CN116396569A - Preparation method of PVC impact modifier - Google Patents
Preparation method of PVC impact modifier Download PDFInfo
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- CN116396569A CN116396569A CN202310671667.3A CN202310671667A CN116396569A CN 116396569 A CN116396569 A CN 116396569A CN 202310671667 A CN202310671667 A CN 202310671667A CN 116396569 A CN116396569 A CN 116396569A
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- chlorinated polyethylene
- impact modifier
- zeolite powder
- pvc
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 76
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 71
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 238000012986 modification Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims description 31
- 239000010457 zeolite Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 10
- 235000013539 calcium stearate Nutrition 0.000 claims description 10
- 239000008116 calcium stearate Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 150000008301 phosphite esters Chemical class 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 claims description 10
- 239000001069 triethyl citrate Substances 0.000 claims description 10
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000013769 triethyl citrate Nutrition 0.000 claims description 10
- 239000002383 tung oil Substances 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- VVSMKOFFCAJOSC-UHFFFAOYSA-L disodium;dodecylbenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1 VVSMKOFFCAJOSC-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 31
- 239000004800 polyvinyl chloride Substances 0.000 description 31
- 239000000543 intermediate Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a PVC impact modifier, which comprises the steps of modifying chlorinated polyethylene and preparing the impact modifier; the modified chlorinated polyethylene comprises preliminary modification and secondary modification; the preparation of the impact modifier comprises the steps of preparing an intermediate and mixing; the preliminary modification is that chlorinated polyethylene powder is subjected to magnetic treatment, firstly placed in a magnetic field with the intensity of 480-510mT for 5-8min, then placed in a magnetic field with the intensity of 380-420mT for 8-12min, and the magnetic field intensity reduction rate is controlled to be 15-25mT/min, so that preliminary modified chlorinated polyethylene is prepared; the PVC impact modifier prepared by the method of the invention can improve the impact resistance of PVC products and ensure the strength performance and weather resistance of PVC products.
Description
Technical Field
The invention relates to a preparation method of a PVC impact modifier, and in particular belongs to the technical field of high polymer materials.
Background
PVC (polyvinyl chloride) is a synthetic material that is now deeply favored, popular and also widely used, and is widely used in a second most highly among various synthetic materials;
however, PVC has poor processability and poor product properties, and cannot meet the use requirements, and various auxiliary agents must be added in the processing process to improve the processability.
Chlorinated Polyethylene (CPE) is a high molecular chloride generated by substituting a secondary carbon atom in polyethylene molecules with a chlorine atom, has good weather resistance, ozone resistance, chemical resistance, cold resistance, flame retardance and excellent electrical insulation property, is low in price, and is widely applied to impact modifiers of PVC;
however, because the impact resistance of PVC is poor, the amount of the chlorinated polyethylene to be added is large, and the strength performance of PVC products can be damaged to a large extent by adding a large amount of the chlorinated polyethylene; meanwhile, the chlorinated polyethylene contains chlorine atoms, so that the chlorinated polyethylene is easy to decompose when heated, and hydrogen chloride is extremely easy to decompose to generate when the consumption is large, and the decomposition of PVC is greatly accelerated by the hydrogen chloride, so that the weather resistance of the product is greatly reduced.
Thus, the prior art preparation of PVC impact modifiers using chlorinated polyethylene has the following problems:
1. the addition amount of the chlorinated polyethylene is small, and the impact resistance of PVC products is poor;
2. the addition of the chlorinated polyethylene is large, and the strength performance and the weather resistance of the PVC product can be influenced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a PVC impact modifier, which can improve the impact resistance of PVC products and ensure the strength performance and weather resistance of the PVC products.
