CN116675941B - Method for preparing chlorinated polyvinyl chloride by acid phase suspension method - Google Patents
Method for preparing chlorinated polyvinyl chloride by acid phase suspension method Download PDFInfo
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- CN116675941B CN116675941B CN202310967123.1A CN202310967123A CN116675941B CN 116675941 B CN116675941 B CN 116675941B CN 202310967123 A CN202310967123 A CN 202310967123A CN 116675941 B CN116675941 B CN 116675941B
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- polyvinyl chloride
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- chlorine
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- 239000004801 Chlorinated PVC Substances 0.000 title claims abstract description 60
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000725 suspension Substances 0.000 title claims abstract description 34
- 239000002253 acid Substances 0.000 title abstract description 12
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 86
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 85
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000460 chlorine Substances 0.000 claims abstract description 68
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 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 abstract description 11
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000661 sodium alginate Substances 0.000 claims abstract description 11
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 11
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims abstract 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000005977 Ethylene Substances 0.000 claims abstract 2
- 229940037312 stearamide Drugs 0.000 claims abstract 2
- 238000005660 chlorination reaction Methods 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 21
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 15
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 10
- 229930195725 Mannitol Natural products 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- 239000000594 mannitol Substances 0.000 claims description 10
- 235000010355 mannitol Nutrition 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 9
- 229920002545 silicone oil Polymers 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940083037 simethicone Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- -1 chloroform-activated carbon tetrachloride Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229940033134 talc Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RXPRRQLKFXBCSJ-GIVPXCGWSA-N vincamine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C[C@](O)(C(=O)OC)N5C2=C1 RXPRRQLKFXBCSJ-GIVPXCGWSA-N 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
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for preparing chlorinated polyvinyl chloride by an acid phase suspension method, which comprises the steps of modifying polyvinyl chloride, preparing modified polyvinyl chloride suspension, chloridizing, post-treating, deacidifying, neutralizing, centrifuging and drying; the post-treatment step comprises the steps of mixing chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene-based bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.08-0.12MPa, controlling the heating temperature of the nitrogen to 78-82 ℃, preserving heat and pressure for 30-40min, and rapidly releasing pressure to normal pressure within 0.2-0.4s after the heat preservation and pressure maintaining are finished, thus obtaining the chlorinated polyvinyl chloride slurry. The chlorine content of the chlorinated polyvinyl chloride prepared by the method is up to 72.4-72.8%, and the prepared chlorinated polyvinyl chloride sample has excellent mechanical property and stability.
Description
Technical Field
The invention belongs to the technical field of chlorinated polyvinyl chloride preparation, and particularly relates to a method for preparing chlorinated polyvinyl chloride by an acid phase suspension method.
Background
Chlorinated polyvinyl chloride (CPVC) is a product of further chloridizing and modifying polyvinyl chloride (PVC), is a novel engineering plastic, has corrosion resistance, heat resistance, solubility, flame retardance and the like which are greatly improved compared with the polyvinyl chloride besides a plurality of excellent performances of the polyvinyl chloride, is widely applied to the fields of construction, chemical industry, metallurgy, electrical appliances, textile and the like, and has very broad application prospect.
The preparation method of the chlorinated polyvinyl chloride comprises a solvent method, a suspension method and a gas-solid phase method;
the solvent method is the earliest method for preparing chlorinated polyvinyl chloride, and the main technical process is to dissolve polyvinyl chloride resin in chloroform-activated carbon tetrachloride solvent and then to carry out chlorination; the solvent method has uniform chlorination, the product has better dissolution performance, but the prepared product has poor mechanical performance and thermal stability, and organic solvents such as chloroform or carbon tetrachloride have high toxicity, are difficult to recover and cause larger pollution to the environment;
the gas-solid phase method is to put PVC resin into a reaction kettle or a fluidized bed in a dry state at normal pressure to directly carry out chlorination reaction; the gas-solid phase method has light environmental pollution and is easy to be continuous, but has the defects of uneven chlorination and the like, thereby limiting the industrialization of the process;
the acid phase suspension method is to suspend powdery chlorinated polyethylene resin in hydrogen chloride solution and to lead chlorine to react in the presence of auxiliary agent; the method has simple process, and the prepared product has better mechanical property and is a production method commonly adopted at home and abroad;
however, the chlorinated polyvinyl chloride product prepared by the acid phase suspension method in the prior art has low chlorine content, materials are easy to agglomerate due to bonding in the reaction process of an acid phase system, the mechanical property is low and unstable, the mechanical property is greatly reduced after high temperature and ultraviolet irradiation, and the mechanical property retention rate is low;
from the above, the following problems exist in the prior art that the acid phase suspension method is adopted to prepare the chlorinated polyvinyl chloride:
1. the chlorinated polyvinyl chloride has low chlorine content;
2. the mechanical properties are low and unstable, the mechanical properties are greatly reduced after high temperature and ultraviolet irradiation, and the retention rate of the mechanical properties is low.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing chlorinated polyvinyl chloride by an acid phase suspension method, which improves the chlorine content of the product, enhances the thermal stability of the product and improves the retention rate of the mechanical properties of the product after high temperature and ultraviolet irradiation.
