CN114854144A - Large-diameter PVC-U pipe and preparation method thereof - Google Patents
Large-diameter PVC-U pipe and preparation method thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
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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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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
Abstract
The invention discloses a large-caliber PVC-U pipe and a preparation method thereof. The large-caliber PVC-U pipe is prepared by the following method: s1, mixing a reaction monomer, an initiator and gamma-alumina nano fibers to obtain active alumina nano fibers; s2, mixing the activated alumina nano-fibers prepared in the step S1 with PVC resin, a heat stabilizer, a lubricant, an impact modifier and a processing aid to obtain a mixed material; and S3, adding the mixed material prepared in the step S2 into an extruder, and performing melt extrusion and mold forming to obtain the large-caliber PVC-U pipe. The thermal stability and the mechanical property of the PVC-U pipe are improved through the synergistic effect of the gamma-alumina nano-fiber and the reaction monomer in a PVC system, and the plasticizing degree of the PVC-U pipe is more uniform.
Description
Technical Field
The invention relates to the technical field of PVC-U pipes, in particular to a large-caliber PVC-U pipe and a preparation method thereof.
Background
With the steady advance of the urbanization process of China, the urban population is more and more, the urban water supply amount is increased rapidly, and the caliber of a water pipeline from a water source to a city is larger and larger. At present, medium and small caliber (DN315 and below) PVC water supply pipe materials are widely applied in China. The large-caliber PVC-U pipe (the caliber is more than or equal to 315mm), due to the large caliber and the thick wall thickness, in the conventional production process, the production line speed is slow, the thermal mechanical process of the melt is long, the thermal stability of the pipe is insufficient, the pipe is easy to degrade, and the mechanical property of the large-caliber PVC-U pipe is poor; along with the increase of the wall thickness, the plasticizing conditions of different positions of the pipe are different, the plasticizing uniformity is poor, and the toughness of the PVC-U pipe is deteriorated and the corrosion resistance is insufficient.
The prior art discloses production equipment and a process for a large-caliber biaxially oriented PVC pipe, wherein a specific stretching and expanding forming device is adopted to perform annular expansion and axial stretching on the PVC pipe, so that the mechanical property of the large-caliber PVC pipe is improved. However, the PVC-U pipe disclosed by the prior art has the disadvantages of complex production process, multiple steps, high cost, and need of using special equipment and process, and is not suitable for traditional PVC-U pipe manufacturers.
Therefore, a large-diameter PVC-U pipe with better thermal stability, high toughness and good corrosion resistance needs to be developed.
Disclosure of Invention
In order to overcome the defects of poor thermal stability and poor mechanical property in the prior art, the invention provides the large-caliber PVC-U pipe, the reaction monomer is adsorbed by the gamma-alumina nano fiber and slowly released in the melting process after being added into the PVC-U pipe material, and the thermal stability of the PVC-U pipe is improved by graft modification in the extrusion process; meanwhile, the gamma-alumina nano fiber is used as a physical crosslinking point, so that macromolecule entanglement is increased, and the mechanical property and heat resistance of the PVC-U pipe are improved; the physical crosslinking points form a heat conducting network, and the heat conducting function of the PVC melt is increased, so that the plasticizing degree of the PVC-U pipe is more uniform, and the toughness and the corrosion resistance of the PVC-U pipe are improved.
The invention also aims to provide a preparation method of the large-caliber PVC-U pipe.
In order to solve the technical problems, the invention adopts the technical scheme that:
a large-caliber PVC-U pipe is characterized by being prepared by the following method:
s1, mixing a reaction monomer, an initiator and gamma-alumina nano fibers to obtain active alumina nano fibers;
the reaction monomer comprises an alkaline grafting monomer and a styrene monomer;
the specific surface area of the gamma-alumina nano fiber is more than or equal to 100m 2 /g；
S2, mixing the activated alumina nanofiber prepared in the step S1 with PVC resin, a heat stabilizer, a lubricant, an impact modifier and a processing aid to obtain a mixed material;
and S3, adding the mixed material prepared in the step S2 into an extruder, and performing melt extrusion and mold forming to obtain the large-caliber PVC-U pipe.
