CN118496679B - Preparation method of special calcium-zinc stabilizer for PVC transparent film - Google Patents
Preparation method of special calcium-zinc stabilizer for PVC transparent film Download PDFInfo
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- CN118496679B CN118496679B CN202410977478.3A CN202410977478A CN118496679B CN 118496679 B CN118496679 B CN 118496679B CN 202410977478 A CN202410977478 A CN 202410977478A CN 118496679 B CN118496679 B CN 118496679B
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 77
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 30
- 150000003751 zinc Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001704 evaporation Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- WFRXSXUDWCVSPI-UHFFFAOYSA-N 3h-benzimidazol-5-amine Chemical compound NC1=CC=C2NC=NC2=C1 WFRXSXUDWCVSPI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- FKYAWWVVKRUUFY-UHFFFAOYSA-L calcium;decanoate Chemical compound [Ca+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O FKYAWWVVKRUUFY-UHFFFAOYSA-L 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- NVKSAUAQUPYOPO-UHFFFAOYSA-L zinc;decanoate Chemical compound [Zn+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O NVKSAUAQUPYOPO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 34
- 239000004800 polyvinyl chloride Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 241001536352 Fraxinus americana Species 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003490 calendering Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000010792 warming 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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Oil, Petroleum & Natural Gas (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a special calcium-zinc stabilizer for a PVC transparent film, and relates to the field of polymer material additives. The calcium-zinc stabilizer is prepared by mixing proper amounts of calcium salt, zinc salt, lubricant, antioxidant and synergist, and reacting and processing under specific conditions. The stabilizer not only can effectively improve the thermal stability of the PVC transparent film, but also can effectively improve the oxidation resistance of the PVC transparent film.
Description
Technical Field
The invention relates to the field of polymer material additives, in particular to a preparation method of a special calcium-zinc stabilizer for a PVC transparent film.
Background
PVC (polyvinyl chloride) transparent films are widely applied to various fields such as food packaging, medical packaging, window film, advertisement materials and the like due to excellent transparency, physical properties and processability. Transparent films are used in a variety of fields and are required to have excellent properties in terms of chemical resistance, light stability, and the like.
The patent with the publication number of CN107964250B discloses a high-efficiency composite lead salt stabilizer prepared by using white ash and a preparation method thereof, wherein the high-efficiency composite lead salt stabilizer comprises the following components in parts by mass: 1 part of basic lead sulfate compound prepared by white ash, 0.1-0.5 part of stearated lead salt compound prepared by white ash, 0.05-0.3 part of dibasic lead phosphite, 0.04-0.3 part of stearate, 0.04-0.3 part of paraffin and 0.005-0.02 part of antioxidant; the high-efficiency composite lead salt stabilizer is prepared by taking white ash as a main raw material through an acid leaching modification procedure, a stearic acid treatment procedure and a compound forming procedure.
The patent with the publication number of CN109825002B discloses a PVC environment-friendly calcium-zinc stabilizer, which comprises the following components in parts by weight: 10-30 parts of calcium salt main stabilizer, 10-30 parts of zinc salt main stabilizer, 15-25 parts of modified hydrotalcite, 10-20 parts of lubricant, 5-10 parts of modified halloysite nanotube, 1-5 parts of antioxidant, 1-5 parts of auxiliary stabilizer and 1-5 parts of ultraviolet absorber. The PVC environment-friendly calcium-zinc stabilizer disclosed by the invention has the advantages of high stability, strong initial tinting strength and good precipitation resistance, and overcomes the defect of easy precipitation in the traditional calcium-zinc processing process.
The patent with the publication number of CN102391592B discloses an environment-friendly calcium-zinc stabilizer for PVC calendered films and a preparation method thereof, wherein the stabilizer consists of the following raw materials in percentage by mass: 10-30% of calcium salt main stabilizer, 10-30% of zinc salt main stabilizer, 30-50% of hydrotalcite, 10-20% of lubricant, 5-15% of thiophene heterocyclic compound, 1-5% of antioxidant, 1-5% of ultraviolet absorber and 1-5% of auxiliary stabilizer. The preparation method of the environment-friendly calcium-zinc stabilizer for the PVC calendered film comprises the following steps: the raw materials are put into a high-speed stirrer in three sections, and stirred for 30min at 55-56 ℃ with the rotating speed of 1000-1500r/min.