In order to solve the technical problems, the invention adopts the following technical scheme:
1. modified polyvinyl chloride
(1) Pretreatment of
Performing plasma ball milling treatment on polyvinyl chloride powder in nitrogen gas for 54-56min at 365-375rpm, wherein the discharge current is 88-92mA, the discharge voltage is 24-28kV, the discharge frequency is 36-40kHz, and the pretreated polyvinyl chloride is obtained after the plasma ball milling treatment is finished;
the polyvinyl chloride powder has the particle size of 115-125 mu m and the apparent density of 0.57-0.59g/ml;
(2) Modification
Mixing the pretreated polyvinyl chloride with gelatin, mannitol and a modifier, performing ultraviolet-ultrasonic treatment, controlling the central wavelength of an ultraviolet lamp in the ultraviolet-ultrasonic treatment to be 310-330nm, the power of the ultraviolet lamp to be 220-240W, and the power of ultrasonic waves to be 360-380W, and drying to obtain modified polyvinyl chloride;
the modifier is a mixture of carboxymethyl cellulose, polyethylene glycol, pentaerythritol, sodium dodecyl benzene sulfonate and deionized water, and the mass ratio of the deionized water to the carboxymethyl cellulose to the polyethylene glycol to the pentaerythritol to the sodium dodecyl benzene sulfonate is 82-90:2.8-3.1:1.7-2.2:2.4-2.6:1.3-1.7;
the mass ratio of the pretreated polyvinyl chloride, gelatin, mannitol and modifier is 120-140:1.7-2.2:1.4-1.6:4.3-4.6.
2. Preparation of modified polyvinyl chloride suspension
(1) Preparation auxiliary agent
Mixing sodium dodecyl benzene sulfonate, talcum powder, dimethyl silicone oil, polyvinylpyrrolidone and fatty alcohol polyoxyethylene ether, placing the mixture in 72-77 ℃ for heat treatment for 23-28min, and naturally cooling to room temperature to obtain an auxiliary agent;
the mass ratio of the sodium dodecyl benzene sulfonate to the talcum powder to the dimethyl silicone oil to the polyvinylpyrrolidone to the fatty alcohol-polyoxyethylene ether is 1.1-1.3:0.3-0.5:0.5-0.7:0.4-0.6:0.3-0.6;
(2) Mixing
Adding a hydrochloric acid solution, an auxiliary agent and azodiisobutyronitrile into modified polyvinyl chloride, controlling the stirring speed to be 115-123rpm, then precooling at 3.8-4.2 ℃ for 18-22min, freezing after precooling is finished for 35-45min, and heating to room temperature at a speed of 0.4-0.6 ℃/min after freezing is finished at-13 to-10 ℃ to prepare modified polyvinyl chloride suspension;
the mass concentration of the hydrochloric acid solution is 16-18%;
the mass ratio of the modified polyvinyl chloride to the hydrochloric acid solution is 1:7-9;
the mass ratio of the modified polyvinyl chloride to the auxiliary agent to the azodiisobutyronitrile is 100:2.6-3.2:0.14-0.16.
