CN110079032B - High-strength polyvinyl chloride pipe for communication protection and preparation method thereof - Google Patents
High-strength polyvinyl chloride pipe for communication protection and preparation method thereof Download PDFInfo
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- CN110079032B CN110079032B CN201910421948.7A CN201910421948A CN110079032B CN 110079032 B CN110079032 B CN 110079032B CN 201910421948 A CN201910421948 A CN 201910421948A CN 110079032 B CN110079032 B CN 110079032B
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- polyvinyl chloride
- butadiene rubber
- styrene
- titanium dioxide
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 92
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 92
- 238000004891 communication Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000004408 titanium dioxide Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 20
- -1 2, 2-dimethylolpropionic acid modified nano titanium dioxide Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000003449 preventive effect Effects 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical group [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011361 granulated particle Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000009412 basement excavation Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of plastic pipes, and discloses a high-strength polyvinyl chloride pipe for communication protection and a preparation method thereof, wherein the high-strength polyvinyl chloride pipe comprises the following raw materials in parts by weight: 90-100 parts of polyvinyl chloride, 8-10 parts of modified nano styrene-butadiene rubber, 3-5 parts of heat stabilizer, 4-6 parts of plasticizer, 4-6 parts of impact resistant agent, 2-3 parts of flexibilizer and 0.5-0.7 part of antioxidant, wherein the modified nano styrene-butadiene rubber is nano styrene-butadiene rubber coated with modified titanium dioxide on the surface, and the preparation method is to mix uniformly; adding the mixed materials into a double-screw extruder, and performing blending granulation at the temperature of 200 ℃; and (3) extruding and molding the granulated particles at the temperature of 200 ℃ by using a single screw rod extruder at the screw rotating speed of 300r/min to obtain the polyvinyl chloride pipe. The invention can keep higher impact strength in the low-temperature environment below zero.
Description
Technical Field
The invention relates to the technical field of plastic pipes, in particular to a high-strength polyvinyl chloride pipe for communication protection and a preparation method thereof.
Background
The communication pipe network is the most important information technology industry in national economic development, and along with the continuous updating of the communication pipe network, the requirements on the quality, safety and environment of products are improved, and more plastic pipes for communication protection are transmitted in a buried and underground pipe gallery mode, so the demand for the plastic pipes for communication protection is increased. With the rapid development of the communication industry in China, plastic communication pipes are more and more adopted in the market at present, most of the communication pipes are made of PVC, PE and PP plastic materials, and polyolefin plastic pipes are high in price and are influenced by a welding process and other factors, so that the requirements for the pipes for underground pipe galleries are difficult to meet. The traditional polyvinyl chloride material is rarely used for non-excavation engineering, and the non-excavation construction is difficult to realize mainly because the polyvinyl chloride material is difficult to weld and construct and the common polyvinyl chloride pipeline has the brittleness problem.
The patent with publication number CN103275442A discloses a modified polyvinyl chloride pipe for trenchless use and a preparation method thereof, wherein the polyvinyl chloride pipe comprises the following raw materials, by weight, 90-110 parts of polyvinyl chloride; 1.0-1.5 of organic tin; 8-9 parts of a modifier; 0.5-1.2 parts of coupling agent; 0.8-1.5 of dioctyl ester; 0.2-0.8 of titanium dioxide; 0.1 to 0.5 of colorant; the preparation method of the polyvinyl chloride pipe comprises the following steps: heating and hot mixing the polyvinyl chloride resin; at 45 ℃, adding an organic tin stabilizer; adding modifier, titanium dioxide and colorant at 85 deg.C; adding dioctyl ester and coupling agent at 105 deg.C; heating and mixing to 110 deg.C, and maintaining for 10-60 s; then the mixture is cooled and mixed to 45 ℃ and discharged; the mixture enters a double-screw extruder for extrusion molding; and then, feeding the tube into a sizing box, spraying and cooling, detecting the wall thickness by ultrasonic waves, spraying and printing marks, and cutting at a fixed length to obtain a finished product tube.
