CN112226018A - High-performance PVC (polyvinyl chloride) plastic pipe and preparation method thereof - Google Patents
High-performance PVC (polyvinyl chloride) plastic pipe and preparation method thereof Download PDFInfo
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- CN112226018A CN112226018A CN202011113520.5A CN202011113520A CN112226018A CN 112226018 A CN112226018 A CN 112226018A CN 202011113520 A CN202011113520 A CN 202011113520A CN 112226018 A CN112226018 A CN 112226018A
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- Prior art keywords
- plastic pipe
- pvc plastic
- parts
- nano montmorillonite
- pvc
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- 229920003023 plastic Polymers 0.000 title claims abstract description 44
- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004800 polyvinyl chloride Substances 0.000 title description 72
- 229920000915 polyvinyl chloride Polymers 0.000 title description 72
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
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- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
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- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
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- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
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- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
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- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
Classifications
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-performance PVC plastic pipe and a preparation method thereof. The PVC plastic pipe comprises the following raw materials in parts by weight: 100 parts of PVC resin, 10-20 parts of chlorinated polyethylene, 1-3 parts of PA-20 processing aid, 10-20 parts of MMA/S-nano montmorillonite composite material, 3-5 parts of stabilizer, 1-2 parts of lubricant, 0.5-2 parts of antioxidant and 1-3 parts of filler. The PVC plastic pipe has the advantages of good impact resistance, heat resistance, pressure resistance, good thermal stability and tensile strength, good plasticizing performance, easy processing and the like, effectively solves the problems of rigidity, toughness, poor impact resistance and cracking resistance, poor processing plasticity and the like of the existing PVC pipe, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of plastic pipes, in particular to a high-performance PVC plastic pipe and a preparation method thereof.
Background
The PVC (polyvinyl chloride) pipe has strong acid and alkali resistance and strong caking propertyHigh structural strength, good electrical insulation and the like, so that the plastic pipe is widely applied to the technical fields of water supply, building drainage, pollution discharge, chemical industry and the like, and is a plastic pipe which has an application range second to polyethylene. In the prior art, most of PVC pipes are produced by using PVC resin as a main material and adding some auxiliary materials, and the main defects of the PVC pipes are poor impact resistance and poor processing plasticity. On one hand, the hard PVC product is brittle, and the cantilever beam notch impact strength of the PVC at normal temperature is only 2.2KJ/m2And the PVC material is very easy to crack and cannot be used as a structural material when being impacted, and on the other hand, the PVC material has poor stability, and factors such as light, oxygen, heat and the like can accelerate the decomposition of PVC, so that the flexibility of the PVC is reduced, and finally the PVC becomes brittle, so that the physical and mechanical properties are rapidly reduced. In addition, the PVC pipe prepared by using pure PVC resin as a main material generally has poor plasticity, and even if plasticizer is added, the plasticity of the prepared PVC pipe cannot be ensured to meet the requirements of most of production.
Aiming at the problems of the PVC pipe, the prior art mainly adds some toughening modifiers and processing aids to improve the impact resistance and the plasticity of the PVC pipe, for example, in the Chinese patent application with the publication number of CN 107964185A, dibutyl phthalate and dioctyl phthalate are added to improve the processing plasticity of the pipe, and ACR aids are added to improve the impact resistance; the Chinese patent application with the publication number of CN 103304914A improves the processing plasticity of the pipe by adding dioctyl phthalate, and improves the shock resistance by adding MBS resin; the Chinese patent application with the publication number of CN 105906980A improves the processing plasticity of the pipe by adding acetyl tributyl citrate, synthetic vegetable ester, polyester and the like, and improves the impact resistance by adding MBS, CPE, EVA and the like. The PVC pipe modified by adding various processing modifiers lacks pertinence, the modification effect is not ideal, and the problems of high processing cost, reduction of other performances of the product and the like are caused.
Disclosure of Invention
The invention aims to provide a high-performance PVC plastic pipe and a preparation method thereof. The PVC plastic pipe has the advantages of good impact resistance, heat resistance, pressure resistance, thermal stability, tensile strength, good plasticizing performance, easy processing and the like.