3. Chlorination
Adding the modified polyvinyl chloride suspension into a chlorination kettle, introducing nitrogen for 28-32min, and discharging oxygen in the chlorination kettle;
the mass ratio of the total chlorine to the modified polyvinyl chloride is 0.9-1.1:1, a step of;
(1) First stage chlorination
Raising the temperature in the kettle to 75-77 ℃, starting chlorine introduction, controlling the chlorine introduction speed to be 1.8-2.1kg/min, and controlling the pressure in the kettle to be 0.11-0.13MPa;
the first stage of chlorination, wherein the chlorine introducing amount is 25-36% of the total chlorine introducing amount;
(2) Second stage chlorination
Controlling the temperature rising rate to be 0.07-0.12 ℃/min, rising the temperature to be 94-96 ℃, continuing to introduce chlorine, controlling the chlorine introducing speed to be 3.8-4.2kg/min, and controlling the pressure in the kettle to be 0.17-0.19MPa;
the second stage of chlorination, wherein the chlorine introducing amount is 38-43% of the total chlorine introducing amount;
(3) Third stage of chlorination
Heating to 101-103 deg.c at a heating rate of 0.18-0.22 deg.c/min and chlorine introducing speed of 4-6kg/min, controlling the pressure inside the kettle to 0.15-0.23MPa, and final stage chlorination to obtain primary chlorinated polyvinyl chloride slurry;
the third stage of chlorination, the chlorine introducing amount is 26-32% of the total chlorine introducing amount.
4. Post-treatment
Mixing the chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.08-0.12MPa, controlling the heating temperature of the nitrogen to 78-82 ℃, preserving heat and pressure for 30-40min, and rapidly releasing pressure to normal pressure within 0.2-0.4s after the heat preservation and pressure maintaining are finished to prepare the chlorinated polyvinyl chloride slurry;
the mass ratio of the chlorinated polyvinyl chloride primary slurry to the 2, 6-tertiary butyl-4-methylphenol to the sodium alginate to the ethylene bis stearamide is 130:0.5-0.7:0.4-0.6:0.3-0.5.
5. Deacidifying, neutralizing, centrifuging, and drying
And deacidifying, neutralizing, centrifugally dewatering and drying the chlorinated polyvinyl chloride slurry to obtain the chlorinated polyvinyl chloride.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the polyvinyl chloride is modified, and the modified polyvinyl chloride suspension is prepared, so that the internal structure of the polyvinyl chloride is more uniform, the uniformity of chlorination is improved, and the mechanical property and stability of the chlorinated polyvinyl chloride product are excellent;
2. the chlorine content of the chlorinated polyvinyl chloride prepared by the invention is 72.4-72.8 percent (GB/T7139-2002);
3. the chlorinated polyvinyl chloride product prepared by the invention is used for producing a chlorinated polyvinyl chloride sample, the tensile strength of the chlorinated polyvinyl chloride sample is 102.9-106.7MPa (GB/T1040.2-2006), and the impact strength of a simply supported beam is 40.7-43.6KJ/m 2 (GB/T1043.1-2008) with flexural strength of 152.8-154.6MPa (GB/T9341-2008);
standing at 80deg.C for 10d, and has tensile strength of 99.7-104.67MPa and impact strength of 38.9-42.1KJ/m 2 The bending strength is 148.2-150.9MPa;
at a strength of 600W/m 2 The tensile strength is 98.8-103.6MPa, and the impact strength of the simple beam is 38.6-41.9KJ/m after 10d of irradiation under ultraviolet light 2 The bending strength is 147.3-150.3MPa;
standing for 10 days at 40% mass concentration, and having tensile strength of 97.8-102.8MPa and impact strength of 38.2-41.3KJ/m 2 The bending strength is 142.1-146.9MPa.
Detailed Description
For a clearer understanding of the technical features, objects and effects of the present invention, specific embodiments of the present invention will be described.
Example 1 method for preparing chlorinated polyvinyl chloride by acid phase suspension method
1. Modified polyvinyl chloride
(1) Pretreatment of
Performing plasma ball milling treatment on polyvinyl chloride powder in nitrogen gas for 55min at a ball milling rotating speed of 370rpm, a discharge current of 90mA, a discharge voltage of 26kV and a discharge frequency of 38kHz, and obtaining pretreated polyvinyl chloride after the plasma ball milling treatment is finished;
the particle size of the polyvinyl chloride powder is 120 mu m, and the apparent density is 0.58g/ml;
(2) Modification
Mixing the pretreated polyvinyl chloride with gelatin, mannitol and a modifier, then performing ultraviolet-ultrasonic treatment, controlling the central wavelength of an ultraviolet lamp in the ultraviolet-ultrasonic treatment to be 320nm, the power of the ultraviolet lamp to be 230W, and the power of ultrasonic waves to be 370W, and drying to obtain modified polyvinyl chloride;
the modifier is a mixture of carboxymethyl cellulose, polyethylene glycol, pentaerythritol, sodium dodecyl benzene sulfonate and deionized water, and the mass ratio of the deionized water to the carboxymethyl cellulose to the polyethylene glycol to the pentaerythritol to the sodium dodecyl benzene sulfonate is 85:3:2:2.5:1.5;
the mass ratio of the pretreated polyvinyl chloride, gelatin, mannitol and the modifier is 130:2:1.5:4.5.