According to the description of the patent application, the polyvinyl chloride pipe has the impact strength of 35MPa at 20 ℃, the tensile strength of 85MPa and the longitudinal shrinkage rate of 1.6 percent at 150 ℃. However, through further tests, the compressive strength of the polyvinyl chloride pipe is reduced to 14Mpa at the temperature of minus 10 ℃, and only reaches 9Mpa at the temperature of minus 20 ℃, so that the polyvinyl chloride pipe has poor low-temperature resistance and cannot meet the normal use of non-excavation construction at the low-temperature of minus.
In the research progress on toughening and modifying polyvinyl chloride of the journal of polyvinyl chloride, article No. 1009-7937(2004)02-0001-06, it is pointed out that in the process of preparing the low-temperature-resistant high-strength polyvinyl chloride pipe, the nano styrene-butadiene rubber has very low glass transition temperature, and can effectively improve the cold resistance of polyvinyl chloride by adding the nano styrene-butadiene rubber into the polyvinyl chloride; however, the nano styrene-butadiene rubber has extremely poor dispersibility, and is easy to agglomerate when added into polyvinyl chloride, so that the nano styrene-butadiene rubber is difficult to disperse uniformly in the polyvinyl chloride, and the non-uniform dispersion of the styrene-butadiene rubber directly causes the polyvinyl chloride pipe to have sites with low temperature resistance, and the existence of the sites with low temperature resistance directly influences the strength of the whole polyvinyl chloride pipe under the low-temperature condition.
Disclosure of Invention
In view of the above, the present invention provides a high strength polyvinyl chloride pipe for communication protection and a preparation method thereof, and the polyvinyl chloride pipe prepared by the preparation method can maintain high impact strength in a low-temperature environment below zero.
The invention solves the technical problems by the following technical means:
a high-strength polyvinyl chloride pipe for communication protection comprises, by mass, 90-100 parts of polyvinyl chloride, 8-10 parts of modified nano styrene-butadiene rubber, 3-5 parts of a heat stabilizer, 4-6 parts of a plasticizer, 4-6 parts of an impact resistant agent, 2-3 parts of a flexibilizer and 0.5-0.7 part of an antioxidant, wherein the modified nano styrene-butadiene rubber is nano styrene-butadiene rubber with the surface coated with modified titanium dioxide.
The titanium dioxide has better dispersibility in water and can be coated on the surface of the nano styrene-butadiene rubber to enhance the dispersibility of the nano styrene-butadiene rubber, but the titanium dioxide is easy to agglomerate in polymers such as polyvinyl chloride due to poor compatibility, the titanium dioxide is modified, the interaction between titanium dioxide particles and a polyvinyl chloride polymer chain is enhanced, the agglomeration among the titanium dioxide particles is reduced, the titanium dioxide particles coated with the nano styrene-butadiene rubber are promoted to be well dispersed in a polyvinyl chloride matrix, and the overall low-temperature resistance strength of the polyvinyl chloride pipe can be greatly enhanced after the styrene-butadiene rubber is uniformly dispersed in the polyvinyl chloride.
Further comprising 95 parts of polyvinyl chloride, 9 parts of modified nano styrene-butadiene rubber, 4 parts of heat stabilizer, 5 parts of plasticizer, 5 parts of impact resistant agent, 2.5 parts of flexibilizer and 0.6 part of antioxidant by mass.
Further, the modified titanium dioxide is 2, 2-dimethylolpropionic acid modified nano titanium dioxide.
Further, the polyvinyl chloride pipe also comprises 1-2 parts of a mildew preventive, and the mildew preventive is copper sulfate. The polyvinyl chloride communication pipe is buried underground, the environment is dark and humid, and the addition of the mildew preventive can prevent the polyvinyl chloride pipe from mildewing to influence the service life of the polyvinyl chloride pipe.
