CN113416367B - PVC-UH pipe with high strength and high pressure resistance and preparation method thereof - Google Patents
PVC-UH pipe with high strength and high pressure resistance and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of high-performance rigid polyvinyl chloride materials, and discloses a PVC-UH pipe with high strength and high pressure resistance and a preparation method thereof. The PVC-UH pipe comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 3-6 parts of modified porous polymer/potassium oxide composite microspheres, 0-8 parts of filler, 0-1.5 parts of lubricant and 0-0.3 part of colorant; the modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of carbamido groups grafted on the surface. According to the invention, the modified porous polymer/potassium oxide composite microspheres are added into the rigid polyvinyl chloride pipe, so that the thermal stability of the pipe can be improved, the pipe is prevented from discoloring in the thermal processing process, and the mechanical property of the pipe is improved.
Description
Technical Field
The invention relates to the field of high-performance rigid polyvinyl chloride materials, in particular to a PVC-UH pipe with high strength and high pressure resistance and a preparation method thereof.
Background
The hard polyvinyl chloride (PVC-U) pipeline is produced with sanitary polyvinyl chloride (PVC) resin as main material and proper amount of stabilizer, lubricant, filler, coloring agent, etc. and through extrusion in plastic extruder, injection in injection molding machine, cooling, solidification, setting, inspection, packing and other steps. The construction method has the advantages of high construction speed, high efficiency and low installation cost, and has more than 70 years of history in the development in the world. Compared with the traditional PVC-U, the high-performance rigid polyvinyl chloride (PVC-UH) pipe is nontoxic and sanitary, has more excellent strength, toughness, corrosion resistance and acid and alkali resistance, and is widely applied to projects such as remote water delivery, urban water supply, airport fire water supply, pipe gallery water supply and drainage and the like.
Polyvinyl chloride is often accompanied by a large amount of side reactions in the actual production process, so that a long-chain structure of the polyvinyl chloride has a thermally unstable structure such as an unsaturated end group, allyl chloride and tertiary chloride, HCl is easily removed under the action of heating and shearing in the extrusion molding process of preparing the polyvinyl chloride into a pipe, a conjugated double-bond structure is formed, the polyvinyl chloride is discolored, and the HCl can further catalyze the degradation of the polyvinyl chloride, so that the color of the polyvinyl chloride is deepened, and the mechanical property of the polyvinyl chloride is reduced. Therefore, in the production process of PVC pipes, a heat stabilizer is often added to reduce the degradation of the PVC. At present, a heat stabilizer commonly used in PVC-U pipes is a calcium zinc stabilizer, for example, chinese patent application No. CN201710508443.5 discloses an environment-friendly PVC solid-wall pipe for underground communication pipes, which is composed of the following components in parts by mass: 100 parts of polyvinyl chloride, 5-40 parts of light calcium carbonate, 2.5-5 parts of calcium zinc stabilizer, 1-1.5 parts of lubricant, 0.5-2 parts of processing aid, 2-6 parts of impact resistant agent and 0.5-3 parts of titanium dioxide. The calcium zinc stabilizer has higher thermal stability effect, and has better environmental protection property because of not containing heavy metal, but also has the following defects: the calcium zinc stabilizer has poor compatibility with polyvinyl chloride and contains a large amount of lubricant, which can affect the strength and impact resistance of the obtained polyvinyl chloride pipe, so that the strength and impact resistance of the obtained polyvinyl chloride pipe can not reach the standard of PVC-UH pipe.
Disclosure of Invention
In order to solve the technical problems, the invention provides a PVC-UH pipe with high strength and high pressure resistance and a preparation method thereof. According to the invention, the modified porous polymer/potassium oxide composite microspheres are added into the rigid polyvinyl chloride pipe, so that the thermal stability of the pipe can be improved, the pipe is prevented from discoloring in the thermal processing process, and the mechanical property of the pipe is improved.