The invention is realized by the following technical scheme:
a high-performance PVC plastic pipe comprises the following raw materials in parts by weight:
preferably, the MMA/S-nano montmorillonite composite material is a methyl methacrylate-styrene copolymer/organic nano montmorillonite composite material, and the organic nano montmorillonite in the composite material forms an intercalation or peeling structure in a methyl methacrylate-styrene copolymer matrix.
Preferably, the weight ratio of the organic nano montmorillonite in the MMA/S-nano montmorillonite composite material is 5-25%, and the weight ratio of methyl methacrylate to styrene in the methyl methacrylate-styrene copolymer is (3-4): 1.
Preferably, the preparation steps of the MMA/S-nano montmorillonite composite material are as follows:
(1) dissolving sodium-based montmorillonite in water to prepare a suspension with the mass fraction of 4-7%, heating to 75-85 ℃, adding cetyl trimethyl ammonium bromide under a stirring state, stirring for reaction for 1-2 hours, standing for layering, filtering, taking a precipitate, washing the precipitate with water, drying in vacuum to constant weight, grinding and sieving to obtain organic nano montmorillonite;
(2) mixing organic nano montmorillonite with water, placing the mixture in a reactor, heating and stirring the mixture in a water bath at the temperature of 80-85 ℃ for reaction for 0.5-1 h under the protection of nitrogen, cooling the mixture to 70-75 ℃, adding methyl methacrylate, styrene and dibenzoyl peroxide, continuing the reaction for 4-6 h, then heating the mixture to 85-90 ℃, reacting for 1-2 h, standing and layering the mixture after the reaction is finished, filtering the mixture, taking precipitate, cleaning the precipitate with water, and drying the precipitate in vacuum to constant weight to obtain the MMA/S-nano montmorillonite composite material.
Specifically, the weight ratio of the hexadecyl trimethyl ammonium bromide to the sodium montmorillonite in the step (1) is 0.25-0.35: 1.
The weight ratio of the organic nano montmorillonite to the methyl methacrylate to the styrene in the step (2) is (0.25-1.35): 3-4): 1, the addition amount of the water is 6-7 times of the total volume of the methyl methacrylate and the styrene, and the addition amount of the dibenzoyl peroxide is 3-4% of the total weight of the methyl methacrylate and the styrene.
Preferably, the stabilizer is at least one selected from calcium-zinc composite heat stabilizer, organic tin stabilizer, rare earth stabilizer and metal soap stabilizer. More preferably, the stabilizer is a calcium-zinc composite heat stabilizer.
Specifically, the organotin stabilizers include, but are not limited to: organotin mercaptides stabilizers (e.g., methyltin mercaptide stabilizer SW-977), organotin maleate stabilizers (e.g., dibutyltin maleate, dibutyltin bis (monobutyl maleate), di-n-octyltin maleate) or organotin fatty acid stabilizers (e.g., dibutyltin dilaurate, di-n-octyltin dilaurate).
The rare earth stabilizers include, but are not limited to: lanthanum salicylate, lanthanum citrate, lanthanum laurate, lanthanum ricinoleate, lanthanum protocatechuate, cerium stearate, praseodymium stearate, neodymium isooctanoate, lanthanum cyanurate.
The metal soap stabilizers include, but are not limited to: barium stearate, calcium ricinoleate and zinc ricinoleate.
Preferably, the lubricant is at least one selected from stearic acid, stearic acid amide, paraffin, polyethylene wax, oxidized polyethylene wax, silicone oil and white oil. More preferably, the lubricant is a combination of stearic acid and oxidized polyethylene wax.
Preferably, the antioxidant is at least one selected from phosphite antioxidants, hindered phenol antioxidants, thioester antioxidants and amine antioxidants. More preferably, the antioxidant is a combination of a phosphite antioxidant and a hindered phenol antioxidant.
Specifically, the phosphite antioxidant includes, but is not limited to: tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite and (nonylphenyl) phosphite.
The hindered phenolic antioxidants include, but are not limited to: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], or triethylene glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.