Further, the heat stabilizer is a barium-zinc heat stabilizer. The barium-zinc heat stabilizer has good heat stability, the barium-zinc heat stabilizer has stronger stability, the effect can be achieved by using a small amount of heat stabilizer, the barium-zinc heat stabilizer has good dispersibility and small precipitation tendency, and the barium-zinc heat stabilizer can be uniformly dispersed in a polyvinyl chloride pipe. The plasticizer is diisononyl phthalate. The diisononyl phthalate serving as the plasticizer has the advantages of low toxicity and better aging resistance. The antioxidant is [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Further, the impact resistant agent is MBS resin, and the toughening agent is chlorinated polyethylene.
Further, the preparation method of the polyvinyl chloride pipe comprises the following steps:
a1, adding 4-6 parts of plasticizer into a container according to parts by weight, heating to 60 ℃, preheating for 5 hours, adding 90-100 parts of polyvinyl chloride into the container, stirring uniformly, heating to 150 ℃, melting and mixing uniformly;
a2, adding 8-10 parts of modified nano styrene-butadiene rubber, 3-5 parts of heat stabilizer, 4-6 parts of impact resistant agent, 2-3 parts of flexibilizer, 0.5-0.7 part of antioxidant and 1-2 parts of mildew preventive into the container in the step A1, and uniformly mixing;
a3, adding the material mixed in the step A2 into a double-screw extruder, and performing blending granulation at the temperature of 200 ℃;
a4, extruding and molding the granules granulated in the step A3 at the temperature of 200 ℃ by using a single screw rod extruder at the screw rotating speed of 300r/min to obtain a polyvinyl chloride pipe;
the modified nano styrene-butadiene rubber is nano styrene-butadiene rubber coated with modified titanium dioxide on the surface.
The method comprises the steps of firstly utilizing a plasticizer to pretreat polyvinyl chloride at the temperature of 150 ℃ to improve the thermal stability of the polyvinyl chloride, then adding the modified nano styrene-butadiene rubber, a heat stabilizer, an impact resistant agent, a toughening agent, an antioxidant and a mildew preventive into the polyvinyl chloride for mixing, and granulating and extruding at the temperature of 200 ℃ to form, so that the overall pressure resistance of the polyvinyl chloride pipe can be improved.
Further, the preparation method of the modified nano styrene butadiene rubber comprises the following steps:
b1, dispersing 11 parts of nano styrene butadiene rubber in 20 parts of acetone solution according to the mass parts, performing ultrasonic dispersion for 15min, and heating to 55 ℃ in the ultrasonic dispersion process to obtain styrene butadiene rubber liquid;
b2, adding 2 parts of nano-polystyrene, 5 parts of calcium chloride solution with the mass concentration of 10%, 1 part of dibenzothiane disulfide and 1 part of diphenylguanidine into styrene butadiene rubber liquid, uniformly stirring, filtering, drying, blending for 30min under the conditions of 80 ℃ and 60r/min, standing for 24h at 25 ℃, finally vulcanizing for 20min at 160 ℃ and 15MPa, and placing in a ball milling kettle for ball milling to obtain the polystyrene filled styrene butadiene rubber composite material; the nano polystyrene is filled in the styrene butadiene rubber to enhance the strength of the styrene butadiene rubber.
B3, adding 10 parts of acetylacetone, 2 parts of sodium stearate and 1 part of sodium alginate into a container, stirring for 15min, heating to 90 ℃, adding 9 parts of butyl titanate, and continuously stirring for reacting for 2h to obtain titanium dioxide solution;
b4, adding 10 parts of 2, 2-dimethylolpropionic acid into the titanium dioxide solution obtained in the step B3 under the protection of nitrogen, ultrasonically dispersing for 1h, heating to 65 ℃, reacting for 20h under the ultrasonic dispersion, centrifuging, filtering, dissolving the separated particles into 30 parts of ethanol solution, centrifuging again, filtering, drying, and ball-milling in a ball-milling kettle to obtain 2, 2-dimethylolpropionic acid modified nano titanium dioxide;
b5, mixing the composite material obtained in the step B2 with the 2, 2-dimethylolpropionic acid modified nano titanium dioxide obtained in the step B4, adding acetone to submerge the composite material and the 2, 2-dimethylolpropionic acid modified nano titanium dioxide, performing ultrasonic dispersion reaction for 2 hours, filtering and drying to obtain the modified nano styrene-butadiene rubber.