Reaction monomers are adsorbed by gamma-alumina nano fibers and slowly released in the melting process after being added into the PVC-U pipe material, and grafting modification is carried out in the extrusion process, so that the thermal stability of the PVC-U pipe is improved. The reactive monomers include basic grafting monomers and styrenic monomers. The alkaline grafting monomer can promote the decomposition of PVC and partial dehydrochlorination, so that a certain double bond is formed inside a PVC molecular chain, and the active points and the grafting points of a PVC grafting skeleton are increased; in the melt extrusion process, under the action of an initiator, an alkaline grafting monomer and a styrene monomer are subjected to graft copolymerization at double bonds of a PVC molecular chain through a chemical grafting reaction, so that a side chain is introduced and is connected with PVC resin. The side chain introduced by grafting destroys an unstable structure (chlorine group) in PVC molecules, thereby improving the thermal stability of the PVC-U pipe.
The styrenic monomer in the reactive monomer can increase the molecular chain length of the introduced side chain. The inventor researches and discovers that after the length of a side chain is moderately increased, the molecular distance of PVC (polyvinyl chloride) can be increased, the intermolecular force is reduced, and the impact strength of the PVC-U pipe is improved, namely the toughness is obviously improved.
The gamma-alumina nano fiber is used as a physical crosslinking point, so that macromolecular entanglement is increased, and the mechanical property and heat resistance of the PVC-U pipe are improved; the physical crosslinking points form a heat conducting network, and the heat conducting function of the PVC melt is increased, so that the melt plasticizing degree of the PVC-U pipe is more uniform under the same shearing condition.
After the reaction monomer is grafted on a PVC molecular chain, the compatibility of PVC molecules and gamma-alumina nano fibers is improved, the gamma-alumina nano fibers are dispersed more uniformly among PVC systems, and the interface binding force between organic macromolecules and inorganic fillers is increased.
Preferably, the basic grafting monomer is one or more of Glycidyl Methacrylate (GMA), dimethylaminoethyl methacrylate (DMAEMA), hydroxyethyl methacrylate (HEMA), Methyl Methacrylate (MMA), dibutyl fumarate (DBF) or dibutyl maleate (DBM).
Preferably, the styrene monomer is one or more of styrene (St), alpha-methyl styrene (a-MS) or Divinylbenzene (DVB).
More preferably, the basic grafting monomer is GMA and the styrenic monomer is St.
Preferably, the mass ratio of the reaction monomer, the initiator and the gamma-alumina nanofiber is (0.35-0.9): (0.05-0.1): 100.
preferably, the mass ratio of the alkaline grafting monomer to the styrene monomer in the reaction monomer is 2 to (0.1-0.6).
When the alkaline grafting monomer and the styrene monomer in the reaction monomer are in the mass ratio range, the grafting rate of the reaction monomer is higher, and the degradation of a PVC matrix can be improved. The inventor researches and discovers that when the adding amount of the styrene monomer is too small, PVC molecules can be degraded in a longer melting process, so that the thermal stability time of the PVC-U pipe is reduced.
Preferably, the diameter of the gamma-alumina nanofiber is 4-8 nm, and the length of the gamma-alumina nanofiber is 200-300 nm.
The length of the gamma-alumina nano fiber is only 200-300 nm, and the length of the gamma-alumina nano fiber can not be greatly changed under the action of shearing force before and after the extrusion of the large-caliber PVC-U pipe.