The thioester antioxidant includes but is not limited to: dioctadecyl thiodipropionate and dilauryl thiodipropionate.
The amine antioxidants include but are not limited to: butyl octylated diphenylamine.
Preferably, the filler is selected from at least one of nano calcium carbonate, talcum powder, titanium dioxide and wollastonite. More preferably, the filler is nano calcium carbonate.
Preferably, the PVC resin is SG-5 type resin.
Preferably, the chlorinated polyethylene has a chlorine content of 36%.
Preferably, the PA-20 processing aid is KANE ACE PA, model PA-20, manufactured by Kazuno chemical industries, Inc., and brand name of Japanese Kozuo.
The invention also provides a method for preparing the heat-resistant high-impact PVC plastic pipe, which comprises the following steps: adding all the raw materials in the formula amount into a high-speed hot mixer for mixing and dispersing, transferring all the raw materials into a cold mixer for stirring and cooling when the temperature reaches 110-120 ℃, and discharging all the raw materials into a hopper for later use when the temperature is reduced to 45-50 ℃; and adding the mixed raw materials to be used in the hopper into a double-screw extruder for plasticizing, and molding by using a mold to obtain the heat-resistant high-impact PVC plastic pipe.
Specifically, the mixed raw materials are extruded and molded by a die through a double-screw extruder, and the first temperature zone of the extruder barrel is as follows: 196-205 ℃; the second area is as follows: 185-195 ℃; the third area is: 180-190 ℃; the fourth area is: 175-186 ℃; the fifth area is: 170-180 ℃; the transition section temperature is: 160-170 ℃; the first mold temperature zone is: 165-180 ℃; the second area is as follows: 165-180 ℃; the third area is: 170-180 ℃; the temperature of the neck ring mold is as follows: 170-210 ℃; the rotating speed of the extruder is as follows: 15-30 r/min; the rotating speed of the feeder is as follows: 15-25 r/min; the head pressure is: 6-20 MPa; the vacuum degree of the water tank is as follows: 0.03 to 0.06 MPa; the traction speed is as follows: 5 to 7 m/min.
The invention uses chlorinated polyethylene with 36 percent of chlorine content and MMA/S-nano montmorillonite composite material to jointly toughen PVC resin, so that the prepared PVC pipe has excellent shock resistance and processability. The chlorinated polyethylene has excellent weather resistance, oil resistance and flame retardance, is well compatible with PVC resin, can obviously improve the impact resistance of PVC, but the single use of the chlorinated polyethylene to toughen the PVC resin can cause poor transparency of the material and reduced tensile strength, bending strength and heat resistance, and the best impact modification effect can be obtained only in a relatively narrow processing range, thereby greatly limiting the application of the chlorinated polyethylene in PVC toughening modification. The MMA/S-nano montmorillonite composite material is formed by compounding inorganic rigid particle nano montmorillonite with methyl methacrylate-styrene copolymer after organic modification, wherein polymer monomers of methyl methacrylate and styrene are firstly intercalated between crystal layers of organic nano montmorillonite in situ, then polymerization is carried out according to the polymerization property of the monomers, polymers are formed among the montmorillonite, and the organic nano montmorillonite in the composite material forms an intercalated or peeled structure in a methyl methacrylate-styrene copolymer matrix, so that the composite material has higher strength and modulus. The inventor finds in earlier researches that the MMA/S-nano montmorillonite composite material has the effects of toughening inorganic rigid particles (nano montmorillonite) and toughening organic rigid particles (methyl methacrylate-styrene copolymer), and after compounding, on one hand, the influence of processing fluidity caused by the fact that inorganic nano particles are large in specific surface area and large in specific surface energy and are easy to agglomerate is avoided, on the other hand, the polarity of polymethyl methacrylate in the methyl methacrylate-styrene copolymer is similar to that of PVC, and similar compatibility plays a role in a transition phase in a blending process, so that the compatibility of the MMA/S-nano montmorillonite composite material and PVC is improved. More importantly, the inventor also finds that the MMA/S-nano montmorillonite composite material and the chlorinated polyethylene are combined, so that the impact resistance of the PVC can be obviously improved, the toughening effect can be cooperatively exerted, the defects existing in the process of toughening by singly using the chlorinated polyethylene can be overcome, the performances of the PVC, such as tensile strength, modulus, heat distortion temperature, processing fluidity and the like, are obviously improved, and the excellent effect is obtained.