In order to solve the technical problems, the invention adopts the following technical scheme:
1. modified chlorinated polyethylene
(1) Preliminary modification
Performing magnetic treatment on chlorinated polyethylene powder, firstly placing the chlorinated polyethylene powder in a magnetic field with the intensity of 480-510mT for 5-8min, then placing the chlorinated polyethylene powder in a magnetic field with the intensity of 380-420mT for 8-12min, and controlling the decreasing rate of the magnetic field intensity to 15-25mT/min to prepare the preliminary modified chlorinated polyethylene;
the powder density of the chlorinated polyethylene powder is 0.942-0.951g/cm 3 The average grain diameter is 180-220 mu m, and the chlorine content is 30-32%.
(2) Again modify
Mixing the prepared preliminary modified chlorinated polyethylene with tung oil, 2, 6-tertiary butyl-4-methylphenol, a stabilizer, triethyl citrate and deionized water, wherein the mixing temperature is 78-82 ℃, carrying out ultrasonic vibration after mixing, controlling the frequency of ultrasonic vibration to be 57-63KHz, and the time of ultrasonic vibration to be 18-22min to prepare the modified chlorinated polyethylene;
the mass ratio of the preliminary modified chlorinated polyethylene, the tung oil, the 2, 6-tertiary butyl-4-methylphenol, the stabilizer and the triethyl citrate to the deionized water is 19-21:4.8-5.2:0.9-1.1:0.7-0.9:1-1.2:78-85;
the preparation method of the stabilizer comprises the steps of mixing modified zeolite powder, zinc stearate, calcium stearate, pentaerythritol, oleic acid and phosphite ester, controlling the stirring speed to be 580-620rpm, stirring for 8-12min, heating to 135-144 ℃ at the speed of 4.8-5.2 ℃/min, preserving heat for 57-62min, and naturally cooling to room temperature to obtain the stabilizer;
the phosphite ester has a density of 0.985-0.989g/cm 3 The phosphorus content is 2.5-2.8%;
the mass ratio of the modified zeolite powder to the zinc stearate to the calcium stearate to the pentaerythritol to the oleic acid to the phosphite ester is 9.8-10.2:5.7-6.2:5.8-6.1:6.2-6.5:0.9-1.1:2.8-3.2;
the preparation method of the modified zeolite powder comprises the steps of placing zeolite powder in a muffle furnace for calcination, wherein the temperature of the muffle furnace is 540-560 ℃, the calcination time is 0.8-1.2h, cooling to room temperature at the speed of 8-12 ℃/min after the calcination is completed, adding deionized water to prepare zeolite powder slurry with the mass concentration of 23-28%, adding sodium hydroxide solution with the mass concentration of 38-42%, controlling the stirring speed to be 900-1100rpm, stirring for 18-22min, filtering and washing, drying the washed zeolite powder at 115-125 ℃ for 3.8-4.3h, then placing at 1.8-2.2 ℃ for 35-43min, and finally heating to room temperature at the speed of 1.5-2.5 ℃/min to obtain the modified zeolite powder;
the particle size of the zeolite powder is 43-48 mu m;
the mass ratio of the zeolite powder slurry to the sodium hydroxide solution is 1:5.5-6.5.
2. Preparation of impact modifier
(1) Preparation of intermediates
Mixing methyl methacrylate, butyl methacrylate, sodium dodecyl sulfate and deionized water, stirring, introducing nitrogen, controlling the pressure to be 0.02-0.04MPa and the stirring speed to be 190-210rpm, heating to 58-62 ℃ at the speed of 3.8-4.2 ℃/min, adding an initiator to react for 1.2-1.4h, reacting for 5.7-6.3h, and finally preserving the temperature for 1.5-1.8h at 82-87 ℃ to obtain an intermediate;
the initiator is a mixture of potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1:0.5-2;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the sodium dodecyl benzene sulfate to the initiator to the deionized water is 100:18-22:1.9-2.1:0.05-0.07:175-185;
(2) Mixing material
Mixing and stirring the modified chlorinated polyethylene, the intermediate, the nekal BX and the white carbon black for 18-22min at 97-105rpm to prepare an impact modifier;
the mass ratio of the modified chlorinated polyethylene to the intermediate to the nekal BX to the white carbon black is 720:14-16:4.8-5.2:26-28.