The specific technical scheme of the invention is as follows:
a PVC-UH pipe with high strength and high pressure resistance comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 3-6 parts of modified porous polymer/potassium oxide composite microspheres, 0-8 parts of filler, 0-1.5 parts of lubricant and 0-0.3 part of colorant; the modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of carbamido groups grafted on the surface.
The modified porous polymer/potassium oxide composite microspheres are added into the rigid polyvinyl chloride pipe, so that the thermal stability of the polyvinyl chloride can be improved, the pipe is prevented from being degraded in the process of preparing the pipe to influence the color and the mechanical property of the pipe, and the polymer is used as a microsphere base material, so that the mechanical property of the pipe cannot be influenced due to poor compatibility with the polyvinyl chloride.
The mechanism for improving the thermal stability of the polyvinyl chloride by the modified porous polymer/potassium oxide composite microspheres is as follows: the carbamido grafted on the surface of the microsphere can replace allyl chloride, so that the discoloration of the pipe caused by the formation of conjugated double bonds is prevented; moreover, the microspheres have a porous structure, so that the microspheres have a good adsorption effect on hydrogen chloride generated by polyvinyl chloride degradation and hydrogen chloride generated by replacement of allyl chloride by carbamido, and potassium oxide loaded in the microspheres can react with the adsorbed hydrogen chloride, so that the hydrogen chloride is prevented from further catalyzing the polyvinyl chloride degradation. In addition, after the allyl chloride is replaced by the carbamido group, the carbamido group can be covalently connected to a polyvinyl chloride side chain, and because a plurality of carbamido groups are grafted on the surface of the microsphere, covalent crosslinking can be formed among polyvinyl chloride molecular chains, which is beneficial to improving the mechanical property of the polyvinyl chloride pipe.
Preferably, the particle size of the modified porous polymer/potassium oxide composite microsphere is 50-80 μm.
Preferably, the preparation method of the modified porous polymer/potassium oxide composite microsphere comprises the following steps:
(1.1) preparation of porous polymeric microspheres: preparing a mixed solution of ethylenediamine, 2, 5-dihydroxybenzaldehyde and water, dropwise adding toluene diisocyanate below the liquid level of the mixed solution, reacting at 60-70 ℃ for 40-60min after dropwise adding, and separating out porous polymer microspheres;
the amino group in the ethylenediamine and the hydroxyl group in the 2, 5-dihydroxybenzaldehyde can react with the isocyanate group in the toluene diisocyanate to form the porous polymer microsphere through an interfacial polymerization method.
(1.2) supporting potassium oxide: immersing the porous polymer microspheres into a potassium nitrate solution, stirring for 15-20h, removing water by rotary evaporation, drying in vacuum, and roasting at 320-330 ℃ for 1.5-2h in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres;
during the impregnation process, potassium nitrate is combined into the pore channels of the porous polymer microspheres through complexation, and then potassium oxide is generated through decomposition at high temperature. The decomposition temperature of the potassium nitrate is higher (above 400 ℃), and roasting at the temperature can cause the collapse of pore channels in the microspheres and influence the adsorption performance of the microspheres on hydrogen chloride.
(1.3) grafted ureido: preparing 2-hydroxyethyl urea and cyclohexane into a modifier solution, adding the porous polymer/potassium oxide composite microspheres into the modifier solution, uniformly dispersing, stirring and reacting at 60-80 ℃ for 30-40min, and separating products to obtain modified porous polymer/potassium oxide composite microspheres;
the hydroxyl and primary amino groups in the 2-hydroxyethyl urea are capable of reacting with the isocyanate groups on the microspheres, thereby grafting urea groups to the microspheres.
Further, in the step (1.1), the mass ratio of ethylenediamine to 2, 5-dihydroxybenzaldehyde is 2.0-3.5: 1.
Further, in the step (1.1), the mass fraction of the ethylenediamine in the mixed solution is 0.10-0.15 wt%; the mass ratio of the ethylenediamine to the toluene diisocyanate is 1: 18-22.
Further, in the step (1.2), the mass fraction of the potassium nitrate solution is 1.5-3.5 wt%; the mass-volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:20-30 mL.
