CN115340709A - Antioxidant stabilizer composition, polypropylene special material and preparation method of polypropylene special material - Google Patents
Antioxidant stabilizer composition, polypropylene special material and preparation method of polypropylene special material Download PDFInfo
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- CN115340709A CN115340709A CN202210955475.0A CN202210955475A CN115340709A CN 115340709 A CN115340709 A CN 115340709A CN 202210955475 A CN202210955475 A CN 202210955475A CN 115340709 A CN115340709 A CN 115340709A
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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 105
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 104
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 67
- -1 polypropylene Polymers 0.000 title claims abstract description 67
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000003381 stabilizer Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007970 thio esters Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000000155 melt Substances 0.000 claims description 13
- 229940043430 calcium compound Drugs 0.000 claims description 6
- 150000001674 calcium compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims 3
- 230000009471 action Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an antioxidant stabilizer composition, which comprises the following components: hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and acid acceptor; the hindered phenol antioxidant is selected from one or more of a compound with a structure shown in a formula (AO-1), a compound with a structure shown in a formula (AO-2) and a compound with a structure shown in a formula (AO-3); the phosphite antioxidant is selected from one or two of a compound with a structure of a formula (PS-1) and a compound with a structure of a formula (PS-2); the thioester antioxidant is selected from a compound with a structure of formula (TS-1); the antioxidant has the combined action, so that the obtained composition has high antioxidant effect, low volatilization and no migration, and the antioxidant performance and quality can be obviously improved by adding the antioxidant into the special material for the polypropylene pipe, and the service cycle of the polypropylene pipe product is prolonged.
Description
Technical Field
The invention relates to the technical field of high polymer material additives, in particular to an antioxidant stabilizer composition, a polypropylene special material and a preparation method of the polypropylene special material.
Background
In the processing and daily use process of the high polymer material, the high polymer material is easily influenced by oxygen, light, heat or metal ion impurities in the air, and free radical reaction occurs, so that the problems of color change, cracking and loss of glossiness of the polymer are caused, on one hand, the appearance becomes unattractive, and on the other hand, the mechanical property is reduced more seriously.
Thermal oxidative aging is a change of polypropylene all the time, is a main cause of oxidative degradation of polypropylene, seriously affects the appearance and processing stability of polypropylene, and needs to add a stabilizer to improve the processing stability and product performance of polypropylene. In the production and storage process of polypropylene, the polypropylene is aged due to the action of heat and oxygen in the air, and in the production process of polypropylene, the residual of catalyst used in the polymerization process, equipment corrosion and other factors cause that the polypropylene contains harmful metal ions of titanium, magnesium, chlorine and the like, and the harmful metal ions play a role in catalyzing the oxidation reaction of the polypropylene, so that the oxidation aging speed of the polypropylene is accelerated.
The national standard GB/T18742.1-2017 part 2 pipe of a polypropylene pipeline system for cold and hot water carries out standardized convention on quality technical indexes of polypropylene pipes, wherein the index which has the closest relationship with a stabilizer is a melt index, and the melt index of the pipe material is required to be not more than 0.5g/10min; secondly, the oxidation induction time is required to be not less than 20 minutes at 210 ℃, the yellow index is an important characterization index of the color characteristic of the plastic without pigment and carbon black, the national standard GB/T2409 plastic yellow index test method makes a standardized agreement on the detection of the index, the smaller the yellow index is, the lighter the yellowing is, and the better the color stability is.
The aging of polypropylene macroscopically shows oxidation chain scission, the yellow index of the polypropylene pipe material is increased due to yellowing of the color after aging, the melt index is increased and the stability is poor due to oxidation chain scission, and the instability of the melt index seriously influences the processing of the polypropylene, the mechanical property of a product and the long-term use stability. In order to prevent aging during the post-treatment processing and storage of polypropylene pipe materials, it is necessary to add suitable stabilizers after the end of polymerization to provide stability protection early on.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an antioxidant stabilizer composition which is high in antioxidant efficiency, resistant to water extraction and capable of remarkably improving the antioxidant performance of a special polypropylene material.