Compared with the prior art, the invention has the beneficial effects that:
1. the PVC impact modifier prepared by the preparation method has the tensile strength of 57.6-58.5MPa and the elongation at break of 457-468% (GB/T1040-2006) after being processed into PVC materials; impact resistance of 43.6-45.9KJ/m 2 （GB/T1043-2008）；
2. The PVC impact modifier prepared by the preparation method of the invention is placed in an environment of-15 ℃ for 168 hours after being processed into PVC materials, the tensile strength is 52.6-55.0MPa, the elongation at break is 386-417%, and the impact resistance is 40.7-43.7KJ/m 2 ；
3. The PVC impact modifier prepared by the preparation method of the invention is placed in an environment of 90 ℃ for 168 hours after being processed into PVC materials, the tensile strength is 48.6-52.7MPa, the elongation at break is 407-426%, and the impact resistance is 34.9-40.4KJ/m 2 ；
4. The PVC impact modifier prepared by the preparation method of the invention is soaked in 20 percent sodium chloride solution for 168 hours after being processed into PVC materials, the tensile strength is 50.3-53.2MPa, the elongation at break is 396-407 percent, and the impact resistance is 39.5-42.2KJ/m 2 。
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 preparation of a PVC impact modifier
1. Modified chlorinated polyethylene
(1) Preliminary modification
Performing magnetic treatment on chlorinated polyethylene powder, firstly placing the chlorinated polyethylene powder in a magnetic field with the strength of 500mT for 6min, then placing the chlorinated polyethylene powder in a magnetic field with the strength of 400mT for 10min, and controlling the decreasing speed of the magnetic field strength to be 20mT/min to prepare the preliminary modified chlorinated polyethylene;
the powder density of the chlorinated polyethylene powder is 0.947g/cm 3 The average particle diameter was 200. Mu.m, and the chlorine content was 31%.
(2) Again modify
Mixing the prepared preliminary modified chlorinated polyethylene with tung oil, 2, 6-tertiary butyl-4-methylphenol, a stabilizer, triethyl citrate and deionized water, wherein the mixing temperature is 80 ℃, carrying out ultrasonic vibration after mixing, controlling the frequency of ultrasonic vibration to be 60KHz, and the time of ultrasonic vibration to be 20min to prepare the modified chlorinated polyethylene;
the mass ratio of the preliminary modified chlorinated polyethylene to the tung oil to the 2, 6-tertiary butyl-4-methylphenol to the stabilizer to the triethyl citrate to the deionized water is 20:5:1:0.8:1.1:80;
the preparation method of the stabilizer comprises the steps of mixing modified zeolite powder, zinc stearate, calcium stearate, pentaerythritol, oleic acid and phosphite ester, controlling the stirring rotation speed to be 600rpm, stirring for 10min, then heating to 140 ℃ at the speed of 5 ℃/min, preserving heat for 60min, and naturally cooling to room temperature to obtain the stabilizer;
the phosphite has a density of 0.987g/cm 3 The phosphorus content was 2.7%;
the mass ratio of the modified zeolite powder to the zinc stearate to the calcium stearate to the pentaerythritol to the oleic acid to the phosphite ester is 10:6:6:6.3:1:3, a step of;
the preparation method of the modified zeolite powder comprises the steps of placing zeolite powder in a muffle furnace for calcination, wherein the temperature of the muffle furnace is 550 ℃, the calcination time is 1h, cooling to room temperature at the speed of 10 ℃/min after the calcination is completed, adding deionized water to prepare zeolite powder slurry with the mass concentration of 25%, adding sodium hydroxide solution with the mass concentration of 40%, controlling the stirring speed to be 1000rpm, stirring for 20min, filtering and washing after stirring, drying the washed zeolite powder at 120 ℃ for 4h, then placing the zeolite powder at 2 ℃ for standing for 40min, and finally heating to room temperature at the speed of 2 ℃/min to obtain the modified zeolite powder;
the particle size of the zeolite powder is 45 mu m;
the mass ratio of the zeolite powder slurry to the sodium hydroxide solution is 1:6.