Further, in the step (1.3), the mass fraction of the 2-hydroxyethyl urea in the modifier solution is 0.2-0.5 wt%; the mass-volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:100-120 mL.
Preferably, the filler is one or more of calcium carbonate, talcum powder and ceramic powder.
Preferably, the lubricant is one or more of stearic acid, stearate, paraffin, microcrystalline wax and polyethylene wax.
A process for the preparation of said PVC-UH pipe comprising the steps of: uniformly mixing all the raw materials at the temperature of 120-130 ℃, cooling to 35-45 ℃ while stirring, extruding, cooling and shaping to obtain the PVC-UH pipe with high strength and high pressure resistance.
Compared with the prior art, the invention has the following advantages:
(1) the crosslinking degree of the polyvinyl chloride can be improved by grafting carbamido on the surface of the porous polymer/potassium oxide composite microsphere, so that the mechanical property of the polyvinyl chloride is improved;
(2) the carbamido grafted on the surface of the microsphere is matched with the porous polymer/potassium oxide composite microsphere, and the hydrogen chloride generated by the replacement of allyl chloride by the carbamido is removed in time by utilizing the microsphere, so that the thermal stability of the polyvinyl chloride can be synergistically improved, and the polyvinyl chloride is prevented from being discolored and reduced in mechanical property due to degradation in the thermal processing process;
(3) in the process of preparing the porous polymer microspheres, 2, 5-dihydroxy benzaldehyde monomer is introduced, so that the decomposition temperature of potassium nitrate can be reduced, and the pores in the microspheres are prevented from collapsing at an excessively high temperature when potassium oxide is loaded.
Detailed Description
The present invention will be further described with reference to the following examples.
A PVC-UH pipe with high strength and high pressure resistance comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 3-6 parts of modified porous polymer/potassium oxide composite microspheres, 0-8 parts of filler, 0-1.5 parts of lubricant and 0-0.3 part of colorant. The modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of urea groups grafted on the surface, and the particle size of the modified porous polymer/potassium oxide composite microsphere is 50-80 mu m. The filler is one or more of calcium carbonate, talcum powder and ceramic powder. The lubricant is one or more of stearic acid, stearate, paraffin, microcrystalline wax and polyethylene wax.
A process for the preparation of said PVC-UH pipe comprising the steps of:
(1) preparing porous polymer/potassium oxide composite microspheres:
(1.1) preparation of porous polymeric microspheres: adding ethylenediamine and 2, 5-dihydroxybenzaldehyde into water in a mass ratio of 2.0-3.5:1 to prepare a mixed solution, wherein the mass fraction of the ethylenediamine is 0.10-0.15 wt%; dropwise adding toluene diisocyanate below the liquid level of the mixed solution, wherein the mass ratio of the ethylenediamine to the toluene diisocyanate is 1:18-22, reacting at 60-70 ℃ for 40-60min after completing dropwise adding, and separating out porous polymer microspheres;
(1.2) supporting potassium oxide: immersing porous polymer microspheres into a potassium nitrate solution with the mass fraction of 1.5-3.5wt%, wherein the mass volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:20-30mL, stirring for 15-20h, removing water by rotary evaporation, drying in vacuum, and roasting for 1.5-2h at 320-330 ℃ in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres; (1.3) grafted ureido: preparing 2-hydroxyethyl urea and cyclohexane into a modifier solution, wherein the mass fraction of the 2-hydroxyethyl urea is 0.2-0.5 wt%; adding the porous polymer/potassium oxide composite microspheres into a modifier solution, wherein the mass volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:100-120mL, uniformly dispersing, stirring and reacting at 60-80 ℃ for 30-40min, and separating products to obtain the modified porous polymer/potassium oxide composite microspheres.
(2) Uniformly mixing all the raw materials at the temperature of 120-130 ℃, cooling to 35-45 ℃ while stirring, extruding, cooling and shaping to obtain the PVC-UH pipe with high strength and high pressure resistance.