Furthermore, compared with the ACR acrylate copolymer processing aid, the PA-20 processing aid has the function of promoting PVC plasticization, reduces the plasticizing temperature, greatly improves the processing performance of PVC resin, and adopts the principle of promoting PVC plasticization: the PA-20 is added into the PVC, when external heating generates shearing, the processing aid surrounded by the PVC is firstly melted and then adhered to the surrounding PVC resin to form a network structure, and meanwhile, external shearing force is transferred to the resin, so that plasticization is promoted.
According to the invention, the heat stabilizer and the antioxidant are added at the same time, the interaction of the heat stabilizer and the antioxidant obviously improves the stability of the PVC pipe, and the discoloration and the reduction of physical and mechanical properties of the product caused by the decomposition and the release of hydrogen chloride under the excitation of heat, oxygen and the like of PVC are avoided.
Compared with the prior art, the invention has the following beneficial effects:
the high-performance PVC pipe provided by the invention takes PVC resin, chlorinated polyethylene, PA-20 processing aid, MMA/S-nano montmorillonite composite material, stabilizer, lubricant, antioxidant and filler as processing raw materials, the components are scientific in proportion and mutually coordinate, and the processing plasticizing performance of the pipe is remarkably improved, so that the pipe has good tensile strength, impact resistance, pressure resistance and thermal stability. Especially, the chlorinated polyethylene and MMA/S-nano montmorillonite composite material can generate better synergistic effect, and has important effect on improving the physical and mechanical properties of the pipe.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The components of the formulations in the following examples are, unless otherwise specified, conventional commercial products.
SG-5 type PVC resin was purchased from Duhua Yao chemical Co., Ltd; the chlorinated polyethylene is general chlorinated polyethylene CPE135 which is purchased from Huana chemical company Limited, Anhui; the PA-20 processing aid is purchased from Shanghai Kayin chemical Co., Ltd; the calcium-zinc composite heat stabilizer 518B is purchased from Macro-far Hua chemical Co., Ltd, Jiangxi; stearic acid is purchased from Shenzhen Shenkang petrochemical Co., Ltd; oxidized polyethylene wax ZG629A was purchased from Jiaxing Zhongcheng environmental protection science and technology, Inc.; bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite is available from chemical Co., Ltd, Wanbei province; octadecyl beta- (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate was purchased from Hebei Tianmen Ganchang chemical Co., Ltd; nano calcium carbonate was purchased from jiang chen xin new materials ltd. The MBS resin is MBS B561 of Japan Chongyuan, which is purchased from Hangzhou Saile chemical Co. The ACR auxiliary agent is ACR 401, and is purchased from Shandong Weifang Dongling chemical Co., Ltd.
Example 1
Preparing an MMA/S-nano montmorillonite composite material:
(1) dissolving 100g of sodium montmorillonite in water to prepare a suspension with the mass fraction of 4%, heating to 75 ℃, adding 25g of hexadecyl trimethyl ammonium bromide under the stirring state, stirring for reacting for 2 hours, standing for layering, filtering, taking a precipitate, washing the precipitate with water, drying in vacuum to constant weight, grinding and sieving to obtain organic nano montmorillonite;
(2) mixing 25g of organic nano montmorillonite with water, placing the mixture in a reactor, wherein the amount of the water is 6 times of the total volume of methyl methacrylate and styrene, heating and stirring the mixture in a water bath at 80 ℃ for reaction for 1 hour under the protection of nitrogen, cooling the mixture to 70 ℃, adding 300g of methyl methacrylate, 100g of styrene and 12g of dibenzoyl peroxide, continuing the reaction for 6 hours, then heating the mixture to 85 ℃, reacting for 2 hours, standing and layering the mixture after the reaction is finished, filtering the mixture, taking precipitate, washing the precipitate with water, and drying the precipitate in vacuum to constant weight to obtain the MMA/S-nano montmorillonite composite material.