In view of the above, the present application provides an antioxidant stabilizer composition comprising: hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and acid acceptor;
the hindered phenol antioxidant is selected from one or more of a compound with a structure shown in a formula (AO-1), a compound with a structure shown in a formula (AO-2) and a compound with a structure shown in a formula (AO-3);
the phosphite antioxidant is selected from one or two of a compound with a structure of a formula (PS-1) and a compound with a structure of a formula (PS-2);
the thioester antioxidant is selected from a compound with a structure of formula (TS-1);
preferably, the acid acceptor is selected from one or two of organic calcium compound and organic zinc compound.
Preferably, the organic calcium compound is selected from calcium stearate.
Preferably, the organozinc compound is selected from zinc stearate.
Preferably, the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant and the acid acceptor is 1: (0.2-1): (0.1-0.5): (0.1-0.5).
Preferably, the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant and the acid acceptor is 1: (0.3-0.8): (0.2-0.4): (0.2-0.4).
The application also provides a special material for polypropylene, which comprises polypropylene and the antioxidant stabilizer composition.
Preferably, the mass ratio of the polypropylene to the antioxidant stabilizer composition is 100: (0.5-1.0).
The application also provides a preparation method of the special polypropylene material, which comprises the following steps:
mixing polypropylene and an antioxidant stabilizer composition to obtain a mixture;
and extruding and granulating the mixture in a double-screw extruder to obtain the special polypropylene material.
Preferably, the temperature of a first zone of the double-screw extruder is 210-230 ℃, the temperature of a second zone is 220-240 ℃, the temperature of a third zone is 230-250 ℃, the temperature of a fourth zone is 230-250 ℃, the temperature of a fifth zone is 220-240 ℃, the temperature of a machine head is 210-230 ℃, and the temperature of a melt is 220-240 ℃; the melt pressure is 0.1-0.2 MPa, the host current is 5.0-6.0A, the host rotating speed is 15-25 r/min, and the main feeding is changed into 15-20 r/min.
The application provides an antioxidant stabilizer composition, which selects specific hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and acid acceptor; the antioxidant has the combined action, so that the obtained composition has the advantages of oxidation resistance, low energy consumption, low volatilization and no migration, and the oxidation resistance and the quality of the special polypropylene material can be obviously improved by adding the antioxidant into a polypropylene pipe product. The experimental results show that: compared with the polypropylene pipe material added with the traditional antioxidant, the polypropylene pipe material added with the antioxidant stabilizer composition has the advantages that the processing stability and the extraction resistance are obviously improved, and the comprehensive thermal-oxidative aging resistance is obviously improved.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problem that the addition amount and performance of an antioxidant stabilizer in the prior art do not reach the standard, the application provides the antioxidant stabilizer, which has high antioxidant efficiency and water extraction resistance by selecting a specific antioxidant stabilizer, and can obviously improve the antioxidant performance of the special polypropylene material under the condition of small addition amount. Specifically, the embodiment of the invention discloses an antioxidant stabilizer composition, which comprises the following components in part by weight: hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and acid acceptor;
the hindered phenol antioxidant is selected from one or more of a compound with a structure of formula (AO-1), a compound with a structure of formula (AO-2) and a compound with a structure of formula (AO-3);
the phosphite antioxidant is selected from one or two of a compound with a structure of a formula (PS-1) and a compound with a structure of a formula (PS-2);
the thioester antioxidant is selected from a compound with a structure of formula (TS-1);
in the antioxidant stabilizer composition provided by the application, the phosphite antioxidant is a bio-based antioxidant which is synthesized by reacting bio-based raw material cardanol instead of chemically synthesized alkylphenol with phosphorus trichloride, does not contain nonylphenol, and is safe and healthy, and comprises a compound with a structure represented by formula (PS-1) and/or a compound with a structure represented by formula (PS-2).
In the present invention, the hindered phenol antioxidant is selected from one or more of a compound having a structure of formula (AO-1), a compound having a structure of formula (AO-2), and a compound having a structure of formula (AO-3):
the sources of the compound having the structure of the formula (AO-1), the compound having the structure of the formula (AO-2) and the compound having the structure of the formula (AO-3) are not particularly limited, and commercially available products can be used or the compounds can be synthesized by a conventional method.