2. preparation of impact modifier
(1) Preparation of intermediates
Mixing methyl methacrylate, butyl methacrylate, sodium dodecyl sulfate and deionized water, stirring, introducing nitrogen, controlling the pressure to be 0.03MPa, stirring at 200rpm, heating to 60 ℃ at the speed of 4 ℃/min, adding an initiator for reaction for 1.3h, reacting for 6h, and finally preserving heat for 1.7h at 85 ℃ to obtain an intermediate;
the initiator is a mixture of potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1:1;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the sodium dodecyl benzene sulfate to the initiator to the deionized water is 100:20:2:0.06:180;
(2) Mixing material
Mixing and stirring the modified chlorinated polyethylene, the intermediate, the nekal BX and the white carbon black for 20min at a stirring speed of 100rpm to prepare an impact modifier;
the mass ratio of the modified chlorinated polyethylene to the intermediate to the nekal BX to the white carbon black is 720:15:5:27.
example 2 preparation of a PVC impact modifier
1. Modified chlorinated polyethylene
(1) Preliminary modification
Performing magnetic treatment on chlorinated polyethylene powder, firstly placing the chlorinated polyethylene powder in a magnetic field with the strength of 510mT for 5min, then placing the chlorinated polyethylene powder in a magnetic field with the strength of 420mT for 8min, and controlling the decreasing speed of the magnetic field strength to be 25mT/min to prepare the preliminary modified chlorinated polyethylene;
the powder density of the chlorinated polyethylene powder is 0.951g/cm 3 The average particle diameter was 220. Mu.m, and the chlorine content was 32%.
(2) Again modify
Mixing the prepared preliminary modified chlorinated polyethylene with tung oil, 2, 6-tertiary butyl-4-methylphenol, a stabilizer, triethyl citrate and deionized water, wherein the mixing temperature is 82 ℃, and performing ultrasonic vibration after mixing, wherein the frequency of ultrasonic vibration is controlled to be 63KHz, and the time of ultrasonic vibration is 18min;
the mass ratio of the preliminary modified chlorinated polyethylene, the tung oil, the 2, 6-tertiary butyl-4-methylphenol, the stabilizer, the triethyl citrate and the deionized water is 21:5.2:1.1:0.9:1.2:85;
the preparation method of the stabilizer comprises the steps of mixing modified zeolite powder, zinc stearate, calcium stearate, pentaerythritol, oleic acid and phosphite ester, controlling the stirring rotation speed to be 620rpm, stirring for 8min, heating to 144 ℃ at the speed of 5.2 ℃/min, preserving heat for 57min, and naturally cooling to room temperature to obtain the stabilizer;
the phosphite has a density of 0.989g/cm 3 The phosphorus content was 2.8%;
the mass ratio of the modified zeolite powder to the zinc stearate to the calcium stearate to the pentaerythritol to the oleic acid to the phosphite is 10.2:6.2:6.1:6.5:1.1:3.2;
the preparation method of the modified zeolite powder comprises the steps of placing zeolite powder into a muffle furnace for calcination, wherein the temperature of the muffle furnace is 560 ℃, the calcination time is 0.8h, cooling to room temperature at a speed of 12 ℃/min after the calcination is completed, adding deionized water to prepare zeolite powder slurry with the mass concentration of 28%, adding a sodium hydroxide solution with the mass concentration of 42%, controlling the stirring speed to be 1100rpm, stirring for 18min, filtering and washing after stirring, drying the washed zeolite powder at 125 ℃ for 3.8h, then placing the zeolite powder at 2.2 ℃ for 35min, and finally raising the temperature to room temperature at a speed of 2.5 ℃/min to obtain the modified zeolite powder;
the particle size of the zeolite powder is 48 mu m;
the mass ratio of the zeolite powder slurry to the sodium hydroxide solution is 1:6.5.