However, conventional stabilizers such as lead salts, although improving the performance of PVC, are increasingly replaced by calcium zinc complex stabilizers because of their high toxicity, which are harmful to the environment and human body. However, existing calcium zinc stabilizers have limited effectiveness in improving thermal stability. Therefore, there is a need for a calcium zinc stabilizer that enhances the thermal stability while maintaining the excellent properties of the PVC transparent film.
Disclosure of Invention
The invention aims to provide a preparation method of a special calcium-zinc stabilizer for a PVC transparent film, which aims to solve the problems in the prior art. According to the calcium-zinc stabilizer provided by the invention, the heat stability of the PVC transparent film is obviously improved and the oxidation resistance of the PVC transparent film is improved by optimizing the raw material proportion and the preparation process.
In order to achieve the above object, the present method proposes the following solution:
The preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
S1: weighing the following raw materials in parts by weight: 10-15 parts of calcium salt, 3-8 parts of zinc salt, 5-10 parts of lubricant, 2-5 parts of antioxidant and 0.2-1 part of synergist;
S2: dissolving calcium salt and zinc salt in 145-160 parts of solvent, and uniformly stirring to obtain a mixed solution;
s3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50-70 ℃;
s4: adding antioxidant, reacting for 1-2 hours, filtering to remove insoluble substances;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
s6: and (3) crushing the calcium-zinc stabilizer solid to the particle size of 10-30 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
Preferably, the calcium salt in S1 is one or more of calcium stearate and calcium caprate.
Preferably, the zinc salt in the S1 is one or more of zinc stearate, zinc caprate and zinc acetate.
Preferably, the lubricant in S1 is one or more of paraffin wax, polyethylene wax or stearic acid.
Preferably, the antioxidant in S1 is one or more of 2, 6-di-tert-butyl-4-methylphenol (BHT), antioxidant 1010 or antioxidant 168.
Preferably, the preparation method of the synergist in the step S1 comprises the following steps:
According to the parts by weight, using nitrogen to replace air in a stirring reaction kettle, wherein the addition amount of trans-epoxy o-methyl diketone is 20-40 parts, and the addition amount of 5-amino benzimidazole is 7-14 parts; the addition amount of the 1, 2-dimercapto-carborane (CAS: 23810-63-1) is 10-20 parts; 200-400 parts of DMF; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 2-15 parts; reacting at 50-60 ℃ and normal pressure; stirring the reaction mixture for 50-120 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
Preferably, the solvent in S2 is one or more of ethanol, propanol and ethyl acetate.
Preferably, the reduced pressure evaporation temperature in the step S5 is 40-70 ℃, the vacuum degree is 200-300mbar, and the rotating speed of the rotary evaporation bottle is 60-100 revolutions per minute.
Reaction mechanism: the introduction of the ortho-methyldiketone provides necessary functional groups for subsequent reactions through the special chemical structure. In the reaction with 5-aminobenzimidazole, the active center of the ortho-methyldiketone promotes the progress of the ring-opening reaction, forming a more stable intermediate.
Next, when this intermediate meets 1, 2-dimercapto-orthocarborane, a mercapto-epoxy ring opening reaction occurs. In this process, the structure of carborane provides additional stability to the reaction, making the overall molecular structure stronger.
The beneficial effects are that: this series of reactions is not simply a chemical change, but they play a key role in enhancing the effectiveness of the calcium zinc stabilizer. First, the addition of the ortho-methyldiketone enhances the polarity of the molecule, making the entire molecule more susceptible to interaction with other materials, thereby increasing the effectiveness of the stabilizer.
And secondly, the introduction of benzimidazole and carborane not only increases the thermal stability of molecules, but also improves the oxidation resistance. This means that the synergist can better maintain its stability in high temperature or oxidizing environment, providing longer protection for the calcium zinc stabilizer.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
s1: weighing the following raw materials: 10kg of calcium salt, 3kg of zinc salt, 5kg of lubricant, 2kg of antioxidant and 0.2kg of synergist;
s2: dissolving calcium salt and zinc salt in 145kg of solvent, and uniformly stirring to obtain a mixed solution;
S3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50 ℃;
s4: adding an antioxidant, reacting for 1 hour, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
S6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 10 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium stearate.