In the present application, the acid acceptor is selected from one or both of an organic calcium compound and an organic zinc compound, more specifically, the organic calcium compound is selected from calcium stearate (CaSt), and the organic zinc compound is selected from zinc stearate (ZnSt).
In the present application, the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant, and the acid acceptor is 1: (0.2-1): (0.1-0.5): (0.1 to 0.5); more specifically, the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant and the acid acceptor is 1: (0.3-0.8): (0.2-0.4): (0.2-0.4).
In the antioxidant stabilizer composition provided by the application, the hindered phenol antioxidant is a core foundation of the stabilizer composition and mainly plays a role in eliminating free radicals, the phosphite antioxidant is an auxiliary component and assists in eliminating hydroperoxide, problems of precipitation, hydrolysis and the like easily occur due to excessive content, the thioester antioxidant also plays a role in eliminating hydroperoxide, bad smell and precipitation risk are caused due to excessive content, the acid-absorbing agent mainly plays a role in neutralizing acidic substances and passivation catalyst residues in materials, and excessive content can cause excessive ash content of products and influence the processing stability, color and long-term stability of the products.
The application also provides a special material for polypropylene, in particular a special material for polypropylene pipes, which comprises polypropylene and the antioxidant stabilizer composition in the scheme.
In the present application, the mass ratio of the polypropylene and the antioxidant stabilizer composition is 100: (0.5 to 1.0); more specifically, the mass ratio of the polypropylene to the antioxidant stabilizer composition is 100: (0.6-0.8). In the polypropylene special material provided by the application, the long-acting stability is influenced by the excessively small addition amount of the antioxidant stabilizer composition, so that the service life of a product is shortened, the requirement on the service life of a pipe material in municipal construction and industrial fields is difficult to meet, the precipitation risk is large due to the excessively large addition amount, and the mechanical property of the special material is also influenced.
The application also provides a preparation method of the special polypropylene material, which comprises the following steps:
mixing polypropylene and an antioxidant stabilizer composition to obtain a mixture;
and extruding and granulating the mixture for three times in a double-screw extruder to obtain the special material for polypropylene.
In the preparation process of the special polypropylene material, the temperature of a first zone of the double-screw extruder is 210-230 ℃, the temperature of a second zone is 220-240 ℃, the temperature of a third zone is 230-250 ℃, the temperature of a fourth zone is 230-250 ℃, the temperature of a fifth zone is 220-240 ℃, the temperature of a machine head is 210-230 ℃, and the temperature of a melt is 220-240 ℃; the melt pressure is 0.1-0.2 MPa, the current of the main machine is 5.0-6.0A, the rotating speed of the main machine is 15-25 r/min, and the main feeding is changed into 15-20 r/min.
In the application, the polypropylene special material is a special material for a polypropylene pipe material.
The invention provides an antioxidant stabilizer composition suitable for improving the oxidation resistance of a polypropylene pipe material aiming at the characteristics of the production and processing processes of the polypropylene pipe material. The antioxidant stabilizer composition provided by the invention has the characteristics of good antioxidant effect, water extraction resistance, no migration and the like, and the antioxidant performance and quality of a polypropylene pipe material can be obviously improved by adding the antioxidant stabilizer composition into the polypropylene pipe material. The experimental results show that: compared with the polypropylene pipe material added with the traditional antioxidant, the polypropylene pipe material added with the antioxidant stabilizer composition has the advantages that the processing stability and the extraction resistance are obviously improved, and the comprehensive thermal-oxidative aging resistance is obviously improved.
The special polypropylene material provided by the invention is added with the antioxidant stabilizer composition provided by the invention, so that the special polypropylene material has higher antioxidant performance and quality. The experimental results show that: compared with a polypropylene pipe material added with a traditional antioxidant, the polypropylene pipe material provided by the application has the advantages that the processing stability and the oxidation induction period time are obviously prolonged, and the comprehensive thermal-oxidative aging resistance is obviously improved.
For further understanding of the present invention, the following examples are provided to illustrate the antioxidant stabilizer composition and its application in detail, and the scope of the present invention is not limited by the following examples.