Preferably, the specific surface area of the gamma-alumina nano fiber is 250-300 m 2 /g。
The specific surface area of the gamma-alumina nano fiber is in a proper range, and is not suitable to be too large or too small. The specific surface area of the gamma-alumina nano fiber is 250-300 m 2 When the monomer is used per gram, the monomer can be effectively adsorbed, and the monomer is slowly released in the melt extrusion process, so that the grafting modification is realized. The inventor researches and discovers that when the specific surface area of the gamma-alumina nano fiber is too large, the gamma-alumina nano fiber can adsorb reaction monomers too firmly, the release rate is too slow, and the grafting effect of the reaction monomers is poor; when the specific surface area of the gamma-alumina nano fiber is too small, the adsorption effect on the reaction monomer is poor, and the graft modification of the reaction monomer on PVC is also influenced.
Alternatively, the initiator may be a peroxide initiator.
Preferably, the peroxide initiator is one or more of dicumyl peroxide (DCP), ethyl 3, -3-bis (t-butylperoxy) butyrate, tert-amyl 2-ethylhexyl peroxide (TAPO) or tert-amyl peroxide (TAHP).
Preferably, in the mixed material, the mass ratio of the PVC resin, the activated alumina nano fibers, the heat stabilizer, the lubricant, the impact modifier and the processing aid is 100: 2-10: 5-8: 0.5-4: 1-8: 0.2-4.
Preferably, the viscosity number of the PVC resin is 107-118 mL/g.
The viscosity number of the PVC resin is tested according to the GB/T3401-2007 standard method.
Preferably, the heat stabilizer is a calcium zinc heat stabilizer.
Preferably, the lubricant is one or more of paraffin, polyethylene wax, oxidized polyethylene wax, fatty acid ester wax or metal soap.
Preferably, the impact modifier is Chlorinated Polyethylene (CPE) and/or methyl methacrylate-butadiene-styrene terpolymer (MBS).
Preferably, the processing aid is an Acrylate Compound (ACR).
Preferably, the mixed material can also comprise 0.1-4 parts by weight of pigment.
Optionally, the pigment is titanium dioxide and/or carbon black.
The caliber DN of the large-caliber PVC-U pipe is more than or equal to 315 mm.
The invention also provides a preparation method of the large-caliber PVC-U pipe, which is characterized by comprising the following steps:
s1, mixing a reaction monomer, an initiator and gamma-alumina nano fibers to obtain active alumina nano fibers;
the reaction monomer comprises an alkaline grafting monomer and a styrene monomer;
the specific surface area of the gamma-alumina nano fiber is more than or equal to 100m 2 /g；
S2, mixing the activated alumina nano-fibers prepared in the step S1 with PVC resin, a heat stabilizer, a lubricant, an impact modifier and a processing aid to obtain a mixed material;
and S3, adding the mixed material prepared in the step S2 into an extruder, and performing melt extrusion and mold forming to obtain the large-caliber PVC-U pipe.
Preferably, in step s1, the γ -alumina nanofibers are dried before mixing.
Specifically, the drying treatment is drying treatment at 110-150 ℃ for 1-1.5 h.
Preferably, in the step S1, the mixing is carried out at 60-90 ℃ for 5-10 minutes.
Preferably, in the step S2, the mixing is performed at a rotating speed of 30-80 rpm and at a temperature of 100-130 ℃, and then at a rotating speed of 10-20 rpm and at a temperature of 40-50 ℃.
Preferably, in the step S3, the extrusion temperature is 160-190 ℃, and the mold forming temperature is 170-220 ℃.
The large-caliber PVC-U pipe can be used in the field of water supply pipes.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops a large-caliber PVC-U pipe which has excellent thermal stability, and the thermal stability time is more than or equal to 33 min; the toughness is good, the elongation at break is more than or equal to 120 percent, and the drop hammer impact damage rate is low; and the corrosion resistance is good, and the pipe is not corroded and damaged or the inner wall of the pipe is slightly changed after the pipe is soaked in dichloromethane for 15min at the temperature of 15 ℃.
