CN118109000A - Composite antioxidant, preparation and application thereof in polypropylene - Google Patents
Composite antioxidant, preparation and application thereof in polypropylene Download PDFInfo
- Publication number
- CN118109000A CN118109000A CN202211509106.5A CN202211509106A CN118109000A CN 118109000 A CN118109000 A CN 118109000A CN 202211509106 A CN202211509106 A CN 202211509106A CN 118109000 A CN118109000 A CN 118109000A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- polypropylene
- carbon black
- white carbon
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 127
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 120
- -1 polypropylene Polymers 0.000 title claims abstract description 103
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 98
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000006229 carbon black Substances 0.000 claims abstract description 57
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000005060 rubber Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000007921 spray Substances 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 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 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 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 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- KMWIPXLIKIAZMT-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanehydrazide Chemical compound CC(C)(C)C1=CC(CCC(=O)NN)=CC(C(C)(C)C)=C1O KMWIPXLIKIAZMT-UHFFFAOYSA-N 0.000 claims description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 2
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 claims description 2
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229950006451 sorbitan laurate Drugs 0.000 claims description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 2
- 229960004274 stearic acid Drugs 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims 1
- 229940080818 propionamide Drugs 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 15
- 238000012360 testing method Methods 0.000 abstract description 13
- 238000001694 spray drying Methods 0.000 abstract description 8
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002861 polymer material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 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 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002516 radical scavenger 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K5/49—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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention provides a preparation method of a high-efficiency composite antioxidant. Adding the white carbon black, the primary antioxidant, the auxiliary antioxidant and the coupling agent into ethanol to prepare a solution, and spray-drying to prepare the white carbon black loaded antioxidant. And adding the ethylene propylene rubber, the dispersing agent and the white carbon black loaded antioxidant into an internal rubber mixer to obtain the white carbon black loaded antioxidant master batch. And finally, extruding and granulating the white carbon black loaded antioxidant master batch to obtain the high-efficiency composite antioxidant. And adding a high-efficiency composite antioxidant in the later polymerization stage of polypropylene, devolatilizing and drying, and granulating by using a double screw to obtain a polypropylene sample bar for testing. The test result shows that the high-efficiency composite antioxidant has obviously better antioxidation effect on polypropylene than the traditional composite antioxidant, wherein the aging coefficient is improved by 24.5-31.5% compared with the traditional composite antioxidant. Meanwhile, compared with the traditional product, the product of the invention has greatly reduced usage amount, and the usage amount of the product of the invention with the same antioxidation effect is only 12.2 to 23.4 percent of that of the traditional product. In another aspect, the product of the invention is a white powder useful for transparent or light colored plastic rubber articles.
Description
Technical Field
The invention relates to a preparation method of a high-efficiency composite antioxidant, belongs to the technical field of high-molecular material antioxidant modification, and particularly relates to a preparation method of a high-efficiency composite antioxidant and application of the high-efficiency composite antioxidant in polypropylene.
Background
The antioxidant is one of the auxiliary agents necessary for the high polymer material, and has the following general functions: (1) And the polymer material acts as a free radical scavenger in the later polymerization period to accelerate the termination of the polymerization reaction. (2) And the polymer is filled in the processing process of the polymer, so that the storage and service life of the polymer material are prolonged. Almost all polymer materials need to use antioxidants in the polymerization or processing process, and the total dosage of the antioxidants is about 1% of that of the polymer materials, so that the dosage is huge. In the prior art, more than two antioxidants are compounded to play a role in synergizing and resisting oxidation of a high polymer material, but the use efficiency of the antioxidant is low, and the antioxidant is easy to change color integrally due to multi-component compounding, so that a plurality of inconveniences are brought to the preparation of transparent and light-colored products. Meanwhile, the high-end polymer material has definite upper limit on the addition amount of various auxiliary agents, namely the smaller the addition amount of the required antioxidant is, the better the addition amount of the required antioxidant is, and the quality requirement of the material cannot be met by the existing antioxidant preparation technology.
