyl chloride materials of examples 1 to 4 is higher than that of comparative example 2, because the self-made mesoporous silica composite particles are adopted in examples 1 to 4, hydrogen chloride gas is adsorbed by the porous structure of the mesoporous silica composite particles, and the hydrogen chloride gas enters the mesoporous silica composite particles and reacts with the amino groups on the surface of the aminated silica microspheres to remove part of adsorbed hydrogen chloride, so that the mesoporous silica cannot reach a saturated state in a short time when adsorbing hydrogen chloride, and more hydrogen chloride gas can be adsorbed in the process of polyvinyl chloride being heated, thereby improving the thermal stability of the polyvinyl chloride pipe.
II, testing mechanical properties:
1. and (3) testing tensile strength: the polyvinyl chloride plastic particles obtained in examples 1 to 4 were hot-pressed at 180 ℃ for 5 minutes to prepare dumbbell-type test bars, and the dumbbell-type test bars were subjected to tensile property testing on a WDW10C microcomputer-controlled electronic universal tester according to GB/T1040-2006 with a tensile speed chuck moving speed of 50mm/min and calculated according to a tensile strength calculation formula σ ═ P/bd, where P is the maximum load (N), b is the sample width (mm), and d is the sample thickness (mm).
2. Testing the notch impact strength of the cantilever beam: the polyvinyl chloride plastic particles obtained in examples 1 to 4 were hot-pressed at 180 ℃ for 5 minutes to prepare strip-shaped plastic sheets of 80mm × 10mm × 4mm, then V-shaped notches were formed in a ZHY-W type universal prototype, and the notched Izod impact strength was measured according to GB/T1843-2008 "determination of Plastic Izod impact Strength", with the temperature being adjusted to 23 ℃ and the relative humidity being 50%, and the temperature being maintained for 48 hours.
The test results can obtain that the polyvinyl chloride pipe prepared by the invention has the tensile strength of more than 50MPa and the notched impact strength of a cantilever beam of 11kJ/m2The method meets the requirements of the physical performance indexes of the pipe.
Claims (8)
1. The preparation method of the heat-resistant polyvinyl chloride pipeline material is characterized by comprising the following steps of:
1) weighing the following raw materials in parts by weight: 100-120 parts of polyvinyl chloride resin, 5-10 parts of nano calcium carbonate, 2-5 parts of a calcium-zinc stabilizer, 2-5 parts of mesoporous silica composite particles, 1-3 parts of calcium stearate, 0.5-1 part of phosphite ester, 0.5-1 part of phenyl salicylate and 0.5-1 part of silane coupling agent;
2) adding polyvinyl chloride resin, nano calcium carbonate, mesoporous silica composite particles, calcium stearate and a silane coupling agent into a high-speed stirrer, and stirring for 20-30min at the temperature of 108-;
3) adding the calcium zinc stabilizer, the phosphite ester and the phenyl salicylate into the premix, and continuously stirring for 10-20min to obtain a blend;
4) and adding the blend into a screw extruder for extrusion granulation to obtain the product.
2. The method for preparing heat-resistant polyvinyl chloride pipeline material according to claim 1, wherein the apparent density of the polyvinyl chloride resin is not less than 0.45g/cm3The viscosity is 85-120mL/g, the degree of polymerization is 800-1200, and the K value is 60-68.
3. The method for preparing a heat-resistant polyvinyl chloride pipe material according to claim 1, wherein the method for preparing the mesoporous silica composite particles comprises the following steps: adding an epoxy silane coupling agent into an ethanol water solution, stirring and dissolving, adjusting the pH to 5-6, heating in a water bath to 40-50 ℃, stirring and hydrolyzing for 1-2h to obtain a silane coupling agent solution, adding silica microspheres into the silane coupling agent solution, stirring and reacting for 20-30min, and then filtering, washing and drying to obtain alkylated silica microspheres; adding 3,3 '-diaminodipropylamine into deionized water, stirring and dissolving to obtain a 3,3' -diaminodipropylamine solution, adding alkylated silica microspheres into the 3,3 '-diaminodipropylamine solution, stirring to form a dispersion, dropwise adding a sodium hydroxide solution into the dispersion, heating to 70-80 ℃, stirring and reacting for 1-2 hours, and then filtering, washing and drying to obtain silica-loaded 3,3' -diaminodipropylamine microspheres; adding the silica-loaded 3,3' -diaminodipropylamine microspheres into an ethanol aqueous solution, then adding ammonia water and hexadecyl trimethyl ammonium bromide, dropwise adding tetraethyl orthosilicate under the stirring condition, reacting for 2-4h after dropwise adding is finished, and then centrifuging, filtering, washing and drying to obtain the mesoporous silica composite particles.
4. The method for preparing the heat-resistant polyvinyl chloride pipeline material according to claim 3, wherein the mass ratio of the silica microspheres to the epoxy silane coupling agent is 1: 1-2.
5. The method for preparing the heat-resistant polyvinyl chloride pipeline material according to claim 3, wherein the mass ratio of the alkylated silica microspheres to the 3,3' -diaminodipropylamine is 1: 3-5.
6. The method for preparing the heat-resistant polyvinyl chloride pipeline material according to claim 3, wherein the mass ratio of the tetraethyl orthosilicate to the silica-supported 3,3' -diaminodipropylamine microspheres is 1: 1-1.6.
7. The method for preparing a heat-resistant polyvinyl chloride pipeline material according to claim 3, wherein the method for preparing the silica microspheres comprises the following steps: adding ammonia water into ethanol water solution, mixing uniformly to obtain mixed solution, heating in water bath to 30-35 ℃, dropwise adding tetraethyl orthosilicate into the mixed solution in the stirring process, keeping the temperature for reaction for 3-5h after dropwise adding, and then centrifuging, filtering, washing and drying to obtain the silicon dioxide microspheres.
8. The method for preparing the heat-resistant polyvinyl chloride pipeline material according to claim 7, wherein the addition amount of the tetraethyl orthosilicate is 5-10% of the mass of the ethanol water solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113416367A (en) * | 2021-05-26 | 2021-09-21 | 浙江中财管道科技股份有限公司 | PVC-UH pipe with high strength and high pressure resistance and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113416367A (en) * | 2021-05-26 | 2021-09-21 | 浙江中财管道科技股份有限公司 | PVC-UH pipe with high strength and high pressure resistance and preparation method thereof |
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