2. preparation of impact modifier
(1) Preparation of intermediates
Mixing and stirring methyl methacrylate, butyl methacrylate, sodium dodecyl sulfate and deionized water, introducing nitrogen, controlling the pressure to be 0.04MPa, stirring at 210rpm, heating to 62 ℃ at the speed of 4.2 ℃/min, adding an initiator for reaction for 1.4 hours, reacting for 6.3 hours, and finally preserving heat for 1.5 hours at 87 ℃ to obtain an intermediate;
the initiator is a mixture of potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1:2;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the sodium dodecyl benzene sulfate to the initiator to the deionized water is 100:22:2.1:0.07:185;
(2) Mixing material
Mixing and stirring the modified chlorinated polyethylene, the intermediate, the nekal BX and the white carbon black for 22min at the stirring speed of 97rpm to prepare an impact modifier;
the mass ratio of the modified chlorinated polyethylene to the intermediate to the nekal BX to the white carbon black is 720:16:5.2:28.
example 3
Preparation method of PVC impact modifier
1. Modified chlorinated polyethylene
(1) Preliminary modification
Performing magnetic treatment on chlorinated polyethylene powder, firstly placing the chlorinated polyethylene powder in a magnetic field with the intensity of 480mT for 8min, then placing the chlorinated polyethylene powder in a magnetic field with the intensity of 380mT for 12min, and controlling the decreasing rate of the magnetic field intensity to be 15mT/min to prepare the preliminary modified chlorinated polyethylene;
the powder density of the chlorinated polyethylene powder is 0.942g/cm 3 The average particle diameter was 180. Mu.m, and the chlorine content was 30%.
(2) Again modify
Mixing the prepared preliminary modified chlorinated polyethylene with tung oil, 2, 6-tertiary butyl-4-methylphenol, a stabilizer, triethyl citrate and deionized water, wherein the mixing temperature is 78 ℃, carrying out ultrasonic vibration after mixing, controlling the frequency of ultrasonic vibration to be 57KHz, and the time of ultrasonic vibration to be 22min to prepare the modified chlorinated polyethylene;
the mass ratio of the preliminary modified chlorinated polyethylene, the tung oil, the 2, 6-tertiary butyl-4-methylphenol, the stabilizer, the triethyl citrate and the deionized water is 19:4.8:0.9:0.7:1:78;
the preparation method of the stabilizer comprises the steps of mixing modified zeolite powder, zinc stearate, calcium stearate, pentaerythritol, oleic acid and phosphite ester, controlling the stirring speed to be 580rpm, stirring for 12min, then heating to 135 ℃ at the speed of 4.8 ℃/min, preserving heat for 62min, and naturally cooling to room temperature to obtain the stabilizer;
the phosphorous isAcid ester with density of 0.985g/cm 3 The phosphorus content was 2.5%;
the mass ratio of the modified zeolite powder to the zinc stearate to the calcium stearate to the pentaerythritol to the oleic acid to the phosphite is 9.8:5.7:5.8:6.2:0.9:2.8;
the preparation method of the modified zeolite powder comprises the steps of placing zeolite powder into a muffle furnace for calcination, wherein the temperature of the muffle furnace is 540 ℃, the calcination time is 1.2h, cooling to room temperature at the speed of 8 ℃/min after the calcination is completed, adding deionized water to prepare zeolite powder slurry with the mass concentration of 23%, adding sodium hydroxide solution with the mass concentration of 38%, controlling the stirring speed to be 900rpm, stirring for 22min, filtering and washing after stirring, drying the washed zeolite powder at 115 ℃ for 4.3h, then placing at 1.8 ℃ for standing for 43min, and finally raising to room temperature at the speed of 1.5 ℃/min to obtain the modified zeolite powder;
the particle size of the zeolite powder is 43 mu m;
the mass ratio of the zeolite powder slurry to the sodium hydroxide solution is 1:5.5.