2. Preparation of modified polyvinyl chloride suspension
(1) Preparation auxiliary agent
Mixing sodium dodecyl benzene sulfonate, talcum powder, dimethyl silicone oil, polyvinylpyrrolidone and fatty alcohol polyoxyethylene ether, placing the mixture at 75 ℃ for heat treatment for 25min, and naturally cooling the mixture to room temperature to obtain an auxiliary agent;
the mass ratio of the sodium dodecyl benzene sulfonate to the talcum powder to the dimethyl silicone oil to the polyvinylpyrrolidone to the fatty alcohol-polyoxyethylene ether is 1.2:0.4:0.6:0.5:0.5;
(2) Mixing
Adding a hydrochloric acid solution, an auxiliary agent and azodiisobutyronitrile into the modified polyvinyl chloride, controlling the stirring speed to be 120rpm, then precooling, wherein the precooling temperature is 4 ℃, the precooling time is 20min, freezing treatment is carried out after precooling is finished, the freezing time is 40min, the freezing temperature is-12 ℃, and the temperature is raised to room temperature at a speed of 0.5 ℃/min after the freezing is finished, so as to prepare a modified polyvinyl chloride suspension;
the mass concentration of the hydrochloric acid solution is 17%;
the mass ratio of the modified polyvinyl chloride to the hydrochloric acid solution is 1:8, 8;
the mass ratio of the modified polyvinyl chloride to the auxiliary agent to the azodiisobutyronitrile is 100:3:0.15.
3. Chlorination
Adding the modified polyvinyl chloride suspension into a chlorination kettle, introducing nitrogen for 30min, and discharging oxygen in the chlorination kettle;
the mass ratio of the total chlorine amount to the modified chlorinated polyvinyl chloride is 1:1, a step of;
(1) First stage chlorination
Raising the temperature in the kettle to 76 ℃, starting chlorine introduction, controlling the chlorine introduction speed to be 2kg/min, and controlling the pressure in the kettle to be 0.12MPa;
the first stage of chlorination, wherein the chlorine introducing amount is 30% of the total chlorine introducing amount;
(2) Second stage chlorination
The temperature rising rate is controlled to be 0.1 ℃/min, the temperature is raised to 95 ℃, the chlorine is continuously introduced, the chlorine introducing speed is controlled to be 4kg/min, and the pressure in the kettle is controlled to be 0.18MPa;
the second stage of chlorination, wherein the chlorine introducing amount is 40% of the total chlorine introducing amount;
(3) Third stage of chlorination
Controlling the heating rate to be 0.2 ℃/min, heating to 102 ℃, continuing to introduce chlorine, controlling the pressure in the kettle to be 0.20MPa, and after the third stage chlorination is completed, preparing chlorinated polyvinyl chloride primary slurry;
and the third stage of chlorination, wherein the chlorine flux is 30% of the total chlorine flux.
4. Post-treatment
Mixing the chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.1MPa, controlling the heating temperature of the nitrogen to 80 ℃, preserving heat and pressure for 35min, and rapidly releasing pressure to normal pressure within 0.3s after the heat preservation and pressure maintaining are finished to prepare the chlorinated polyvinyl chloride slurry;
the mass ratio of the chlorinated polyvinyl chloride primary slurry to the 2, 6-tertiary butyl-4-methylphenol to the sodium alginate to the ethylene bis stearamide is 130:0.6:0.5:0.4.
5. Deacidifying, neutralizing, centrifuging, and drying
And deacidifying, neutralizing, centrifugally dewatering and drying the chlorinated polyvinyl chloride slurry to obtain the chlorinated polyvinyl chloride.