Example 1
A PVC-UH pipe with high strength and high pressure resistance comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin and 6 parts of modified porous polymer/potassium oxide composite microspheres. The modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of urea groups grafted on the surface, and the particle size of the modified porous polymer/potassium oxide composite microsphere is 50-80 mu m.
A process for the preparation of said PVC-UH pipe comprising the steps of:
(1) preparing modified porous polymer/potassium oxide composite microspheres:
(1.1) preparation of porous polymeric microspheres: adding ethylenediamine and 2, 5-dihydroxybenzaldehyde into water in a mass ratio of 3.5:1 to prepare a mixed solution, wherein the mass fraction of the ethylenediamine is 0.15 wt%; dropwise adding toluene diisocyanate below the liquid level of the mixed solution, wherein the mass ratio of ethylenediamine to toluene diisocyanate is 1:18, reacting at 70 ℃ for 40min after dropwise adding, centrifugally separating microspheres, washing with acetone, and drying to obtain porous polymer microspheres;
(1.2) supporting potassium oxide: immersing porous polymer microspheres into a potassium nitrate solution with the mass fraction of 3.5wt%, wherein the mass-volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:20mL, stirring for 15h, removing water by rotary evaporation, drying in vacuum, and roasting for 1.5h at 330 ℃ in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres;
(1.3) grafted ureido: preparing 2-hydroxyethyl urea and cyclohexane into a modifier solution, wherein the mass fraction of the 2-hydroxyethyl urea is 0.5 wt%; adding porous polymer/potassium oxide composite microspheres into a modifier solution, wherein the mass-to-volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:120mL, uniformly dispersing, stirring and reacting at 80 ℃ for 30min, centrifugally separating the microspheres, washing with acetone, and drying to obtain modified porous polymer/potassium oxide composite microspheres;
(2) adding all the raw materials into a hot mixer, uniformly mixing at 120 ℃, adding into a cold mixer, and cooling to 35 ℃ while stirring to obtain a mixture; and then extruding, cooling and shaping the mixture to obtain the rigid polyvinyl chloride pipe.
Example 2
A PVC-UH pipe with high strength and high pressure resistance comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 4 parts of modified porous polymer/potassium oxide composite microspheres, 3 parts of superfine calcium carbonate, 0.8 part of stearic acid and 0.2 part of titanium dioxide. The modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of urea groups grafted on the surface, and the particle size of the modified porous polymer/potassium oxide composite microsphere is 50-80 mu m.
A process for the preparation of said PVC-UH pipe comprising the steps of:
(1) preparing modified porous polymer/potassium oxide composite microspheres:
(1.1) preparation of porous polymeric microspheres: adding ethylenediamine and 2, 5-dihydroxybenzaldehyde into water in a mass ratio of 3.0:1 to prepare a mixed solution, wherein the mass fraction of the ethylenediamine is 0.12 wt%; dropwise adding toluene diisocyanate below the liquid level of the mixed solution, wherein the mass ratio of ethylenediamine to toluene diisocyanate is 1:18-22, reacting at 65 ℃ for 50min after dropwise adding, centrifugally separating microspheres, washing with acetone, and drying to obtain porous polymer microspheres;
(1.2) supporting potassium oxide: immersing porous polymer microspheres into a potassium nitrate solution with the mass fraction of 2.5 wt%, wherein the mass-volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:25mL, stirring for 17.5h, removing water by rotary evaporation, drying in vacuum, and roasting for 2h at 325 ℃ in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres;
(1.3) grafted ureido: preparing 2-hydroxyethyl urea and cyclohexane into a modifier solution, wherein the mass fraction of the 2-hydroxyethyl urea is 0.3 wt%; adding porous polymer/potassium oxide composite microspheres into a modifier solution, wherein the mass-to-volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:110mL, uniformly dispersing, stirring and reacting at 70 ℃ for 35min, centrifugally separating the microspheres, washing with acetone, and drying to obtain modified porous polymer/potassium oxide composite microspheres;
(2) adding all the raw materials into a hot mixer, uniformly mixing at 125 ℃, adding into a cold mixer, and cooling to 40 ℃ while stirring to obtain a mixture; and then extruding, cooling and shaping the mixture to obtain the PVC-UH pipe with high strength and high pressure resistance.