Hydrolyzing butyl titanate under the action of acetylacetone to generate titanium dioxide particles, modifying the surface of titanium dioxide by using 2, 2-dimethylolpropionic acid, condensing titanium dioxide and the 2, 2-dimethylolpropionic acid containing-C00H functional groups, enhancing the interaction between titanium dioxide particles and polymer chains, reducing the agglomeration among the particles, and promoting the titanium dioxide particles coated with nano styrene-butadiene rubber to be well dispersed in a polyvinyl chloride matrix; under the activation action of sodium stearate and sodium alginate, the modified titanium dioxide particles are coated on the partial surface of the styrene butadiene rubber, and finally, the modified styrene butadiene rubber particles coated with the titanium dioxide are obtained through the steps of filtering, drying, crushing and the like, the modified titanium dioxide has good dispersibility in polyvinyl chloride, and the agglomeration phenomenon of the styrene butadiene rubber in the polyvinyl chloride can be avoided, so that the styrene butadiene rubber can be uniformly and stably dispersed in the polyvinyl chloride, the prepared polyvinyl chloride pipe has better overall low temperature resistance, and the condition that the polyvinyl chloride pipe is integrally scrapped due to poor low temperature resistance of the point position of the polyvinyl chloride pipe can be avoided.
The invention has the beneficial effects that:
(1) according to the invention, the performance of the polyvinyl chloride pipe is improved by adding the heat stabilizer, the plasticizer, the impact resistant agent, the flexibilizer, the antioxidant and the like into polyvinyl chloride, the low temperature resistance of the polyvinyl chloride pipe is improved by adding the nano styrene-butadiene rubber with the surface coated with the modified titanium dioxide, the modified titanium dioxide has good dispersibility in the polyvinyl chloride, the agglomeration phenomenon of the styrene-butadiene rubber in the polyvinyl chloride can be avoided, the styrene-butadiene rubber can be uniformly and stably dispersed in the polyvinyl chloride, and the overall low temperature resistance of the prepared polyvinyl chloride pipe can reach-25 ℃;
(2) the invention utilizes tetrabutyl titanate to hydrolyze under the action of acetylacetone to generate titanium dioxide particles, modifies the surface of titanium dioxide by 2, 2-dimethylolpropionic acid, condenses titanium dioxide and the 2, 2-dimethylolpropionic acid containing-C00H functional group, enhances the interaction between titanium dioxide particles and polymer, reduces the agglomeration among particles, promotes the titanium dioxide particles coated with nano styrene-butadiene rubber to be well dispersed in a polyvinyl chloride matrix, coats the modified titanium dioxide particles on the partial surface of the styrene-butadiene rubber under the activation action of sodium stearate and sodium alginate, and finally obtains the styrene-butadiene rubber particles coated with modified titanium dioxide through the steps of filtering, drying, crushing and the like, the operation of the whole preparation process is simple, the obtained modified styrene-butadiene rubber particles have strong dispersibility, can be uniformly dispersed in polyvinyl chloride.