Example 2
Preparing an MMA/S-nano montmorillonite composite material:
(1) dissolving 200g of sodium montmorillonite in water to prepare a suspension with the mass fraction of 7%, heating to 85 ℃, adding 70g of hexadecyl trimethyl ammonium bromide under the stirring state, stirring for reaction for 1 hour, standing for layering, filtering, taking a precipitate, washing the precipitate with water, drying in vacuum to constant weight, grinding and sieving to obtain organic nano montmorillonite;
(2) mixing 135g of organic nano montmorillonite with water, placing the mixture in a reactor, wherein the using amount of the water is 7 times of the total volume of methyl methacrylate and styrene, heating and stirring the mixture in a water bath at 85 ℃ for reaction for 0.5h under the protection of nitrogen, cooling the mixture to 75 ℃, adding 400g of methyl methacrylate, 100g of styrene and 20g of dibenzoyl peroxide, continuing the reaction for 4h, then heating the mixture to 90 ℃, reacting for 1h, standing and layering the mixture after the reaction is finished, filtering the mixture, taking precipitate, washing the precipitate with water, and drying the precipitate in vacuum to constant weight to obtain the MMA/S-nano montmorillonite composite material.
Example 3
Preparing an MMA/S-nano montmorillonite composite material:
(1) dissolving 100g of sodium montmorillonite in water to prepare a suspension with the mass fraction of 5%, heating to 80 ℃, adding 30g of hexadecyl trimethyl ammonium bromide under the stirring state, stirring for reaction for 1.5 hours, standing for layering, filtering, taking a precipitate, washing the precipitate with water, drying in vacuum to constant weight, grinding and sieving to obtain organic nano montmorillonite;
(2) mixing 75g of organic nano montmorillonite with water, placing the mixture in a reactor, wherein the using amount of the water is 7 times of the total volume of methyl methacrylate and styrene, heating and stirring the mixture in a water bath at 80 ℃ for reaction for 1 hour under the protection of nitrogen, cooling the mixture to 70 ℃, adding 350g of methyl methacrylate, 100g of styrene and 18g of dibenzoyl peroxide, continuing the reaction for 6 hours, then heating the mixture to 90 ℃, reacting for 1 hour, standing and layering the mixture after the reaction is finished, filtering the mixture, taking precipitate, cleaning the precipitate with water, and drying the precipitate in vacuum to constant weight to obtain the MMA/S-nano montmorillonite composite material.
Examples 4 to 9
Examples 4-9 preparation of high performance PVC plastic tubing comprises the following raw materials in parts by weight as shown in table 1:
TABLE 1
The preparation method comprises the following steps: adding all the raw materials in the formula amount into a high-speed hot mixer for mixing and dispersing, transferring all the raw materials into a cold mixer for stirring and cooling when the temperature reaches 110-120 ℃, and discharging all the raw materials into a hopper for later use when the temperature is reduced to 45-50 ℃; adding the mixed raw materials for standby in the hopper into a double-screw extruder for plasticizing, and molding by using a mold, wherein the first temperature zone of an extruder barrel is as follows: 196 ℃ below zero; the second area is as follows: 185 ℃ of temperature; the third area is: 180 ℃; the fourth area is: 175 ℃; the fifth area is: 170 ℃; the transition section temperature is: 160 ℃; the first mold temperature zone is: 165 ℃; the second area is as follows: 165 ℃; the third area is: 170 ℃; the temperature of the neck ring mold is as follows: 170 ℃; the rotating speed of the extruder is as follows: 15 r/min; the rotating speed of the feeder is as follows: 15 r/min; the head pressure is: 6 MPa; the vacuum degree of the water tank is as follows: 0.06 MPa; the traction speed is as follows: 7m/min, and preparing the heat-resistant high-impact PVC plastic pipe.