The zinc salt in the S1 is zinc stearate.
The lubricant in the step S1 is paraffin.
The antioxidant in the S1 is 2, 6-di-tert-butyl-4-methylphenol (BHT).
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred reaction kettle, air is replaced by nitrogen, the addition amount of trans-epoxy-o-methyldione is 20kg, and the addition amount of 5-aminobenzimidazole is 7kg; the addition amount of 1, 2-dimercapto-orthocarborane (CAS: 23810-63-1) was 10kg; 200kg of DMF; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 2kg; carrying out reaction at 50 ℃ and normal pressure; the reaction mixture was stirred for 50 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in the S2 is ethanol.
The reduced pressure evaporation temperature in the step S5 is 40 ℃, the vacuum degree is 200mbar, and the rotating speed of the rotary evaporation bottle is 60 revolutions per minute.
Example 2: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
S1: weighing the following raw materials: 12kg of calcium salt, 5kg of zinc salt, 7kg of lubricant, 3kg of antioxidant and 0.5kg of synergist;
S2: dissolving calcium salt and zinc salt in 150kg of solvent, and uniformly stirring to obtain a mixed solution;
s3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 60 ℃;
s4: adding an antioxidant, reacting for 1 hour, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
s6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 20 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium stearate.
The zinc salt in S1 is zinc caprate.
The lubricant in the step S1 is paraffin.
The antioxidant in the step S1 is antioxidant 1010.
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred reaction kettle, air is replaced by nitrogen, the addition amount of trans-epoxy-o-methyldione is 30kg, and the addition amount of 5-aminobenzimidazole is 9kg; the addition amount of 1, 2-dimercapto-orthocarborane (CAS: 23810-63-1) was 13kg; the addition amount of DMF was 300kg; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 6kg; carrying out reaction at 55 ℃ and normal pressure; the reaction mixture was stirred for 75 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in S2 is propanol.
The reduced pressure evaporation temperature in S5 is 50 ℃, the vacuum degree is 235mbar, and the rotating speed of the rotary evaporation bottle is 75 revolutions per minute.
Example 3: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
S1: weighing the following raw materials: 14kg of calcium salt, 6.5kg of zinc salt, 8.5kg of lubricant, 4kg of antioxidant and 0.8kg of synergist;
s2: dissolving calcium salt and zinc salt in 155kg of solvent, and uniformly stirring to obtain a mixed solution;
s3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 60 ℃;
S4: adding an antioxidant, reacting for 2 hours, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
s6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 20 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium caprate.
The zinc salt in S1 is zinc caprate.
The lubricant in the step S1 is polyethylene wax.
The antioxidant in S1 is antioxidant 168.
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred reaction kettle, air is replaced by nitrogen, the addition amount of trans-epoxy-o-methyldione is 30kg, and the addition amount of 5-aminobenzimidazole is 11.5kg; the addition amount of 1, 2-dimercapto-orthocarborane (CAS: 23810-63-1) was 17.5kg; the addition amount of DMF was 300kg; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 12kg; carrying out reaction at 55 ℃ and normal pressure; stirring the reaction mixture for 100 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in the S2 is ethyl acetate.
The reduced pressure evaporation temperature in the step S5 is 60 ℃, the vacuum degree is 250mbar, and the rotating speed of the rotary evaporation bottle is 85 revolutions per minute.
Example 4: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
s1: weighing the following raw materials: 15kg of calcium salt, 8kg of zinc salt, 10kg of lubricant, 5kg of antioxidant and 1kg of synergist;
S2: dissolving calcium salt and zinc salt in 160kg of solvent, and uniformly stirring to obtain a mixed solution;
s3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 70 ℃;
S4: adding an antioxidant, reacting for 2 hours, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
s6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 30 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium caprate.
The zinc salt in S1 is zinc acetate.
The lubricant in the step S1 is paraffin.
The antioxidant in the S1 is 2, 6-di-tert-butyl-4-methylphenol (BHT).