Reaction monomers are adsorbed by gamma-alumina nano fibers and slowly released in the melting process after being added into a PVC-U pipe material, grafting modification is carried out in the extrusion process, the thermal stability of the PVC-U pipe material is improved, the compatibility of PVC molecules and the gamma-alumina nano fibers is improved, the gamma-alumina nano fibers are more uniformly dispersed among PVC systems, and the interface binding force between organic macromolecules and inorganic fillers is increased. Meanwhile, the gamma-alumina nano fiber is used as a physical crosslinking point, so that macromolecule entanglement is increased, and the mechanical property and heat resistance of the PVC-U pipe are improved; the physical crosslinking points form a heat conducting network, and the heat conducting function of the PVC melt is increased, so that the plasticizing degree of the PVC-U pipe is more uniform.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples and comparative examples are all commercially available, wherein:
the gamma-alumina nano-fiber-1 is purchased from Jiangsu Xiifeng nano-material XFJ52, has the diameter of 4-8 nm, the length of 200-300 nm and the specific surface area of 250-300 m 2 /g；
The gamma-alumina nano-fiber-2 is purchased from T-1700 of Jiahua crystal fiber company of Zhejiang, has the diameter of 1-6 nm, the length of 10-150 nm and the specific surface area of 420-560 m 2 /g；
Gamma-alumina nano fiber-3, purchased from Ningbo Jinlei nano material company JL-6, with a diameter of 50-200 nm, a length of 1-15 μm, and a specific surface area of 32-39 m 2 /g。
GMA, purchased from shanghai yinshi chemistry;
HEMA, purchased from shanghai yinshi chemistry;
st, Purchase chemical industry of Jinming Wei of Jinan province;
DVB, purchased from golden brocade chemistry;
DCP, available from the Dongguan university company LUPEROX DC brand;
PVC resin, SG5 type resin, viscosity number 112mL/g, purchased from Xinjiang Zhongtai;
heat stabilizers, calcium zinc heat stabilizers, available from Guangdong Xinda QY-2021A 1;
lubricant, polyethylene wax, available from Lu' an group LA-W110;
impact modifier, CPE, purchased from shandongyike 135A;
a processing aid, ACR, purchased from Shandong Ruifeng LP-90;
pigment, titanium dioxide, purchased from Bailey bis BLR-688;
maleic anhydride, purchased from Shandong Longhui chemical Co., Ltd;
calcium carbonate whiskers purchased from Shandong Jiaying chemical NP-CW 2;
mesoporous silica nanoparticles (specific surface area: 665.6-765.7 m) 2 Per gram), purchased from Jiangsu Xiancheng nano material XFF 34-1.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Example 1 provides a PVC-U pipe, the preparation method of which is as follows:
s1, drying gamma-alumina nano fibers at 110 ℃ for 1h, and mixing a reaction monomer, DCP and the gamma-alumina nano fibers at 80 ℃ for 5min to obtain activated alumina nano fibers;
the reaction monomer is a mixture of GMA and St according to the mass ratio of 2: 0.5;
the mass ratio of the reaction monomer, the DCP and the gamma-alumina nano fiber is 0.35: 0.05: 100;
s2, mixing the activated alumina nanofiber prepared in the step S1 with PVC resin, a calcium-zinc heat stabilizer, polyethylene wax, CPE, ACR and titanium dioxide to obtain a mixed material;
the contents of the components in the mixed material are as follows (parts by weight): 100 parts of PVC resin, 2 parts of activated alumina nano fiber, 5 parts of calcium-zinc heat stabilizer, 0.6 part of polyethylene wax, 2 parts of CPE, 1 part of ACR and 2.5 parts of titanium dioxide;
s3, adding the mixed material prepared in the step S2 into a conical double-screw extruder, wherein the temperature of a machine barrel is 160-200 ℃, and performing melt extrusion; and (3) molding at 170-220 ℃ to obtain the PVC-U pipe with the nominal diameter dn being 400 multiplied by 12.3 mm.
Example 2
Example 2 provides a PVC-U pipe, the difference between the preparation method and example 1 is:
GMA in the reaction monomer is replaced by hydroxyethyl methacrylate (HEMA).