Example 10
The preparation method of the high-performance PVC plastic pipe comprises the following raw materials in parts by weight: 100 parts of SG-5 type PVC resin, 15 parts of chlorinated polyethylene, 202 parts of PA-202, 15 parts of MMA/S-nano montmorillonite composite material (prepared in example 2), 2 parts of dibutyltin maleate, 1 part of lanthanum ricinoleate, 1 part of stearic acid, 1 part of oxidized polyethylene wax, 0.5 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate and 2 parts of talcum powder.
The preparation procedure was as described above for examples 4 to 9.
Example 11
The preparation method of the high-performance PVC plastic pipe comprises the following raw materials in parts by weight: 100 parts of SG-5 type PVC resin, 15 parts of chlorinated polyethylene, 202 parts of PA-202, 15 parts of MMA/S-nano montmorillonite composite material (prepared in example 1), 3 parts of dibutyltin dilaurate, 2 parts of calcium ricinoleate, 1 part of silicone oil, 0.2 part of dioctadecyl pentaerythritol diphosphite, 0.3 part of butyl octylated diphenylamine and 3 parts of nano calcium carbonate.
The preparation procedure was as described above for examples 4 to 9.
Example 12
The preparation method of the high-performance PVC plastic pipe comprises the following raw materials in parts by weight: 100 parts of SG-5 type PVC resin, 15 parts of chlorinated polyethylene, 202 parts of PA-P, 15 parts of MMA/S-nano montmorillonite composite material (prepared in example 3), 2 parts of di-n-octyltin dilaurate, 2 parts of lanthanum laurate, 1 part of stearic acid amide, 1 part of paraffin, 2 parts of dilauryl thiodipropionate and 1 part of titanium dioxide.
The preparation procedure was as described above for examples 4 to 9.
Comparative example 1
Comparative example 1PVC plastic tubing was prepared in comparison to example 5, except that the MMA/S-nanomontmorillonite composite of the present invention was replaced with a methyl methacrylate-styrene copolymer resin. The methyl methacrylate-styrene copolymer resin is prepared by taking methyl methacrylate and styrene as functional monomers through a conventional emulsion polymerization method in the field, and specifically comprises the following steps: under the atmosphere of protective gas, sodium dodecyl sulfate is taken as an emulsifier to be dissolved in deionized water, the functional monomers with the selected weight ratio are added and mixed evenly, the temperature is raised to 55-65 ℃, sodium persulfate is added as an initiator, and the mixture is continuously stirred and reacted to obtain white emulsion; and demulsifying the emulsion, washing and drying in vacuum to obtain the required polymer. The weight ratio of methyl methacrylate to styrene in the copolymer resin was 4: 1.
The procedure for the preparation of PVC plastic tubing was as described above in examples 4-9.
Comparative example 2
Comparative example 2 preparation of PVC plastic pipe compared with example 5, except that the MMA/S-nanomontmorillonite composite of the present invention was replaced with sodium-based montmorillonite treated with a silane coupling agent. The silane coupling agent treatment steps of the montmorillonite are as follows: adding 3.6g of sodium-based montmorillonite, 5 drops of silane coupling agent KH570 and a proper amount of acetone into a beaker, heating and stirring for 0.5h, standing to volatilize the acetone, drying and sieving with a 200-mesh sieve to obtain the silane coupling agent treated sodium-based montmorillonite.
The procedure for the preparation of PVC plastic tubing was as described above in examples 4-9.
Comparative example 3
Comparative example 3PVC plastic tubing was prepared as compared to example 5, except that the MMA/S-nanomontmorillonite composite was not included.
The procedure for the preparation of PVC plastic tubing was as described above in examples 4-9.
Comparative example 4
Comparative example 4PVC plastic tubing is a conventional formulation, and its preparation comprises the following raw materials in parts by weight: 100 parts of SG-5 type PVC resin, 15 parts of MBS resin, 2 parts of dibutyl phthalate, 5 parts of ACR auxiliary agent, 4 parts of calcium-zinc composite heat stabilizer, 1 part of stearic acid, 1 part of paraffin, 10101 parts of antioxidant and 2 parts of nano calcium carbonate.