Example 2 method for preparing chlorinated polyvinyl chloride by acid phase suspension method
1. Modified polyvinyl chloride
(1) Pretreatment of
Performing plasma ball milling treatment on polyvinyl chloride powder in nitrogen gas for 54min at 365rpm, discharging current of 88mA, discharging voltage of 24kV and discharging frequency of 36kHz to obtain pretreated polyvinyl chloride after the plasma ball milling treatment is finished;
the polyvinyl chloride powder has a particle size of 115 mu m and an apparent density of 0.57g/ml;
(2) Modification
Mixing the pretreated polyvinyl chloride with gelatin, mannitol and a modifier, then performing ultraviolet-ultrasonic treatment, controlling the central wavelength of an ultraviolet lamp in the ultraviolet-ultrasonic treatment to be 310nm, controlling the power of the ultraviolet lamp to be 240W, controlling the ultrasonic power to be 360W, and drying to obtain modified polyvinyl chloride;
the modifier is a mixture of carboxymethyl cellulose, polyethylene glycol, pentaerythritol, sodium dodecyl benzene sulfonate and deionized water, and the mass ratio of the deionized water to the carboxymethyl cellulose to the polyethylene glycol to the pentaerythritol to the sodium dodecyl benzene sulfonate is 82:2.8:1.7:2.4:1.3;
the mass ratio of the pretreated polyvinyl chloride, gelatin, mannitol and the modifier is 120:1.7:1.4:4.3.
2. Preparation of modified polyvinyl chloride suspension
(1) Preparation auxiliary agent
Mixing sodium dodecyl benzene sulfonate, talcum powder, dimethyl silicone oil, polyvinylpyrrolidone and fatty alcohol polyoxyethylene ether, placing the mixture at 72 ℃ for heat treatment for 23min, and naturally cooling the mixture to room temperature to obtain an auxiliary agent;
the mass ratio of the sodium dodecyl benzene sulfonate to the talcum powder to the dimethyl silicone oil to the polyvinylpyrrolidone to the fatty alcohol-polyoxyethylene ether is 1.1:0.3:0.5:0.4:0.3;
(2) Mixing
Adding a hydrochloric acid solution, an auxiliary agent and azodiisobutyronitrile into the modified polyvinyl chloride, controlling the stirring speed to be 115rpm, then precooling at 3.8 ℃ for 18min, freezing after precooling is finished for 45min, and heating to room temperature at a speed of 0.4 ℃/min after freezing is finished to obtain a modified polyvinyl chloride suspension;
the mass concentration of the hydrochloric acid solution is 16%;
the mass ratio of the modified polyvinyl chloride to the hydrochloric acid solution is 1:7, preparing a base material;
the mass ratio of the modified polyvinyl chloride to the auxiliary agent to the azodiisobutyronitrile is 100:2.6:0.14.
3. Chlorination
Adding the modified polyvinyl chloride suspension into a chlorination kettle, introducing nitrogen for 28min, and discharging oxygen in the chlorination kettle;
the mass ratio of the total chlorine to the modified polyvinyl chloride is 0.9:1, a step of;
(1) First stage chlorination
Raising the temperature in the kettle to 75 ℃, starting chlorine introduction, controlling the chlorine introduction speed to be 1.8kg/min, and controlling the pressure in the kettle to be 0.11MPa;
the first stage of chlorination, wherein the chlorine introducing amount is 25% of the total chlorine introducing amount;
(2) Second stage chlorination
The temperature rising rate is controlled to be 0.07 ℃/min, the temperature is raised to 94 ℃, the chlorine is continuously introduced, the chlorine introducing speed is 3.8kg/min, and the pressure in the kettle is controlled to be 0.17MPa;
the second stage of chlorination, wherein the chlorine introducing amount is 43% of the total chlorine introducing amount;
(3) Third stage of chlorination
The temperature rising rate is controlled to be 0.18 ℃/min, the temperature is raised to 101 ℃, chlorine is continuously introduced, the chlorine introducing speed is controlled to be 4kg/min, the pressure in the kettle is controlled to be 0.15MPa, and the chlorinated polyvinyl chloride primary slurry is prepared after the third stage of chlorination is completed;
and the third stage of chlorination, wherein the chlorine flux is 32% of the total chlorine flux.