Example 3
Example 3 provides a PVC-U pipe, the preparation method differs from example 1 in that:
st in the reaction monomers was replaced with Divinylbenzene (DVB).
Example 4
Example 4 provides a PVC-U pipe, the preparation method differs from example 1 in that:
the gamma-alumina nanofiber-1 is replaced by the gamma-alumina nanofiber-2.
Example 5
Example 5 provides a PVC-U pipe, the preparation method differs from example 1 in that:
in the reaction monomer, the mass ratio of GMA to St is 2: 0.1;
the mass ratio of the reaction monomer, the DCP and the gamma-alumina nano fiber is 0.5: 0.07: 100.
Example 6
Example 6 provides a PVC-U pipe, the preparation method differs from example 1 in that:
in the reaction monomer, the mass ratio of GMA to St is 2: 0.6;
the mass ratio of the reaction monomer, the DCP and the gamma-alumina nano fiber is 0.9: 0.1: 100.
Example 7
Example 7 provides a PVC-U pipe, the preparation method differs from example 1 in that:
in the reaction monomer, the mass ratio of GMA to St is 2: 0.05;
the mass ratio of the reaction monomer, the DCP and the gamma-alumina nano fiber is 0.2: 0.05: 100.
Example 8
Embodiment 8 provides a PVC-U pipe, the method of making is as follows:
s1, drying gamma-alumina nano fibers at 130 ℃ for 1h, and mixing a reaction monomer, DCP and the gamma-alumina nano fibers at 70 ℃ for 10min to obtain activated alumina nano fibers;
the reaction monomer is a mixture of GMA and St according to the mass ratio of 2: 0.5;
the mass ratio of the reaction monomer, the DCP and the gamma-alumina nano fiber is 0.9: 0.1: 100;
s2, mixing the activated alumina nanofiber prepared in the step S1 with PVC resin, a calcium-zinc heat stabilizer, polyethylene wax, CPE, ACR and titanium dioxide to obtain a mixed material;
the contents of the components in the mixed material are as follows (parts by weight): 100 parts of PVC resin, 10 parts of active alumina nano fiber, 8 parts of calcium-zinc heat stabilizer, 0.7 part of polyethylene wax, 5 parts of CPE, 4 parts of ACR and 4 parts of titanium dioxide;
s3, adding the mixed material prepared in the step S2 into a conical double-screw extruder, wherein the temperature of a machine barrel is 160-200 ℃, and performing melt extrusion; and (3) molding at 170-220 ℃ to obtain the PVC-U pipe with the nominal diameter dn being 400 multiplied by 12.3 mm.
Comparative example 1
Comparative example 1 provides a PVC-U pipe, the preparation method is as follows:
s1, mixing gamma-alumina nano fibers with PVC resin, a calcium-zinc heat stabilizer, polyethylene wax, CPE, ACR and titanium dioxide to obtain a mixed material;
the contents of the components in the mixed material are as follows (parts by weight): 100 parts of PVC resin, 2 parts of gamma-alumina nano fiber, 5 parts of calcium-zinc heat stabilizer, 0.6 part of polyethylene wax, 2 parts of CPE (chlorinated polyethylene), 1 part of ACR (acrylic copolymer), and 2.5 parts of titanium dioxide;
s2, adding the mixed material prepared in the step S1 into a conical double-screw extruder, wherein the temperature of a machine barrel is 160-200 ℃, and performing melt extrusion; and (3) molding at 170-220 ℃ to obtain the PVC-U pipe with the nominal diameter dn being 400 multiplied by 12.3 mm.
Namely, the difference from example 1 is that: the gamma-alumina nano fiber is not modified and is directly mixed with other components in the PVC-U pipe.
Comparative example 2
Comparative example 2 provides a PVC-U pipe, the preparation method differing from example 1 in that:
the gamma-alumina nano fiber is replaced by calcium carbonate crystal whisker.
Comparative example 3
Comparative example 3 provides a PVC-U pipe, the preparation method differing from example 1 in that:
the gamma-alumina nano-fiber is replaced by mesoporous silica nano-particles.