The procedure for the preparation of PVC plastic tubing was as described above in examples 4-9.
Performance detection
The following performance index tests were performed on the PVC plastic pipes prepared in examples 4-12 and comparative examples 1-4, respectively, and the results are shown in table 2, specifically:
1. and (3) detection of impact strength: the impact resistance of the pipe is evaluated by using the notch impact strength of the cantilever beam, and the method specifically comprises the following steps: the materials with the formula ratio are put into a high-speed mixer to be uniformly mixed, and then are extruded and granulated at 180 ℃. The obtained PVC granules are hot-pressed for 5min at 180 ℃ to prepare sample strips with the thickness of 80mm multiplied by 10mm multiplied by 4mm, V-shaped notches are prepared, and the notch impact strength of the cantilever beam is determined according to the national standard GB/T1843-. The temperature is adjusted to 23 ℃ according to GB/T2918-1998 Standard Environment for Conditioning and testing Plastic samples, the relative humidity is 50%, and the temperature is maintained for 48 h.
2. Detection of tensile strength: the materials with the formula ratio are put into a high-speed mixer to be uniformly mixed, and then are extruded and granulated at 180 ℃. The obtained PVC granules are hot-pressed for 5min at 180 ℃ to prepare sample strips with the thickness of 75mm multiplied by 4mm multiplied by 2mm, and the tensile strength is measured according to the national standard GB/T16421-1996 test method for small samples of plastic tensile property. The temperature is adjusted to 23 ℃ according to GB/T2918-1998 Standard Environment for Conditioning and testing Plastic samples, the relative humidity is 50%, and the temperature is maintained for 48 h.
3. Detection of Vicat softening temperature: the materials with the formula ratio are put into a high-speed mixer to be uniformly mixed, and then are extruded and granulated at 180 ℃. The obtained PVC pellets were hot-pressed at 180 ℃ for 5 minutes to prepare 10 mm. times.10 mm. times.4 mm sample pieces, and the Vicat softening temperature was measured according to the national standard GB/T1633-. The test condition is that under the action of force of 10N, the temperature rise rate is 50 ℃/h. The temperature is adjusted to 23 ℃ according to GB/T2918-1998 Standard Environment for Conditioning and testing Plastic samples, the relative humidity is 50%, and the temperature is maintained for 48 h.
4. Hydrostatic pressure test: the pressure resistance of the PVC pipe is detected according to the specification of GB/T13664-2006, and the detection conditions are as follows: the ring stress is 42MPa at 20 ℃ and 1 h.
5. And (3) detecting thermal stability: the accelerated aging of a plastic pipe sample in high-temperature oxygen at 210 ℃ is tested by adopting a differential thermal analysis method, and an oxidation induction period (OIT) (min) is taken as an index.
TABLE 2
As shown in Table 2, the PVC pipes prepared in examples 4-12 of the present invention have good impact resistance, heat resistance, pressure resistance, thermal stability and tensile strength, and the notched Izod impact strength is 14.1-16.7 KJ/m2The Vicat softening temperature is 101-109 ℃, the hydrostatic pressure test is qualified, the oxidation induction period is 250-285 min, the tensile strength is 59.8-62.4 MPa, and the performance is superior to that of the PVC pipe prepared in comparative examples 1-4. In addition, the PVC pipes prepared in the embodiments 4 to 12 of the invention have good extrusion processability, and the surfaces of the inner wall and the outer wall of the pipes are flat and bright.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. The high-performance PVC plastic pipe is characterized by comprising the following raw materials in parts by weight:
2. the high-performance PVC plastic pipe according to claim 1, wherein the MMA/S-nano montmorillonite composite material is a methyl methacrylate-styrene copolymer/organic nano montmorillonite composite material, and the organic nano montmorillonite in the composite material forms an intercalated or exfoliated structure in a methyl methacrylate-styrene copolymer matrix.
3. The high-performance PVC plastic pipe as claimed in claim 2, wherein the weight ratio of the organic nano montmorillonite in the MMA/S-nano montmorillonite composite material is 5-25%, and the weight ratio of the methyl methacrylate to the styrene in the methyl methacrylate-styrene copolymer is (3-4): 1.