4. Post-treatment
Mixing the chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.08MPa, controlling the heating temperature of the nitrogen to 78 ℃, preserving heat and pressure for 40min, and rapidly releasing pressure to normal pressure within 0.2s after the heat preservation and pressure maintaining are finished to prepare the chlorinated polyvinyl chloride slurry;
the mass ratio of the chlorinated polyvinyl chloride primary slurry to the 2, 6-tertiary butyl-4-methylphenol to the sodium alginate to the ethylene bis stearamide is 130:0.5:0.4:0.3.
5. Deacidifying, neutralizing, centrifuging, and drying
And deacidifying, neutralizing, centrifugally dewatering and drying the chlorinated polyvinyl chloride slurry to obtain the chlorinated polyvinyl chloride.
Example 3 method for preparing chlorinated polyvinyl chloride by acid phase suspension method
1. Modified polyvinyl chloride
(1) Pretreatment of
Performing plasma ball milling treatment on polyvinyl chloride powder in nitrogen gas for 56min at a ball milling rotating speed of 375rpm, a discharge current of 92mA, a discharge voltage of 28kV, a discharge frequency of 40kHz, and obtaining pretreated polyvinyl chloride after the plasma ball milling treatment is finished;
the polyvinyl chloride powder has a particle size of 125 mu m and an apparent density of 0.59g/ml;
(2) Modification
Mixing the pretreated polyvinyl chloride with gelatin, mannitol and a modifier, then performing ultraviolet-ultrasonic treatment, controlling the central wavelength of an ultraviolet lamp in the ultraviolet-ultrasonic treatment to be 330nm, the power of the ultraviolet lamp to be 220W, and the power of ultrasonic waves to be 380W, and drying to obtain modified polyvinyl chloride;
the modifier is a mixture of carboxymethyl cellulose, polyethylene glycol, pentaerythritol, sodium dodecyl benzene sulfonate and deionized water, and the mass ratio of the deionized water to the carboxymethyl cellulose to the polyethylene glycol to the pentaerythritol to the sodium dodecyl benzene sulfonate is 90:3.1:2.2:2.6:1.7;
the mass ratio of the pretreated polyvinyl chloride, gelatin, mannitol and the modifier is 140:2.2:1.6:4.6.
2. Preparation of modified polyvinyl chloride suspension
(1) Preparation auxiliary agent
Mixing sodium dodecyl benzene sulfonate, talcum powder, dimethyl silicone oil, polyvinylpyrrolidone and fatty alcohol polyoxyethylene ether, placing the mixture in a 77 ℃ for heat treatment for 28min, and naturally cooling the mixture to room temperature to obtain an auxiliary agent;
the mass ratio of the sodium dodecyl benzene sulfonate to the talcum powder to the dimethyl silicone oil to the polyvinylpyrrolidone to the fatty alcohol-polyoxyethylene ether is 1.3:0.5:0.7:0.6:0.6;
(2) Mixing
Adding a hydrochloric acid solution, an auxiliary agent and azodiisobutyronitrile into the modified polyvinyl chloride, controlling the stirring speed to be 123rpm, then precooling at 4.2 ℃ for 22min, freezing after precooling, wherein the freezing time is 35min, the freezing temperature is-10 ℃, and heating to room temperature at a speed of 0.6 ℃/min after freezing to prepare a modified polyvinyl chloride suspension;
the mass concentration of the hydrochloric acid solution is 18%;
the mass ratio of the modified polyvinyl chloride to the hydrochloric acid solution is 1:9, a step of performing the process;
the mass ratio of the modified polyvinyl chloride to the auxiliary agent to the azodiisobutyronitrile is 100:3.2:0.16.
3. Chlorination
Adding the modified polyvinyl chloride suspension into a chlorination kettle, introducing nitrogen for 32min, and discharging oxygen in the chlorination kettle;
the mass ratio of the total chlorine to the modified polyvinyl chloride is 1.1:1, a step of;
(1) First stage chlorination
Raising the temperature in the kettle to 77 ℃, starting chlorine introduction, controlling the chlorine introduction speed to be 2.1kg/min, and controlling the pressure in the kettle to be 0.13MPa;
the first stage of chlorination, wherein the chlorine introducing amount is 36% of the total chlorine introducing amount;
(2) Second stage chlorination
The temperature rising rate is controlled to be 0.12 ℃/min, the temperature is raised to 96 ℃, the chlorine is continuously introduced, the chlorine introducing speed is controlled to be 4.2kg/min, and the pressure in the kettle is controlled to be 0.19MPa;
the second stage of chlorination, wherein the chlorine introducing amount is 38% of the total chlorine introducing amount;
(3) Third stage of chlorination
Controlling the heating rate to be 0.22 ℃/min, heating to 103 ℃, continuing to introduce chlorine, controlling the pressure in the kettle to be 0.23MPa, and after the third stage chlorination is completed, preparing chlorinated polyvinyl chloride primary slurry;
and the third stage of chlorination, wherein the chlorine flux is 26% of the total chlorine flux.