Example 3
A PVC-UH pipe with high strength and high pressure resistance comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 3 parts of modified porous polymer/potassium oxide composite microspheres, 8 parts of talcum powder, 1.5 parts of polyethylene wax and 0.3 part of titanium dioxide. The modified porous polymer/potassium oxide composite microsphere is a porous polymer/potassium oxide composite microsphere with a plurality of urea groups grafted on the surface, and the particle size of the modified porous polymer/potassium oxide composite microsphere is 50-80 mu m.
A process for the preparation of said PVC-UH pipe comprising the steps of:
(1) preparing modified porous polymer/potassium oxide composite microspheres:
(1.1) preparation of porous polymeric microspheres: adding ethylenediamine and 2, 5-dihydroxybenzaldehyde into water in a mass ratio of 2.0:1 to prepare a mixed solution, wherein the mass fraction of the ethylenediamine is 0.10 wt%; dropwise adding toluene diisocyanate below the liquid level of the mixed solution, wherein the mass ratio of ethylenediamine to toluene diisocyanate is 1:22, reacting at 60 ℃ for 60min after dropwise adding, centrifugally separating microspheres, washing with acetone, and drying to obtain porous polymer microspheres;
(1.2) supporting potassium oxide: immersing porous polymer microspheres into a potassium nitrate solution with the mass fraction of 1.5 wt%, wherein the mass-volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:30mL, stirring for 20h, removing water by rotary evaporation, drying in vacuum, and roasting for 2h at 320 ℃ in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres;
(1.3) grafted ureido: preparing 2-hydroxyethyl urea and cyclohexane into a modifier solution, wherein the mass fraction of the 2-hydroxyethyl urea is 0.2 wt%; adding porous polymer/potassium oxide composite microspheres into a modifier solution, wherein the mass-to-volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:100mL, uniformly dispersing, stirring and reacting at 60 ℃ for 40min, centrifugally separating the microspheres, washing with acetone, and drying to obtain modified porous polymer/potassium oxide composite microspheres;
(2) adding all the raw materials into a hot mixer, uniformly mixing at 130 ℃, adding into a cold mixer, and cooling to 45 ℃ while stirring to obtain a mixture; and then extruding, cooling and shaping the mixture to obtain the PVC-UH pipe with high strength and high pressure resistance.
Comparative example 1
The difference between the comparative example and the example 2 is that the modified porous polymer/potassium oxide composite microspheres are replaced by calcium zinc stabilizer with equal mass, and the rest of the raw materials and the preparation process are the same as those in the example 2.
Comparative example 2
The comparative example is different from example 2 in that the step (1.2) is not performed in the process of preparing the modified porous polymer/potassium oxide composite microspheres, the obtained microspheres are not loaded with potassium oxide, and the rest of the raw materials and the preparation process are the same as those of example 2.
Comparative example 3
This comparative example is different from example 2 in that 2, 5-dihydroxybenzaldehyde was replaced with ethylenediamine in an equimolar amount in the step (1.1) during the preparation of modified porous polymer/potassium oxide composite microspheres, and the remaining raw materials and preparation process were the same as those of example 2.
Comparative example 4
The comparative example is different from example 2 in that the step (1.3) is not performed in the process of preparing the modified porous polymer/potassium oxide composite microsphere, urea groups are not grafted on the surface of the obtained microsphere, and the rest of the raw materials and the preparation process are the same as those of example 2.
Comparative example 5
The comparative example is different from example 2 in that the step (1.3) is not performed in the process of preparing the modified porous polymer/potassium oxide composite microspheres, urea groups are not grafted on the surfaces of the obtained microspheres, 2-hydroxyethyl urea of equal mass is separately added to the step (2) as a raw material, and the rest of the raw materials and the preparation process are the same as example 2.