4. The high-performance PVC plastic pipe as claimed in claim 2 or 3, wherein the preparation of the MMA/S-nano montmorillonite composite material comprises the following steps:
(1) dissolving sodium-based montmorillonite in water to prepare a suspension with the mass fraction of 4-7%, heating to 75-85 ℃, adding cetyl trimethyl ammonium bromide under a stirring state, stirring for reaction for 1-2 hours, standing for layering, filtering, taking a precipitate, washing the precipitate with water, drying in vacuum to constant weight, grinding and sieving to obtain organic nano montmorillonite;
(2) mixing organic nano montmorillonite with water, placing the mixture in a reactor, heating and stirring the mixture in a water bath at the temperature of 80-85 ℃ for reaction for 0.5-1 h under the protection of nitrogen, cooling the mixture to 70-75 ℃, adding methyl methacrylate, styrene and dibenzoyl peroxide, continuing the reaction for 4-6 h, then heating the mixture to 85-90 ℃, reacting for 1-2 h, standing and layering the mixture after the reaction is finished, filtering the mixture, taking precipitate, cleaning the precipitate with water, and drying the precipitate in vacuum to constant weight to obtain the MMA/S-nano montmorillonite composite material.
5. The high-performance PVC plastic pipe as claimed in claim 4, wherein the weight ratio of the cetyl trimethyl ammonium bromide to the sodium montmorillonite in the step (1) is 0.25-0.35: 1; the weight ratio of the organic nano montmorillonite to the methyl methacrylate to the styrene in the step (2) is (0.25-1.35): 3-4): 1, the addition amount of the water is 6-7 times of the total volume of the methyl methacrylate and the styrene, and the addition amount of the dibenzoyl peroxide is 3-4% of the total weight of the methyl methacrylate and the styrene.
6. The high-performance PVC plastic pipe according to claim 1, wherein the stabilizer is at least one selected from calcium-zinc composite heat stabilizer, organic tin stabilizer, rare earth stabilizer and metal soap stabilizer.
7. The high performance PVC plastic pipe according to claim 1, wherein said lubricant is at least one selected from stearic acid, stearic acid amide, paraffin wax, polyethylene wax, oxidized polyethylene wax, silicone oil, white oil.
8. The high-performance PVC plastic pipe as claimed in claim 1, wherein the antioxidant is at least one selected from phosphite antioxidants, hindered phenol antioxidants, thioester antioxidants and amine antioxidants.
9. The high-performance PVC plastic pipe according to claim 1, wherein the filler is at least one selected from nano calcium carbonate, talcum powder, titanium dioxide and wollastonite.
10. A method for preparing the high-performance PVC plastic pipe according to any one of claims 1 to 9, comprising the steps of: adding all the raw materials in the formula amount into a high-speed hot mixer for mixing and dispersing, transferring all the raw materials into a cold mixer for stirring and cooling when the temperature reaches 110-120 ℃, and discharging all the raw materials into a hopper for later use when the temperature is reduced to 45-50 ℃; and adding the mixed raw materials to be used in the hopper into a double-screw extruder for plasticizing, and molding by using a mold to obtain the high-performance PVC plastic pipe.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114656731A (en) * | 2022-04-25 | 2022-06-24 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
| CN114854144A (en) * | 2022-04-26 | 2022-08-05 | 海南联塑科技实业有限公司 | Large-diameter PVC-U pipe and preparation method thereof |
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2020
- 2020-10-17 CN CN202011113520.5A patent/CN112226018A/en active Pending
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| Title |
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| 刘云才等: "PVC/蒙脱土复合材料的制备与性能研究", 《武汉理工大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656731A (en) * | 2022-04-25 | 2022-06-24 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
| CN114656731B (en) * | 2022-04-25 | 2022-09-20 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
| CN114854144A (en) * | 2022-04-26 | 2022-08-05 | 海南联塑科技实业有限公司 | Large-diameter PVC-U pipe and preparation method thereof |
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