According to the invention, the white carbon black, the antioxidant and the coupling agent are subjected to spray drying technology to generate the white carbon black loaded antioxidant, and then the white carbon black loaded antioxidant, the ethylene propylene rubber and other auxiliary agents are mixed and granulated to prepare the efficient composite antioxidant.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention provides a preparation method of a high-efficiency composite antioxidant.
The invention provides a preparation method of a high-efficiency composite antioxidant, which comprises the following steps and conditions:
According to the invention, a spray dryer is used for mixing and drying white carbon black, a main antioxidant, an auxiliary antioxidant and a coupling agent to prepare a white carbon black loaded antioxidant, and then in an internal rubber mixer, the propyl rubber, a dispersing agent and the white carbon black loaded antioxidant are sequentially added to prepare the white carbon black loaded antioxidant master batch. And finally, extruding and granulating the white carbon black loaded antioxidant master batch to obtain the high-efficiency composite antioxidant. Compared with the traditional product, the product of the invention can obviously improve the ageing resistance of polypropylene, and simultaneously, the product of the invention greatly reduces the use amount compared with the traditional product, and can be used for transparent or light-colored plastic rubber products.
The spray dryer used in the invention is not limited to model and condition parameters, and can be used for preparing various white carbon black, antioxidants and auxiliaries into spray drying;
The single screw extruder, the internal rubber mixer, the double screw extruder and the injection molding machine used in the invention are not limited in model and condition parameters, and only the polypropylene, the antioxidant and the auxiliary agent can be uniformly mixed;
the white carbon black adopted by the invention is fumed silica and precipitated silica hydrate, the fumed silica grade is A200, and the precipitated silica grade is WL-80.
The main antioxidants adopted in the invention are pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), n-stearyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate (1076), 2, 6-di-tert-butyl-p-methylphenol (264), 2' -methylenebis (4-methyl-6-tert-butylphenol) (2246) and 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (330).
The auxiliary antioxidants used in the invention are N, N '-1, 6-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ] (1098), N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (1024), tris (2, 4-di-tert-butylphenyl) phosphite (168) and 2, 2-oxamido-bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) ] propionate (697).
The coupling agent used in the invention is one or more of vinyl tri (beta-methoxyethoxy) silane (A172), vinyl trichlorosilane (A150), gamma-aminopropyl triethoxysilane (A-1100), vinyl triethoxysilane (A151), methyl mercaptopropyl dimethoxysilane, bis [ (3-triethoxysilyl) propyl ] tetrasulfide (Si-69), preferably vinyl triethoxysilane (A151) and bis [ (3-triethoxysilyl) propyl ] tetrasulfide (Si-69).
The ethylene propylene rubber adopted by the invention is produced by medium petroleum Ji chemical company and has the marks of 4045, 3080 and 3092.
The dispersing agent used in the present invention includes sodium dodecyl benzene sulfonate, stearic acid, sorbitan laurate (SP-20), sorbitan fatty acid ester (SP-80), polyoxyethylene sorbitan monooleate (TWEEN 80), polyoxyethylene sorbitan tristearate (TWEEN 65).
The invention is implemented as follows
(A) In a spray dryer, white carbon black, a main antioxidant, an auxiliary antioxidant and a coupling agent are mixed according to the mass ratio of 100: 50-80: 30-50: 5-10 (preferably 100:65-75:35-45:7-9) of the raw materials are added into ethanol with the mass which is 5-10 times that of the raw materials to prepare a solution, and the solution is stirred, sprayed and dried, the temperature of a spray dryer is 150-250 ℃, and the spraying speed is 20-80 ml/min, so that the white carbon black loaded antioxidant is obtained;
(b) In an internal mixer, adding ethylene propylene rubber, a dispersing agent and a white carbon black loaded antioxidant into the internal mixer, wherein the mass ratio of the components is 50-100: 1 to 5: 20-80 (preferably 60-90:2-4:30-70), wherein the temperature of the internal mixer is 50-100 ℃, the rotating speed is 20-120 r/min, and after mixing for 5-10 minutes, rubber is discharged to prepare the white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 25-100 ℃, extruding at 10-30 rpm, extruding the rubber strips, and then air-cooling and granulating to obtain the composite antioxidant.