Performance testing
The compounds prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to a thermal stability test as follows: according to the method in GB/T15595-2008 whiteness method for testing thermal stability of polyvinyl chloride resin, after heating at 160 ℃ for 10min, the whiteness of the mixture is detected, and the results are recorded in Table 1.
The rigid polyvinyl chloride pipes obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to mechanical property tests by the following methods: according to the method in CJ/T493-2016 high-performance rigid polyvinyl chloride pipe and connecting piece for water supply, the pipe is subjected to drop hammer impact test, apparent hoop tensile strength detection, crush test and hydrostatic test, wherein the temperature of the hydrostatic test is 20 ℃, the ring stress is 42MPa, the test time is 1h, and the results are recorded in Table 1.
TABLE 1
According to the test results of examples 1-3, it can be seen that the inventive compound for producing pipes has a high thermal stability and that the produced pipes meet the standard for PVC-UH pipes.
Compared with the comparative example 1, the thermal stability of the mixture of the example 2 is higher, and the mechanical property of the pipe is obviously improved. The reason for this is that: the calcium zinc stabilizer has poor compatibility with polyvinyl chloride, and contains a large amount of lubricant, which can cause adverse effect on the strength of the pipe; the modified porous polymer/potassium oxide composite microsphere adopts the polymer as the microsphere base material, has good compatibility with polyvinyl chloride, does not need to add a lubricant to facilitate the processing of a stabilizer and the mixing of the stabilizer and the polyvinyl chloride, can be covalently connected to a polyvinyl chloride side chain after the ureido on the surface replaces allyl chloride, and can form covalent crosslinking among polyvinyl chloride molecular chains because a plurality of ureidos are grafted on the surface of the microsphere, thereby being beneficial to improving the mechanical property of a polyvinyl chloride pipe.
Compared with example 2, the modified porous polymer/potassium oxide composite microspheres of comparative example 2 are not loaded with potassium oxide, and the thermal stability of the mixture and the mechanical properties of the pipe are reduced. The reason for this is that: the potassium oxide can neutralize hydrogen chloride adsorbed by the heat-resistant reinforced modifier, and prevent hydrogen chloride which is not removed in time from being separated from the microspheres to catalyze the degradation of polyvinyl chloride.
Comparative example 3, in which 2, 5-dihydroxybenzaldehyde was not added during the preparation of porous polymer microspheres and the firing temperature was increased to decompose potassium nitrate into potassium oxide, had a decreased thermal stability and mechanical properties of the mix compared to example 2. The reason for this is that: the decomposition temperature of the potassium nitrate is higher, and the roasting at the temperature can cause the collapse of pore channels in the microspheres and influence the adsorption performance of the microspheres on hydrogen chloride.
Compared with example 2, the microspheres of comparative example 4 have no carbamido grafted on the surface, and the thermal stability of the mixture and the mechanical properties of the pipe are both obviously reduced. The reason for this is that: the carbamido on the surface of the microsphere can replace allyl chloride in a polyvinyl chloride molecular chain, so that the tubular product is prevented from discoloring due to the formation of conjugated double bonds after dehydrochlorination of the allyl chloride; and the crosslinking degree of the polyvinyl chloride can be improved after the ureido replaces the allyl chloride, so that the mechanical strength of the pipe is improved.