Detailed Description
Example 1
The preparation of the modified nano styrene-butadiene rubber is carried out, and the preparation process comprises the following steps:
b1, firstly, taking 11kg of nano styrene-butadiene rubber with the particle size of 50-80nm, pouring and dispersing the nano styrene-butadiene rubber into 20kg of 99% acetone solution with the mass concentration, ultrasonically dispersing for 15min by using 25000HZ ultrasonic waves, and heating to 55 ℃ in the ultrasonic dispersion process to obtain styrene-butadiene rubber liquid;
b2, adding 2kg of nano-polystyrene, 5kg of calcium chloride solution with the mass concentration of 10%, 1kg of dibenzothia disulfide and 1kg of diphenylguanidine into styrene butadiene rubber liquid, uniformly stirring, filtering, drying, blending for 30min under the conditions of 80 ℃ and 60r/min, standing for 24h at 25 ℃, finally vulcanizing for 20min under the pressure of 160 ℃ and 15MPa, and placing in a ball milling kettle for ball milling to obtain the polystyrene filled styrene butadiene rubber composite material;
b3, adding 10kg of acetylacetone with 99% mass concentration, 2kg of sodium stearate and 1kg of sodium alginate into a container, stirring for 15min at a rotating speed of about 100r/min by using a stirrer, heating to 90 ℃ after stirring, adding 9kg of butyl titanate into the container again at the moment, and stirring and reacting for 2h at a rotating speed of about 100r/min by using the stirrer to obtain titanium dioxide liquid;
b4, under the protection of nitrogen, adding 10kg of 2, 2-dimethylolpropionic acid into the titanium dioxide solution, ultrasonically dispersing for 1h by using 25000HZ ultrasonic waves, heating to 65 ℃, reacting for 20h under the ultrasonic dispersion of 25000HZ ultrasonic waves, centrifuging, filtering, dissolving the separated particles into 30kg of ethanol solution, centrifuging again, filtering, drying, and ball-milling in a ball-milling kettle to obtain 2, 2-dimethylolpropionic acid modified nano titanium dioxide;
b5, mixing the composite material obtained in the step B2 and the 2, 2-dimethylolpropionic acid modified nano titanium dioxide obtained in the step B4, adding the mixture into an acetone solution with the mass concentration of 99% to submerge the composite material and the 2, 2-dimethylolpropionic acid modified nano titanium dioxide, performing ultrasonic dispersion reaction for 2 hours by using 25000HZ, filtering and drying to obtain the modified nano styrene-butadiene rubber.
Example 2
Preparing a polyvinyl chloride pipe by the following steps:
adding 4kg of diisononyl phthalate into a container, heating to 60 ℃, preheating for 5 hours, adding 90kg of polyvinyl chloride into the container, uniformly stirring, heating to 150 ℃, and uniformly melting and mixing;
weighing 8kg of the modified nano styrene-butadiene rubber prepared in the example 1, 3kg of barium-zinc heat stabilizer, 4kg of MBS resin, 2kg of chlorinated polyethylene, 0.5kg of [ beta- (3, 5-di-90 tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1kg of copper sulfate, adding into a container, stirring at a rotating speed of 60r/min for about 15min, and uniformly mixing;
then adding the mixed materials into a double-screw extruder, and carrying out blending granulation at the temperature of 200 ℃;
and finally, extruding and molding the granulated particles at the temperature of 200 ℃ by using a single screw rod extruder at the screw rotating speed of 300r/min to prepare the polyvinyl chloride pipe with the pipe diameter of 15cm and the wall thickness of 5 mm.
Example 3 to example 6
Examples 3-6 are compared with example 2, differing only in that the mixing of the mixed materials is carried out according to the respective proportions in the table below. The following table specifically shows:
example 7 (comparative example)
The polyvinyl chloride pipe comprises the following raw materials (Kg):
polyvinyl chloride: 100, organotin: 1.2, methacrylic acid-butadiene-styrene copolymer: 8.4, silane: 0.9, dioctyl ester: 1.2, titanium dioxide: 0.4, 0.2 carbon black.