The beneficial effects are that:
compared with the prior art, the invention has the following beneficial effects:
(a) The high-efficiency composite antioxidant can obviously improve the antioxidation effect of a high polymer material, particularly polypropylene, wherein the aging coefficient is improved by 24.5-31.5 percent compared with that of the traditional composite antioxidant, and the aging coefficient is shown in a table 1 in detail.
(B) The high-efficiency composite antioxidant has the same antioxidation effect, the usage amount is less than that of the traditional composite antioxidant, and the usage amount is only 12.2-23.4% of that of the traditional composite antioxidant, and is shown in table 1.
(C) The high-efficiency composite antioxidant can improve the physical and mechanical properties of polypropylene, wherein the tensile strength is improved by 5.6 to 12.1 percent, and the elongation at break is improved by 29.0 to 225.0 percent.
(D) The high-efficiency composite antioxidant is white particles, and can be used for preparing transparent or light-colored high-molecular plastic rubber products.
Detailed Description
Example 1:
the preparation method comprises the following steps and conditions:
(a) In a spray dryer, white carbon black A200, a primary antioxidant 1010, an auxiliary antioxidant 168 and a coupling agent A172 are mixed according to the mass ratio of 100:50:30:5, adding the mixture into ethanol with the mass being 5 times of that of the mixture to prepare a solution, stirring, spray drying, and spraying at the temperature of 150 ℃ and the spraying speed of 20 ml/min to obtain the white carbon black loaded antioxidant;
(b) In an internal mixer, ethylene propylene rubber 4045, sodium dodecyl benzene sulfonate serving as a dispersing agent and a white carbon black loaded antioxidant are added into the internal mixer, wherein the mass ratio of the components is 50:1:20, mixing for 10 minutes at the temperature of 50 ℃ at the rotating speed of 20 rpm in an internal mixer, and discharging rubber to prepare a white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 25 ℃, extruding at 10 revolutions per minute, extruding the adhesive tape, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant;
(d) Adding high-efficiency composite antioxidant (0.5% of the total mass of polypropylene) after the polymerization process of polypropylene, then placing the polypropylene into a 115 ℃ oven for devolatilization drying, taking out polypropylene powder after 12 hours of drying, placing the polypropylene powder into a double-screw extruder for pelleting, placing the polypropylene particles into an injection machine for sample preparation, and obtaining polypropylene sample bars at 180 ℃ of the injection machine for testing.
Example 2:
the preparation method comprises the following steps and conditions:
(a) In a spray dryer, white carbon black WL-80, a primary antioxidant 1010, a primary antioxidant 1076, an auxiliary antioxidant 168 and a coupling agent 151 are mixed according to a mass ratio of 100:40:30:40:8, adding the mixture into ethanol with the mass being 8 times of that of the mixture to prepare a solution, stirring, spray drying, and obtaining the white carbon black loaded antioxidant at the spray speed of 50 ml/min at the temperature of 180 ℃ of a spray dryer;
(b) In an internal mixer, adding ethylene propylene rubber 3092, dispersant stearic acid and white carbon black loaded antioxidant into the internal mixer, wherein the mass ratio of the components is 80:3:40, mixing for 8 minutes at the temperature of 60 ℃ at the rotating speed of 40 rpm in an internal mixer, and discharging rubber to prepare a white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 80 ℃, extruding at 20 rpm, extruding the adhesive tape, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant;
(d) Adding a high-efficiency composite antioxidant (1% of the total mass of the polypropylene) after the polymerization process of the polypropylene, then putting the polypropylene into a baking oven at 120 ℃ for devolatilization drying, taking out polypropylene powder after drying for 8 hours, putting the polypropylene powder into a double-screw extruder for granulating, putting the polypropylene particles into an injection machine for sample preparation, and obtaining a polypropylene sample bar at the temperature of 195 ℃ of the injection machine for testing.