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred reaction kettle, air is replaced by nitrogen, the addition amount of trans-epoxy-o-methyldione is 40kg, and the addition amount of 5-aminobenzimidazole is 14kg; the addition amount of 1, 2-dimercapto-carborane (CAS: 23810-63-1) was 20kg; the addition amount of DMF is 400kg; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 15kg; carrying out reaction at 60 ℃ and normal pressure; the reaction mixture was stirred for 120 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in the S2 is ethanol.
The reduced pressure evaporation temperature in the step S5 is 70 ℃, the vacuum degree is 300mbar, and the rotating speed of the rotary evaporation bottle is 100 revolutions per minute.
Comparative example 1: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
S1: weighing the following raw materials: 10kg of calcium salt, 3kg of zinc salt, 5kg of lubricant and 2kg of antioxidant;
s2: dissolving calcium salt and zinc salt in 145kg of solvent, and uniformly stirring to obtain a mixed solution;
S3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50 ℃;
s4: adding an antioxidant, reacting for 1 hour, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
S6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 10 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium stearate.
The zinc salt in the S1 is zinc stearate.
The lubricant in the step S1 is paraffin.
The antioxidant in the S1 is 2, 6-di-tert-butyl-4-methylphenol (BHT).
The solvent in the S2 is ethanol.
The reduced pressure evaporation temperature in the step S5 is 40 ℃, the vacuum degree is 200mbar, and the rotating speed of the rotary evaporation bottle is 60 revolutions per minute.
Comparative example 2: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
s1: weighing the following raw materials: 10kg of calcium salt, 3kg of zinc salt, 5kg of lubricant, 2kg of antioxidant and 0.2kg of synergist;
s2: dissolving calcium salt and zinc salt in 145kg of solvent, and uniformly stirring to obtain a mixed solution;
S3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50 ℃;
s4: adding an antioxidant, reacting for 1 hour, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
S6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 10 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium stearate.
The zinc salt in the S1 is zinc stearate.
The lubricant in the step S1 is paraffin.
The antioxidant in the S1 is 2, 6-di-tert-butyl-4-methylphenol (BHT).
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred reaction kettle, air is replaced by nitrogen, the addition amount of trans-epoxy-o-methyldione is 20kg, and the addition amount of 5-aminobenzimidazole is 7kg; 200kg of DMF; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 2kg; carrying out reaction at 50 ℃ and normal pressure; the reaction mixture was stirred for 50 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in the S2 is ethanol.
The reduced pressure evaporation temperature in the step S5 is 40 ℃, the vacuum degree is 200mbar, and the rotating speed of the rotary evaporation bottle is 60 revolutions per minute.
Comparative example 3: the preparation method of the special calcium-zinc stabilizer for the PVC transparent film comprises the following operation steps:
s1: weighing the following raw materials: 10kg of calcium salt, 3kg of zinc salt, 5kg of lubricant, 2kg of antioxidant and 0.2kg of synergist;
s2: dissolving calcium salt and zinc salt in 145kg of solvent, and uniformly stirring to obtain a mixed solution;
S3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50 ℃;
s4: adding an antioxidant, reacting for 1 hour, and filtering to remove insoluble matters;
s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;
S6: and (3) crushing the calcium-zinc stabilizer solid to a particle size of 10 microns to obtain the calcium-zinc stabilizer special for the PVC transparent film.
The calcium salt in S1 is calcium stearate.
The zinc salt in the S1 is zinc stearate.
The lubricant in the step S1 is paraffin.
The antioxidant in the S1 is 2, 6-di-tert-butyl-4-methylphenol (BHT).
The preparation method of the synergist in the S1 comprises the following steps:
In a stirred tank reactor, air was replaced with nitrogen, the amount of trans-epoxyo-methyldione added was 20kg, and the amount of 1, 2-dimercapto-carborane (CAS: 23810-63-1) added was 10kg; 200kg of DMF; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 2kg; carrying out reaction at 50 ℃ and normal pressure; the reaction mixture was stirred for 50 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
The solvent in the S2 is ethanol.
The reduced pressure evaporation temperature in the step S5 is 40 ℃, the vacuum degree is 200mbar, and the rotating speed of the rotary evaporation bottle is 60 revolutions per minute.