Compared with example 2, in comparative example 5, the thermal stability of the mixture and the mechanical property of the pipe are reduced when the 2-hydroxyethyl urea and the porous polymer/potassium oxide composite microspheres are added into the polyvinyl chloride in a dispersing way. The reason for this is that: when the 2-hydroxyethyl urea and the porous polymer/potassium oxide composite microspheres are dispersedly added, the 2-hydroxyethyl urea cannot form covalent crosslinking among polyvinyl chloride molecular chains, so that the mechanical strength of the pipe cannot be improved; moreover, hydrogen chloride generated after 2-hydroxyethyl urea replaces allyl chloride cannot be absorbed and neutralized by the microspheres in time, although amino groups in the 2-hydroxyethyl urea can be combined with the hydrogen chloride and have lower binding capacity than the microspheres, and the hydrogen chloride which is not removed in time can catalyze the degradation of the polyvinyl chloride.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A PVC-UH pipe with high strength and high pressure resistance is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 3-6 parts of modified porous polymer/potassium oxide composite microspheres, 0-8 parts of filler, 0-1.5 parts of lubricant and 0-0.3 part of colorant; the modified porous polymer/potassium oxide composite microspheres are porous polymer/potassium oxide composite microspheres with a plurality of urea groups grafted on the surfaces; the preparation method of the modified porous polymer/potassium oxide composite microsphere comprises the following steps:
(1.1) preparation of porous polymeric microspheres: preparing a mixed solution of ethylenediamine, 2, 5-dihydroxybenzaldehyde and water, dropwise adding toluene diisocyanate below the liquid level of the mixed solution, reacting at 60-70 ℃ for 40-60min after dropwise adding, and separating out porous polymer microspheres;
(1.2) supporting potassium oxide: immersing the porous polymer microspheres into a potassium nitrate solution, stirring for 15-20h, removing water by rotary evaporation, drying in vacuum, and roasting at 320-330 ℃ for 1.5-2h in an oxygen-free environment to obtain porous polymer/potassium oxide composite microspheres;
(1.3) grafted ureido: preparing a modifier solution from 2-hydroxyethyl urea and cyclohexane, adding the porous polymer/potassium oxide composite microspheres into the modifier solution, uniformly dispersing, stirring and reacting at 60-80 ℃ for 30-40min, and separating products to obtain the modified porous polymer/potassium oxide composite microspheres.
2. The PVC-UH pipe according to claim 1, wherein the modified porous polymer/potassium oxide composite microspheres have a particle size of 50 to 80 μm.
3. The PVC-UH-pipe according to claim 1, wherein in step (1.1) the mass ratio of ethylenediamine to 2, 5-dihydroxybenzaldehyde is 2.0-3.5: 1.
4. The PVC-UH-pipe according to claim 1, wherein in step (1.1), the mass fraction of ethylenediamine in the mixed solution is 0.10 to 0.15 wt.%; the mass ratio of the ethylenediamine to the toluene diisocyanate is 1: 18-22.
5. The PVC-UH pipe according to claim 1, wherein in step (1.2) the mass fraction of potassium nitrate solution is between 1.5 and 3.5 wt.%; the mass-volume ratio of the porous polymer microspheres to the potassium nitrate solution is 1g:20-30 mL.
6. The PVC-UH pipe according to claim 1, wherein in step (1.3) the mass fraction of 2-hydroxyethyl urea in the modifier solution is 0.2 to 0.5 wt.%; the mass-volume ratio of the porous polymer/potassium oxide composite microspheres to the modifier solution is 1g:100-120 mL.
7. The PVC-UH pipe according to claim 1, wherein the filler is one or more of calcium carbonate, talc and ceramic powder.
8. The PVC-UH pipe according to claim 1, wherein the lubricant is one or more of stearic acid, stearate, paraffin, microcrystalline wax, polyethylene wax.
9. Process for the production of the PVC-UH pipe according to any of the claims 1 to 8, characterized in that it comprises the following steps: uniformly mixing all the raw materials at the temperature of 120-130 ℃, cooling to 35-45 ℃ while stirring, extruding, cooling and shaping to obtain the PVC-UH pipe with high strength and high pressure resistance.
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| CA1339984C (en) * | 1988-09-12 | 1998-08-04 | Mitsui Chemicals Inc. | Heat resistant polyvinyl chloride copolymer and preparation process of the copolymer |
| CN105693941A (en) * | 2016-04-11 | 2016-06-22 | 叶青 | High-strength PVC-U (polyvinyl chloride unplasticized) pipe |
| CN110240595A (en) * | 2019-07-10 | 2019-09-17 | 河南龙湖生物技术有限公司 | The preparation method and application of phentriazine class compound as polyvinyl chloride light stabilizer |
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