Example 3:
the preparation method comprises the following steps and conditions:
(a) In a spray dryer, white carbon black A200, a primary antioxidant 2246, an auxiliary antioxidant 1098 and a coupling agent Si-69 are mixed according to the mass ratio of 100:80:50:10 is added into ethanol with the mass of 10 times to prepare solution, and the solution is stirred, sprayed and dried, the temperature of a spray dryer is 250 ℃, and the spraying speed is 80 ml/min, so as to obtain the white carbon black loaded antioxidant;
(b) In an internal mixer, adding ethylene propylene rubber 3080, a dispersing agent SP-20 and a white carbon black load antioxidant into the internal mixer, wherein the mass ratio of each component is 100:5:80, mixing for 5 minutes at the temperature of 100 ℃ at the rotating speed of 120 r/min in an internal mixer, and discharging rubber to prepare a white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 100 ℃, extruding at 30 rpm, extruding the rubber strips, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant.
(D) Adding high-efficiency composite antioxidant (2% of the total mass of polypropylene) after the polymerization process of polypropylene, then placing the polypropylene into a 125 ℃ oven for devolatilization drying, taking out polypropylene powder after drying for 12 hours, placing the polypropylene powder into a double-screw extruder for pelleting, placing polypropylene particles into an injection machine for sample preparation, and obtaining polypropylene sample bars at the temperature of 200 ℃ of the injection machine for testing.
Example 4:
the preparation method comprises the following steps and conditions:
(a) In a spray dryer, white carbon black WL-80, a primary antioxidant 264, a primary antioxidant 330, an auxiliary antioxidant 1024 and a coupling agent A150 are mixed according to a mass ratio of 100:35:25:45:7, adding the mixture into ethanol with the mass being 7 times to prepare a solution, stirring, spray drying, and obtaining the white carbon black loaded antioxidant at the spray speed of 60 ml/min at the temperature of 185 ℃ of a spray dryer;
(b) In an internal mixer, ethylene propylene rubber 4045, a dispersing agent SP-80 and a white carbon black loaded antioxidant are added into the internal mixer, wherein the mass ratio of the components is 80:3:40, mixing for 9 minutes at the temperature of 65 ℃ at the rotating speed of 50 revolutions per minute in an internal mixer, and discharging rubber to prepare a white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 70 ℃, extruding at 30 rpm, extruding the adhesive tape, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant;
(d) Adding a high-efficiency composite antioxidant (1% of the total mass of the polypropylene) after the polymerization process of the polypropylene, then putting the polypropylene into a drying oven at 125 ℃ for devolatilization drying, taking out polypropylene powder after drying for 7 hours, putting the polypropylene powder into a double-screw extruder for granulating, putting the polypropylene particles into an injection machine for sample preparation, and obtaining a polypropylene sample bar at the temperature of 200 ℃ of the injection machine for testing.