Examples
1) Uniformly mixing an antioxidant stabilizer according to a specified amount in a table 2 (the mass percentage in the table is based on 100g of polypropylene tube material base stock) with 500 g of polypropylene tube material base stock (PPR, the mark is PA14D, the initial melt index is 0.2, and the initial yellow index is-0.3);
2) Carrying out three times of extrusion granulation in a double-screw extruder, wherein the sample of the first time extrusion granulation particle and the sample of the third time extrusion granulation particle are about 50 g, and the sample of the second time extrusion particle is about 100 g; about 100 grams before the first extrusion and about 50 grams before the second and third extrusion after each formula switching are used as transition materials, and the effectiveness of the sample retention particle characteristics is kept.
3) The melt index, yellowness index of the second extruded pellet, OIT of each sample were measured.
The information of the double-screw extruder and the detection instrument is as follows:
a double-screw extruder: SHJ-20 Co-rotating twin screw extruder, with a1 hour throughput of about 5 kg, the main extruder operating parameters are shown in Table 1:
TABLE 1 Main operating parameters of the twin-screw extruder
And (3) detecting the yellow index: SC-80C full-automatic color difference meter;
and (3) detecting the melt index: GT-7100MI fusion instrument, chengde Jin Jian instruments, inc.
The results are shown in table 2:
TABLE 2 statistical table of the melt index, yellow index, and oxidation induction period
Note: other numbered antioxidants are known to those skilled in the art.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An antioxidant stabilizer composition comprising: hindered phenol antioxidant, phosphite antioxidant, thioester antioxidant and acid acceptor;
the hindered phenol antioxidant is selected from one or more of a compound with a structure of formula (AO-1), a compound with a structure of formula (AO-2) and a compound with a structure of formula (AO-3);
the phosphite antioxidant is selected from one or two of a compound with a structure of a formula (PS-1) and a compound with a structure of a formula (PS-2);
the thioester antioxidant is selected from a compound with a structure of formula (TS-1);
2. the antioxidant stabilizer composition of claim 1, wherein the acid scavenger is selected from one or both of an organic calcium compound and an organic zinc compound.
3. The antioxidant stabilizer composition of claim 2, wherein the organic calcium compound is selected from calcium stearate.
4. The antioxidant stabilizer composition of claim 2, wherein the organozinc compound is selected from zinc stearate.
5. The antioxidant stabilizer composition as set forth in claim 1 or 2, wherein the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant and the acid scavenger is 1: (0.2-1): (0.1-0.5): (0.1-0.5).
6. The antioxidant stabilizer composition as claimed in claim 5, wherein the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant and the acid scavenger is 1: (0.3-0.8): (0.2-0.4): (0.2-0.4).
7. A polypropylene special material, comprising polypropylene and the antioxidant stabilizer composition as claimed in any one of claims 1 to 6.
8. The polypropylene special material as claimed in claim 7, wherein the mass ratio of the polypropylene to the antioxidant stabilizer composition is 100: (0.5-1.0).
9. The method for preparing the polypropylene special material as claimed in claim 7, which comprises the following steps:
mixing polypropylene and an antioxidant stabilizer composition to obtain a mixture;
and extruding and granulating the mixture in a double-screw extruder to obtain the special polypropylene material.
10. The preparation method of claim 9, wherein the temperature of the first zone of the twin-screw extruder is 210 to 230 ℃, the temperature of the second zone is 220 to 240 ℃, the temperature of the third zone is 230 to 250 ℃, the temperature of the fourth zone is 230 to 250 ℃, the temperature of the fifth zone is 220 to 240 ℃, the temperature of the head is 210 to 230 ℃, and the temperature of the melt is 220 to 240 ℃; the melt pressure is 0.1-0.2 MPa, the host current is 5.0-6.0A, the host rotating speed is 15-25 r/min, and the main feeding is changed into 15-20 r/min.
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| CN116396558A (en) * | 2023-03-13 | 2023-07-07 | 天津大学 | High dielectric property polypropylene film based on ash removal and preparation method thereof |
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