4. Post-treatment
Mixing the chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.12MPa, controlling the heating temperature of the nitrogen to 82 ℃, preserving heat and pressure for 30min, and rapidly releasing pressure to normal pressure within 0.4s after the heat preservation and pressure maintaining are finished to prepare the chlorinated polyvinyl chloride slurry;
the mass ratio of the chlorinated polyvinyl chloride primary slurry to the 2, 6-tertiary butyl-4-methylphenol to the sodium alginate to the ethylene bis stearamide is 130:0.7:0.6:0.5.
5. Deacidifying, neutralizing, centrifuging, and drying
And deacidifying, neutralizing, centrifugally dewatering and drying the chlorinated polyvinyl chloride slurry to obtain the chlorinated polyvinyl chloride.
Comparative example 1
On the basis of example 1, the modification step of polyvinyl chloride was omitted, polyvinyl chloride without any treatment was directly used, and the rest of the operations were the same.
Comparative example 2
The modified polyvinyl chloride suspension was prepared by directly mixing modified polyvinyl chloride with sodium dodecylbenzenesulfonate, talc, simethicone, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether, and azobisisobutyronitrile in the modified polyvinyl chloride suspension, and the other operations were the same, except that the modified polyvinyl chloride suspension was prepared on the basis of example 1.
Product performance detection
1. Testing the chlorine content of chlorinated polyvinyl chloride products according to the method in GB/T7139-2002
2. Mechanical and stability Properties
The chlorinated polyvinyl chloride products prepared in examples 1 to 3 and comparative examples 1 to 3 were used to produce chlorinated polyvinyl chloride samples, specifically: the raw materials comprise, by weight, 100 parts of chlorinated polyvinyl chloride products, 3 parts of calcium stearate, 4 parts of titanium dioxide, 18 parts of calcium carbonate and 0.5 part of paraffin wax, and the raw materials are uniformly mixed by weight and then are subjected to melt extrusion, and the temperature of an extruder is controlled to be 180 ℃;
the mechanical properties and stability of chlorinated polyvinyl chloride samples were tested, wherein the tensile strength was according to the method in GB/T1040.2-2006, the simply supported beam impact strength was according to the method in GB/T1043.1-2008, and the flexural strength was according to the method in GB/T9341-2008, with the following specific results:
the percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The method for preparing the chlorinated polyvinyl chloride by using the acid-phase suspension method is characterized by comprising the steps of modifying the polyvinyl chloride, preparing a modified polyvinyl chloride suspension, chloridizing, post-treating, deacidifying, neutralizing, centrifuging and drying;
the modified polyvinyl chloride comprises pretreatment and modification steps;
the pretreatment step comprises the steps of carrying out plasma ball milling treatment on polyvinyl chloride powder in nitrogen for 54-56min at 365-375rpm, discharging current of 88-92mA at 24-28kV, and discharging frequency of 36-40kHz, and obtaining pretreated polyvinyl chloride after the plasma ball milling treatment is finished;
the particle size of the polyvinyl chloride powder is 115-125 mu m, and the apparent density is 0.57-0.59g/mL;
the modification step comprises the steps of mixing pretreated polyvinyl chloride with gelatin, mannitol and a modifier, then carrying out ultraviolet-ultrasonic treatment, wherein the central wavelength of an ultraviolet lamp is 310-330nm, the power of the ultraviolet lamp is 220-240W, the power of ultrasonic waves is 360-380W, and drying to obtain modified polyvinyl chloride;
the mass ratio of the pretreated polyvinyl chloride, gelatin, mannitol and modifier is 120-140:1.7-2.2:1.4-1.6:4.3-4.6;