Example 5:
the preparation method comprises the following steps and conditions:
(a) In a spray dryer, white carbon black WL-80, a primary antioxidant 1010, a primary antioxidant 1076, an auxiliary antioxidant 697 and a coupling agent A-1100 are mixed according to a mass ratio of 100:45:35:45: adding the mixture into ethanol with the mass being 8 times to prepare a solution, stirring, spray drying, and obtaining the white carbon black loaded antioxidant, wherein the temperature of a spray dryer is 185 ℃ and the spray speed is 60 ml/min;
(b) In an internal mixer, adding ethylene propylene rubber 3092, dispersant stearic acid and white carbon black loaded antioxidant into the internal mixer, wherein the mass ratio of the components is 85:3:35, mixing for 7 minutes at 50 ℃ at 50 rpm in an internal mixer, and discharging rubber to prepare a white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 70 ℃, extruding at 25 rpm, extruding the adhesive tape, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant;
(d) Adding high-efficiency composite antioxidant (1.5% of the total mass of polypropylene) after the polymerization process of polypropylene, then placing the polypropylene into a 115 ℃ oven for devolatilization drying, taking out polypropylene powder after drying for 7 hours, placing the polypropylene powder into a double-screw extruder for pelleting, placing the polypropylene particles into an injection machine for sample preparation, and obtaining polypropylene sample bars at the temperature of 190 ℃ of the injection machine for testing.
Comparative example 1:
Adding a compound antioxidant (a main antioxidant 1010: an auxiliary antioxidant 168 is 5:3, namely 1010 is added with 0.313 percent of the weight of the polypropylene, and 168 is added with 0.187 percent of the weight of the polypropylene) after the polymerization process of the polypropylene, then placing the polypropylene into a 115 ℃ oven for devolatilization drying, taking out polypropylene powder after 12 hours of drying, putting the polypropylene powder into a double-screw extruder for granulation, putting the polypropylene particles into an injector for sample preparation, and testing the polypropylene sample bars obtained at the temperature of 180 ℃ of the injector, wherein the oxidation resistance and the color state are shown in Table 1 in detail.
Comparative example 2:
adding a compound antioxidant (main antioxidant 1010: main antioxidant 1076: auxiliary antioxidant 168 is 4:3:4, namely 1010 is added with 0.364% of the weight of the polypropylene, 1076 is added with 0.272% of the weight of the polypropylene, 168 is added with 0.364% of the weight of the polypropylene) after the polymerization process of the polypropylene, then putting the polypropylene into a baking oven at 120 ℃ for devolatilization drying, taking out polypropylene powder after 8 hours of drying, putting the polypropylene powder into a double-screw extruder for pelleting, putting the polypropylene particles into an injection machine for sample preparation, and obtaining a polypropylene sample bar at the temperature of 190 ℃ of the injection machine for testing, wherein the oxidation resistance and the color state are shown in Table 1 in detail.
Comparative example 3:
Adding a compound antioxidant (main antioxidant 2246: auxiliary antioxidant 1098 is 8:5, namely 2246, 1.230 percent of the weight of the polypropylene is added, and 0.770 percent of the weight of the polypropylene is added into 1098) after the polymerization process of the polypropylene, then placing the polypropylene into a 125 ℃ oven for devolatilization drying, taking out polypropylene powder after 12 hours of drying, putting the polypropylene powder into a double-screw extruder for pelleting, putting the polypropylene particles into an injection machine for sample preparation, and testing the polypropylene sample bars obtained at the temperature of 200 ℃ of the injection machine, wherein the oxidation resistance and the color state are shown in Table 1 in detail.
Comparative example 4:
(a) In a spray dryer, white carbon black WL-80, a primary antioxidant 1010, a primary antioxidant 1076, an auxiliary antioxidant 168 and a coupling agent 151 are mixed according to a mass ratio of 100:40:30:40:8, adding the mixture into ethanol with the mass being 5 times of that of the mixture to prepare a solution, stirring, spray drying, and obtaining the white carbon black loaded antioxidant at the spray speed of 50 ml/min at the temperature of 180 ℃ of a spray dryer;
(b) Adding a white carbon black loaded antioxidant (1% of the total mass of the polypropylene) after the polymerization process of the polypropylene, then placing the polypropylene into a 115 ℃ oven for devolatilization drying, taking out polypropylene powder after drying for 8 hours, placing the polypropylene powder into a double-screw extruder for pelleting, placing the polypropylene particles into an injection machine for sample preparation, and obtaining a polypropylene sample bar at 185 ℃ of the injection machine for testing, wherein the oxidation resistance and the color state are shown in Table 1 in detail.