Comparative example 4
Comparative example 4 provides a PVC-U pipe, the preparation method differing from example 1 in that:
GMA in the reaction monomer is replaced by maleic anhydride.
Comparative example 5
Comparative example 5 provides a PVC-U pipe, the preparation method differing from example 1 in that:
st is excluded from the reaction monomers, i.e. 100% GMA.
Comparative example 6
Comparative example 3 provides a PVC-U pipe, the preparation method differing from example 1 in that:
the gamma-alumina nanofiber-1 is replaced by the gamma-alumina nanofiber-3.
Performance testing
The PVC-U pipes prepared in the above examples and comparative examples were subjected to a performance test, which specifically comprises the following steps:
(1) thermal stability performance: performing dynamic thermal stability test on each material formula system by using a torque rheometer, sampling every 5min, and performing color test until the color changes, wherein the length of thermal stability time represents the thermal stability of the material system;
(2) drop hammer impact test: the detection method is that the test is carried out according to GB/T141522001, 50 times of impact is carried out at the temperature of 0 ℃, and the number of unbroken parts is calculated;
(3) methylene chloride impregnation test: the detection method is determined according to GB/T13526-;
(4) elongation at break: the detection method is determined according to GB/T8804.2-2003;
(5) hydrostatic pressure test: the detection method is determined according to GB/T6111-2018, the ring stress is 38MPa, and the test time is 1 hour.
The test results are shown in Table 1.
TABLE 1 test results of examples and comparative examples
According to the test results in Table 1, it can be seen that the PVC-U pipe with the caliber of 400mm prepared by the embodiments of the invention has excellent thermal stability, and the thermal stability time is more than or equal to 33 min; the PVC-U pipe has excellent toughness, the elongation at break is more than or equal to 120 percent, and the drop hammer impact breakage rate is extremely low, which indicates that the plasticizing degree of each position of the PVC-U pipe is relatively uniform; no corrosion damage or only slight change of the inner wall is caused by dichloromethane dipping at 15 ℃ for 15min, which shows that the PVC-U pipe has good corrosion resistance.
According to the test results of example 1 combined with examples 5-7, the thermal stability time of the PVC-U pipe prepared in example 7 is relatively shorter, the toughness is slightly worse than that of examples 1, 5 and 6, the elongation at break is 121%, and the number of impact breakage by falling weight is 8. Therefore, the mass ratio of the reaction monomer, the initiator and the gamma-alumina nano fiber is (0.35-0.9): (0.05-0.1): when the mass ratio of the alkaline grafting monomer to the styrene monomer in the reaction monomer is within the range of 2: 0.1-0.6 within 100, the prepared PVC-U pipe has better comprehensive performance.
According to the comparison results of example 1 and example 4, when the specific surface area of the gamma-alumina nanofibers is large, 400m is reached 2 When the specific molecular weight is more than g, the adsorption capacity to the reaction monomer is too strong, and the grafting effect of the reaction monomer in the melt extrusion process is influenced, so that the corrosion resistance of the PVC-U pipe is slightly poor, and the elongation at break is slightly poorThe rate is also reduced to some extent.
In the comparative example 1, the gamma-alumina nano fiber is not modified and is directly mixed with other components in the PVC-U pipe, and the thermal stability time is only 26min, which shows that the thermal stability of the PVC-U pipe is poor; and the gamma-alumina nano fiber is used as an inorganic material and has poor compatibility with other components, the plasticizing degree of the large-caliber PVC-U pipe is uneven in the long-time melting extrusion and plasticizing processes, and the prepared PVC-U pipe has low toughness and poor hydrostatic test and corrosion resistance.