The preparation method comprises the following steps:
(1) firstly, heating and hot mixing polyvinyl chloride resin;
(2) when the temperature is raised to 45 ℃, adding the organic tin stabilizer, and continuing hot mixing;
(3) when the temperature is raised to 85 ℃, adding the modifier, the titanium dioxide and the colorant, and continuing hot mixing;
(4) when the temperature is raised to 105 ℃, adding dioctyl ester and a coupling agent, and continuing to carry out hot mixing;
(5) heating and mixing to 110 deg.C, and maintaining for 30 s;
(6) then cooling and cold mixing to 45 ℃ and discharging;
(7) and (3) feeding the mixture into a double-screw extruder for extrusion molding, wherein the current of a main machine of the double-screw extruder is 70A and 18 revolutions, the rotation of a feeding motor is 70 revolutions, the pressure of a mold cavity is 25MPa, and the torque of a melt is 60%. The temperature of the hot zone 1-6 is 198 deg.C, 196 deg.C, 190 deg.C, 185 deg.C, 180 deg.C. The temperature of the 1-5 area of the machine head die is 175 ℃, 180 ℃, 185 ℃, 190 ℃, 210 ℃, the temperature of the screw is 120 ℃, and the temperature in the core rod is cut off after being heated to 165 ℃;
(8) then the tube blank is put into a sizing box with the tube diameter of 15cm and the wall thickness of 5mm to form a tube blank, and then the tube blank is sprayed and cooled, the wall thickness is detected by ultrasonic waves, marks are sprayed and printed, and the tube blank is cut at fixed length to obtain a finished product of the tube.
Physical properties of the polyvinyl chloride pipes produced in examples 2 to 7 were measured, and specific measurement data are shown in the following table:
from the physical property test data of the polyvinyl chloride pipe obtained in the above example, it can be seen that:
1. from the comparison of examples 2-4 with example 7, it can be seen that the impact strength of the polyvinyl chloride pipes prepared in examples 2-4 is greater than that of example 7 at all temperature conditions, and that the polyvinyl chloride pipes prepared in examples 2-4 also have good impact strength at low temperatures of-20 ℃;
2. from the comparison of examples 2 to 4, it can be seen that the impact strength of the prepared polyvinyl chloride pipe is the maximum by using the mixture ratio of the components in example 3, and the impact strength is more than 8 times that of the common polyvinyl chloride pipe;
3. from the comparison between example 2 and example 5, it can be seen that the compressive strength of the polyvinyl chloride pipe can be obviously increased by adding the modified nano styrene-butadiene rubber prepared in example 1 into the formula of the polyvinyl chloride pipe;
4. from the comparison between example 2 and example 6, it can be seen that the use of copper sulfate as an antibacterial agent in example 2 can significantly increase the antibacterial performance of the polyvinyl chloride pipe and prolong the service life of the underground communication pipe.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (6)
1. The utility model provides a communication protection is with high strength polyvinyl chloride pipe which characterized in that: the modified nano styrene-butadiene rubber is prepared from 90-100 parts of polyvinyl chloride, 8-10 parts of modified nano styrene-butadiene rubber, 3-5 parts of heat stabilizer, 4-6 parts of plasticizer, 4-6 parts of impact resistant agent, 2-3 parts of toughening agent and 0.5-0.7 part of antioxidant by mass, wherein the surface of the modified nano styrene-butadiene rubber is coated with modified titanium dioxide; the modified titanium dioxide is 2, 2-dimethylolpropionic acid modified nano titanium dioxide; the preparation method of the modified nano styrene-butadiene rubber comprises the following steps:
b1, adding 11 parts by mass of nano styrene-butadiene rubber into 20 parts by mass of acetone solution, carrying out ultrasonic dispersion for 15min, and heating to 55 ℃ in the ultrasonic dispersion process to obtain styrene-butadiene rubber liquid;