2. preparation of impact modifier
(1) Preparation of intermediates
Mixing and stirring methyl methacrylate, butyl methacrylate, sodium dodecyl sulfate and deionized water, introducing nitrogen, controlling the pressure to be 0.02MPa, stirring at 190rpm, heating to 58 ℃ at the speed of 3.8 ℃/min, adding an initiator for reaction for 1.2h, reacting for 5.7h, and finally preserving heat at 82 ℃ for 1.8h to obtain an intermediate;
the initiator is a mixture of potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1:0.5;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the sodium dodecyl benzene sulfate to the initiator to the deionized water is 100:18:1.9:0.05:175;
(2) Mixing material
Mixing and stirring the modified chlorinated polyethylene, the intermediate, the nekal BX and the white carbon black for 18min at a stirring speed of 105rpm to prepare an impact modifier;
the mass ratio of the modified chlorinated polyethylene to the intermediate to the nekal BX to the white carbon black is 720:14:4.8:26.
comparative example 1
On the basis of example 1, the following were changed: omitting the step of modifying chlorinated polyethylene and replacing the modified chlorinated polyethylene with chlorinated polyethylene; the rest of the operations are the same.
Comparative example 2
On the basis of example 1, the following were changed: in the step of modifying the modified chlorinated polyethylene again, the step of modifying the zeolite powder is omitted, and the modified zeolite powder is replaced by the zeolite powder; the rest of the operations are the same.
Comparative example 3
On the basis of example 1, the following were changed: in the step of modifying the chlorinated polyethylene, the primary modification is omitted; the rest of the operations are the same.
Performance testing
The PVC processing aids prepared in examples 1-3 and comparative examples 1-3 were mixed with PVC materials at high speed for 5min at a mixing speed of 350rpm, and then melt-extruded at 180℃to prepare PVC materials; wherein the mass ratio of the PVC processing aid to the PVC material is 1.2:100.
The test results are as follows:
1. impact strength was tested according to GB/T1043-2008 method;
2. tensile properties were tested according to GB/T1040-2006 method;
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 (9)
1. The preparation method of the PVC impact modifier is characterized by comprising the steps of modifying chlorinated polyethylene and preparing the impact modifier;
the modified chlorinated polyethylene comprises preliminary modification and secondary modification; the preparation of the impact modifier comprises the steps of preparing an intermediate and mixing;
the preliminary modification is that chlorinated polyethylene powder is subjected to magnetic treatment, firstly placed in a magnetic field with the intensity of 480-510mT for 5-8min, then placed in a magnetic field with the intensity of 380-420mT for 8-12min, and the magnetic field intensity reduction rate is controlled to be 15-25mT/min, so that preliminary modified chlorinated polyethylene is prepared;
the secondary modification is that the prepared preliminary modified chlorinated polyethylene is mixed with tung oil, 2, 6-tertiary butyl-4-methylphenol, a stabilizer, triethyl citrate and deionized water, the mixing temperature is 78-82 ℃, ultrasonic vibration is carried out after mixing, the frequency of the ultrasonic vibration is controlled to be 57-63KHz, and the time of the ultrasonic vibration is 18-22min, so that the modified chlorinated polyethylene is prepared;
the preparation method of the stabilizer comprises the steps of mixing modified zeolite powder, zinc stearate, calcium stearate, pentaerythritol, oleic acid and phosphite ester, controlling the stirring speed to be 580-620rpm, stirring for 8-12min, heating to 135-144 ℃ at the speed of 4.8-5.2 ℃/min, preserving heat for 57-62min, and naturally cooling to room temperature to obtain the stabilizer;
the preparation method of the modified zeolite powder comprises the steps of placing zeolite powder into a muffle furnace for calcination, wherein the temperature of the muffle furnace is 540-560 ℃, the calcination time is 0.8-1.2h, cooling to room temperature at the speed of 8-12 ℃/min after the calcination is completed, adding deionized water to prepare zeolite powder slurry, adding sodium hydroxide solution, controlling the stirring speed to 900-1100rpm, stirring for 18-22min, filtering and washing after stirring, drying the washed zeolite powder at 115-125 ℃ for 3.8-4.3h, placing the zeolite powder at 1.8-2.2 ℃ for 35-43min, and finally heating to room temperature at the speed of 1.5-2.5 ℃/min to obtain the modified zeolite powder.
2. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the powder density of the chlorinated polyethylene powder is 0.942-0.951g/cm 3 The average grain diameter is 180-220 mu m, and the chlorine content is 30-32%.
3. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the mass ratio of the preliminary modified chlorinated polyethylene, the tung oil, the 2, 6-tertiary butyl-4-methylphenol, the stabilizer and the triethyl citrate to the deionized water is 19-21:4.8-5.2:0.9-1.1:0.7-0.9:1-1.2:78-85.
4. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the phosphite ester has a density of 0.985-0.989g/cm 3 The phosphorus content is 2.5-2.8%;
the mass ratio of the modified zeolite powder to the zinc stearate to the calcium stearate to the pentaerythritol to the oleic acid to the phosphite ester is 9.8-10.2:5.7-6.2:5.8-6.1:6.2-6.5:0.9-1.1:2.8-3.2.
5. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the particle size of the zeolite powder is 43-48 mu m;
the mass concentration of the zeolite powder slurry is 23-28%;
the mass concentration of the sodium hydroxide solution is 38-42%;
the mass ratio of the zeolite powder slurry to the sodium hydroxide solution is 1:5.5-6.5.
6. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the preparation method comprises the steps of mixing and stirring methyl methacrylate, butyl methacrylate, sodium dodecyl sulfate and deionized water, introducing nitrogen, controlling the pressure to be 0.02-0.04MPa, the stirring speed to be 190-210rpm, heating to 58-62 ℃ at the speed of 3.8-4.2 ℃/min, adding an initiator for reaction for 1.2-1.4h, reacting for 5.7-6.3h, and finally preserving heat for 1.5-1.8h at the temperature of 82-87 ℃ to obtain the intermediate.
7. A process for the preparation of a PVC impact modifier as claimed in claim 6, wherein,
the initiator is a mixture of potassium persulfate and sodium persulfate, and the mass ratio of the potassium persulfate to the sodium persulfate is 1:0.5-2;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the sodium dodecyl benzene sulfate to the initiator to the deionized water is 100:18-22:1.9-2.1:0.05-0.07:175-185.
8. A process for the preparation of a PVC impact modifier as claimed in claim 1, wherein,
the mixing is that the modified chlorinated polyethylene, the intermediate, the nekal BX and the white carbon black are mixed and stirred for 18-22min at 97-105rpm, so as to prepare the impact modifier.
9. A process for the preparation of a PVC impact modifier as claimed in claim 8, wherein,
the mass ratio of the modified chlorinated polyethylene to the intermediate to the nekal BX to the white carbon black is 720:14-16:4.8-5.2:26-28.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571087A (en) * | 2013-09-30 | 2014-02-12 | 芜湖航天特种电缆厂 | Environment-friendly filled cable material |
| CN106046627A (en) * | 2016-08-15 | 2016-10-26 | 东莞市悠悠美居家居制造有限公司 | Polyvinyl chloride massage pad and preparation method thereof |
| CN112898714A (en) * | 2021-03-25 | 2021-06-04 | 广东鑫达新材料科技有限公司 | Preparation and application of multifunctional efficient PVC modified processing aid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571087A (en) * | 2013-09-30 | 2014-02-12 | 芜湖航天特种电缆厂 | Environment-friendly filled cable material |
| CN106046627A (en) * | 2016-08-15 | 2016-10-26 | 东莞市悠悠美居家居制造有限公司 | Polyvinyl chloride massage pad and preparation method thereof |
| CN112898714A (en) * | 2021-03-25 | 2021-06-04 | 广东鑫达新材料科技有限公司 | Preparation and application of multifunctional efficient PVC modified processing aid |
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