In comparative example 2, the gamma-alumina nanofibers were replaced with calcium carbonate whiskers; in comparative example 3, the gamma-alumina nanofibers were replaced with mesoporous silica nanoparticles. It can be seen that the whisker material with non-porous structure and without adsorption function, or the whisker material with adsorption function but without fibrous material, can not achieve the technical effect of the gamma-alumina nano fiber in the PVC-U pipe, i.e. the whisker material can not have the functions of adsorbing and slowly releasing reaction monomers, and enhancing the mechanical property and the thermal conductivity.
In comparative example 4, GMA in the reaction monomer is replaced by maleic anhydride, maleic anhydride non-basic monomer is difficult to promote the decomposition of PVC to partially dehydrochlorinate, and the PVC-U pipe prepared in comparative example 4 has poor thermal stability performance due to the damage of unstable structures (chlorine groups) in PVC molecules, and the thermal stability time is only 20 min. The reaction monomer of comparative example 5 does not contain St, and although the basic grafting monomer is grafted in the PVC molecule, the length of the grafted side chain is too short, so that the effective improvement on the toughness of the PVC-U pipe is difficult to achieve.
In comparative example 5, the specific surface area of the gamma-alumina nanofiber is too small, the adsorption effect on the reaction monomer is poor, the amount of the adsorbed reaction monomer is very small, and the graft modification of the reaction monomer on PVC is influenced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A large-caliber PVC-U pipe is characterized by being prepared by the following method:
s1, mixing a reaction monomer, an initiator and gamma-alumina nano fibers to obtain active alumina nano fibers;
the reaction monomer comprises an alkaline grafting monomer and a styrene monomer;
the specific surface area of the gamma-alumina nano fiber is more than or equal to 100m 2 /g；
S2, mixing the activated alumina nanofiber prepared in the step S1 with PVC resin, a heat stabilizer, a lubricant, an impact modifier and a processing aid to obtain a mixed material;
and S3, adding the mixed material prepared in the step S2 into an extruder, and performing melt extrusion and mold forming to obtain the large-caliber PVC-U pipe.
2. The large-caliber PVC-U pipe according to claim 1, wherein the mass ratio of the reaction monomer, the initiator and the gamma-alumina nanofiber is (0.35-0.9): (0.05-0.1): 100.
3. the large-caliber PVC-U pipe according to claim 1, wherein the mass ratio of the alkaline grafting monomer to the styrene monomer in the reaction monomer is 2: 0.1-0.6.
4. The large-caliber PVC-U pipe according to claim 1, wherein the gamma-alumina nanofibers have a diameter of 4-8 nm and a length of 200-300 nm.
5. The large-caliber PVC-U pipe according to claim 1, wherein the specific surface area of the gamma-alumina nanofiber is 250-300 m 2 /g。
6. The heavy gauge PVC-U tubing of claim 1, wherein the initiator is a peroxide initiator.
7. The large-caliber PVC-U pipe according to claim 1, wherein the mass ratio of the PVC resin, the activated alumina nanofibers, the heat stabilizer, the lubricant, the impact modifier and the processing aid in the mixed material is 100: 2-10: 5-8: 0.5-4: 1-8: 0.2-4.
8. The preparation method of the large-caliber PVC-U pipe material as recited in any one of claims 1 to 7, characterized by comprising the following steps:
s1, mixing a reaction monomer, an initiator and gamma-alumina nano fibers to obtain active alumina nano fibers;
the reaction monomer comprises an alkaline grafting monomer and a styrene monomer;
the specific surface area of the gamma-alumina nano fiber is more than or equal to 100m 2 /g；
S2, mixing the activated alumina nano-fibers prepared in the step S1 with PVC resin, a heat stabilizer, a lubricant, an impact modifier and a processing aid to obtain a mixed material;
and S3, adding the mixed material prepared in the step S2 into an extruder, and performing melt extrusion and mold forming to obtain the large-caliber PVC-U pipe.
9. The preparation method according to claim 8, wherein in step S1, the γ -alumina nanofibers are dried before mixing.
10. The preparation method according to claim 8, wherein in step S3, the extrusion temperature is 160-190 ℃ and the die forming temperature is 170-220 ℃.
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