the modifier is a mixture of carboxymethyl cellulose, polyethylene glycol, pentaerythritol, sodium dodecyl benzene sulfonate and deionized water, and the mass ratio of the deionized water to the carboxymethyl cellulose to the polyethylene glycol to the pentaerythritol to the sodium dodecyl benzene sulfonate is 82-90:2.8-3.1:1.7-2.2:2.4-2.6:1.3-1.7;
the preparation of the modified polyvinyl chloride suspension comprises the steps of preparing an auxiliary agent and mixing;
the preparation method comprises the steps of mixing sodium dodecyl benzene sulfonate, talcum powder, simethicone, polyvinylpyrrolidone and fatty alcohol-polyoxyethylene ether, placing the mixture in 72-77 ℃ for heat treatment for 23-28min, and naturally cooling to room temperature to obtain the auxiliary agent;
the mass ratio of the sodium dodecyl benzene sulfonate to the talcum powder to the dimethyl silicone oil to the polyvinylpyrrolidone to the fatty alcohol-polyoxyethylene ether is 1.1-1.3:0.3-0.5:0.5-0.7:0.4-0.6:0.3-0.6;
adding a hydrochloric acid solution, an auxiliary agent and azodiisobutyronitrile into the modified polyvinyl chloride, uniformly mixing, pre-cooling at the pre-cooling temperature of 3.8-4.2 ℃ for 18-22min, freezing for 35-45min after pre-cooling, and cooling at the freezing temperature of-13 to-10 ℃ at the speed of 0.4-0.6 ℃/min to room temperature to prepare a modified polyvinyl chloride suspension;
the mass concentration of the hydrochloric acid solution is 16-18%;
the mass ratio of the modified polyvinyl chloride to the hydrochloric acid solution is 1:7-9;
the mass ratio of the modified polyvinyl chloride to the auxiliary agent to the azodiisobutyronitrile is 100:2.6-3.2:0.14-0.16;
the chlorination comprises first-stage chlorination, second-stage chlorination and third-stage chlorination;
the first stage chloridizing, namely adding the modified polyvinyl chloride suspension into a chloridizing kettle, introducing nitrogen for 28-32min, discharging oxygen in the chloridizing kettle, raising the temperature in the kettle to 75-77 ℃, starting chlorine introduction, controlling the chlorine introduction speed to be 1.8-2.1kg/min, and controlling the pressure in the kettle to be 0.11-0.13MPa;
the first stage of chlorination, wherein the chlorine introducing amount is 25-36% of the total chlorine introducing amount;
the second stage of chlorination, the heating rate is controlled to be 0.07-0.12 ℃/min, the temperature is increased to 94-96 ℃, the chlorine is continuously introduced, the chlorine introducing speed is 3.8-4.2kg/min, and the pressure in the kettle is controlled to be 0.17-0.19MPa;
the second stage of chlorination, wherein the chlorine introducing amount is 38-43% of the total chlorine introducing amount;
the third stage of chlorination, wherein the heating rate is controlled to be 0.18-0.22 ℃/min, the temperature is increased to be 101-103 ℃, the chlorine is continuously introduced, the chlorine introducing speed is controlled to be 4-6kg/min, the pressure in the kettle is controlled to be 0.15-0.23MPa, and the chlorinated polyvinyl chloride primary slurry is prepared after the third stage of chlorination is completed;
the third stage of chlorination, wherein the chlorine introducing amount is 26-32% of the total chlorine introducing amount;
mixing the chlorinated polyvinyl chloride primary slurry with 2, 6-tertiary butyl-4-methylphenol, sodium alginate and ethylene-based bis stearamide, then placing the mixture in a closed container, introducing high-temperature and high-pressure nitrogen, pressurizing to 0.08-0.12MPa, controlling the heating temperature of the nitrogen to 78-82 ℃, preserving heat and pressure for 30-40min, and rapidly releasing pressure to normal pressure within 0.2-0.4s after the heat preservation and pressure maintaining are finished to prepare the chlorinated polyvinyl chloride slurry;
in the post-treatment step, the mass ratio of the chlorinated polyvinyl chloride primary slurry to the 2, 6-tertiary butyl-4-methylphenol to the sodium alginate to the ethylene bis stearamide is 130:0.5-0.7:0.4-0.6:0.3-0.5.
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