b2, adding 2 parts of nano-polystyrene, 5 parts of calcium chloride solution with the mass concentration of 10%, 1 part of dibenzothiane disulfide and 1 part of diphenylguanidine into styrene butadiene rubber liquid, uniformly stirring, filtering, drying, blending for 30min under the conditions of 80 ℃ and 60r/min, standing for 24h at 25 ℃, finally vulcanizing for 20min at 160 ℃ and 15MPa, and placing in a ball milling kettle for ball milling to obtain the polystyrene filled styrene butadiene rubber composite material;
b3, adding 10 parts of acetylacetone, 2 parts of sodium stearate and 1 part of sodium alginate into a container, stirring for 15min, heating to 90 ℃, adding 9 parts of butyl titanate, and continuously stirring for reacting for 2h to obtain titanium dioxide solution;
b4, adding 10 parts of 2, 2-dimethylolpropionic acid into the titanium dioxide solution obtained in the step B3 under the protection of nitrogen, ultrasonically dispersing for 1h, heating to 65 ℃, reacting for 20h under the ultrasonic dispersion, centrifuging, filtering, dissolving the separated particles into 30 parts of ethanol solution, centrifuging again, filtering, drying, and ball-milling in a ball-milling kettle to obtain 2, 2-dimethylolpropionic acid modified nano titanium dioxide;
b5, mixing the composite material obtained in the step B2 with the 2, 2-dimethylolpropionic acid modified nano titanium dioxide obtained in the step B4, adding acetone to submerge the composite material and the 2, 2-dimethylolpropionic acid modified nano titanium dioxide, performing ultrasonic dispersion reaction for 2 hours, filtering and drying to obtain the modified nano styrene-butadiene rubber.
2. The high-strength polyvinyl chloride pipe for communication protection as claimed in claim 1, wherein: according to the mass portion, the material comprises 95 portions of polyvinyl chloride, 9 portions of modified nano styrene-butadiene rubber, 4 portions of heat stabilizer, 5 portions of plasticizer, 5 portions of impact resistant agent, 2.5 portions of flexibilizer and 0.6 portion of antioxidant.
3. The high-strength polyvinyl chloride pipe for communication protection as claimed in claim 2, wherein: the polyvinyl chloride pipe also comprises 1-2 parts of a mildew preventive, and the mildew preventive is copper sulfate.
4. The high-strength polyvinyl chloride pipe for communication protection as claimed in claim 3, wherein: the heat stabilizer is a barium-zinc heat stabilizer, the plasticizer is diisononyl phthalate, and the antioxidant is [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
5. The high-strength polyvinyl chloride pipe for communication protection as claimed in claim 4, wherein: the impact resistant agent is MBS resin, and the toughening agent is chlorinated polyethylene.
6. A preparation method of a high-strength polyvinyl chloride pipe for communication protection is characterized by comprising the following steps: a1, adding 4-6 parts of plasticizer into a container according to parts by weight, heating to 60 ℃, preheating for 5 hours, adding 90-100 parts of polyvinyl chloride into the container, uniformly stirring, heating to 150 ℃, and melting and uniformly mixing;
a2, adding 8-10 parts of modified nano styrene-butadiene rubber, 3-5 parts of heat stabilizer, 4-6 parts of impact resistant agent, 2-3 parts of flexibilizer, 0.5-0.7 part of antioxidant and 1-2 parts of mildew preventive into the container in the step A1, and uniformly mixing;
a3, adding the material mixed in the step A2 into a double-screw extruder, and performing blending granulation at the temperature of 200 ℃;
a4, extruding and molding the granules granulated in the step A3 at the temperature of 200 ℃ by using a single screw rod extruder at the screw rotating speed of 300r/min to obtain a polyvinyl chloride pipe; the modified nano styrene-butadiene rubber is nano styrene-butadiene rubber coated with modified titanium dioxide on the surface.
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| CN106519358A (en) * | 2016-11-25 | 2017-03-22 | 陕西品达石化有限公司 | Preparation method for polystyrene-filled styrene butadiene rubber composite |
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Denomination of invention: A high-strength polyvinyl chloride pipe for communication protection and its preparation method Granted publication date: 20210309 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Hangzhou Fuyang sub branch Pledgor: HANGZHOU UNICOM. PIPING INDUSTRY Co.,Ltd. Registration number: Y2024980038171 |