Test method and results:
In order to verify the effect of the calcium zinc stabilizer in the invention, systematic tests are carried out on the prepared stabilizer, mainly comprising oxidation resistance and thermal stability tests. The following are specific test methods and test results.
1. Oxidation resistance test
The device comprises: oxidation induction time tester (OIT, oxidation induction time)
Sample preparation: the calcium zinc stabilizers prepared in example 1-example 4 and comparative example 1-comparative example 3 were prepared as test samples weighing 10mg, respectively.
Test conditions: the sample was warmed from room temperature to 200 ℃ at a warming rate of 10 ℃/min under nitrogen atmosphere, then oxygen was introduced at 200 ℃ and the oxidation induction time was recorded.
Table 1: results of antioxidant tests of examples and comparative examples
The results show that the calcium zinc stabilizer has long oxidation induction time and can effectively improve the oxidation resistance of PVC.
2. Thermal stability test
The device comprises: thermogravimetric analyzer (TGA)
Sample preparation: 5 parts of the calcium zinc stabilizers prepared in examples 1 to 4 and comparative examples 1 to 3 of the present invention were weighed respectively, mixed with 100 parts of PVC, and a transparent film was prepared, and the prepared PVC transparent film was cut into small pieces having a weight of 10mg for thermogravimetric analysis test.
Test conditions: the temperature was increased from room temperature to 600℃at a heating rate of 10℃per minute under a nitrogen atmosphere.
Table 2: results of the thermal stability test of each of examples and comparative examples
From the test results, the weight retention rate of the PVC transparent film containing the calcium zinc stabilizer of the embodiment of the invention at different temperatures is superior to that of the comparative example, which shows that the heat stability of the PVC transparent film is obviously improved.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (7)
- The preparation method of the special calcium-zinc stabilizer for the PVC transparent film is characterized by comprising the following steps of: the operation steps are as follows:S1: weighing the following raw materials in parts by weight: 10-15 parts of calcium salt, 3-8 parts of zinc salt, 5-10 parts of lubricant, 2-5 parts of antioxidant and 0.2-1 part of synergist;S2: dissolving calcium salt and zinc salt in 145-160 parts of solvent, and uniformly stirring to obtain a mixed solution;s3: adding the lubricant into the mixed solution, continuously stirring, and keeping the temperature at 50-70 ℃;s4: adding antioxidant, reacting for 1-2 hours, filtering to remove insoluble substances;s5: evaporating the reaction solution to dryness under reduced pressure to obtain calcium zinc stabilizer solid;S6: crushing the calcium zinc stabilizer solid to the particle size of 10-30 microns to obtain the calcium zinc stabilizer special for the PVC transparent film;The preparation method of the synergist in the S1 comprises the following steps:according to the parts by weight, using nitrogen to replace air in a stirring reaction kettle, wherein the addition amount of trans-epoxy o-methyl diketone is 20-40 parts, and the addition amount of 5-amino benzimidazole is 7-14 parts; the addition amount of the 1, 2-dimercapto-carborane is 10-20 parts; 200-400 parts of DMF; sodium ethoxide is used as a catalyst, and the addition amount of the sodium ethoxide is 2-15 parts; reacting at 50-60 ℃ and normal pressure; stirring the reaction mixture for 50-120 minutes; the post-treatment mode comprises rotary steaming to remove DMF, thus obtaining the synergist.
- 2. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the calcium salt in the S1 is one or more of calcium stearate and calcium caprate.
- 3. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the zinc salt in the S1 is one or more of zinc stearate, zinc caprate and zinc acetate.
- 4. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the lubricant in the S1 is one or more of paraffin wax, polyethylene wax or stearic acid.
- 5. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the antioxidant in the S1 is one or more of 2, 6-di-tert-butyl-4-methylphenol (BHT), antioxidant 1010 or antioxidant 168.
- 6. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the solvent in the S2 is one or more of ethanol, propanol and ethyl acetate.
- 7. The method for preparing the calcium-zinc stabilizer special for the PVC transparent film, which is characterized in that: the reduced pressure evaporation temperature in the step S5 is 40-70 ℃, the vacuum degree is 200-300mbar, and the rotating speed of the rotary evaporation bottle is 60-100 revolutions per minute.
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