Comparative example 5:
(a) In an internal rubber mixer, ethylene propylene rubber 3092, dispersant stearic acid, a main antioxidant 1010, a main antioxidant 1076 and an auxiliary antioxidant 168 are added into the internal rubber mixer, and the mass ratio of the components is 80:3:14.5:11.0:14.5, mixing for 8 minutes at the temperature of 60 ℃ and the rotating speed of 40 revolutions per minute in an internal mixer, and discharging rubber to prepare a white carbon black load antioxidant master batch;
(b) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 50 ℃, extruding at 20 rpm, extruding the adhesive tape, and then air-cooling and granulating to obtain the high-efficiency composite antioxidant.
(C) Adding high-efficiency composite antioxidant (1% of the total mass of polypropylene) after the polymerization process of polypropylene, then placing the polypropylene into a baking oven at 120 ℃ for devolatilization drying, taking out polypropylene powder after drying for 8 hours, placing the polypropylene powder into a double-screw extruder for pelleting, placing polypropylene particles into an injection machine for sample preparation, and obtaining polypropylene sample bars at 190 ℃ of the temperature of the injection machine for testing, wherein the oxidation resistance and the color state are shown in Table 1 in detail.
TABLE 1 mechanical Properties, aging coefficient and color State of high-efficiency composite antioxidant
* Tensile Strength and elongation at Break according to "determination of tensile Properties of plastics of GB/T1040.2-2006 part 2: test conditions for molded and extruded plastics.
* Aging coefficient: aging conditions (100 ℃ C..times.96 hours) were calculated according to the following formula: aging coefficient = [ tensile strength after aging (MPa) x elongation at break (%) after aging ] = [ tensile strength before aging (MPa) x elongation at break (%) before aging ];
Examples 1 and comparative example 1, examples 2 and comparative example 2, and examples 3 and comparative example 3 are the same compounding ratio, and the performance data of the antioxidant prepared by the method of the present invention and the prior art. As can be seen from data comparison, the mechanical property, the ageing resistance and the color state of the high-efficiency composite antioxidant prepared by the method are better than those of the polypropylene prepared by the prior art in the same mixing proportion, and the high-efficiency composite antioxidant is one of the invention points of the invention.
The same compounding ratio is adopted in the example 3 and the comparative example 3, the comparative example 4 and the comparative example 5, and the performance indexes of the antioxidants prepared in different process steps are shown. The data comparison shows that any step of the method can be reduced to have influence on the mechanical property, ageing resistance and color state of the antioxidant matched with polypropylene. Examples 4 and 5 show the antioxidant properties of the antioxidants according to the process of the invention in different proportions and under different process conditions, respectively, and from the data in the table, the antioxidant effect of the antioxidants prepared according to the process of the invention is better than that of the products of the prior art. This also demonstrates the novelty and novelty of the technical route of the present invention, which is also one of the inventive aspects of the present invention.
On the other hand, as can be seen from the data in Table 1, the high-efficiency composite antioxidant prepared by the method of the invention is added into polypropylene in the late polymerization stage, and the tensile strength and elongation at break of the polypropylene are obviously superior to those of the polypropylene product of the traditional composite antioxidant. Wherein, the tensile strength is improved by 5.6 to 12.1 percent, and the elongation at break is improved by 29.0 to 225.0 percent. The antioxidation effect is more remarkable, the aging coefficient is improved by 24.5% -31.5%, and the high-compound antioxidant with the antioxidant content of 12.2% -23.4% can achieve the more excellent antioxidation effect of the traditional compound antioxidant. Therefore, the high-efficiency compound antioxidant can replace the existing compound antioxidant to be applied to high-end polymer materials.
Claims (8)
1. A preparation method of a composite antioxidant is characterized in that,
The preparation method comprises the following steps:
(a) In a spray dryer, white carbon black, a main antioxidant, an auxiliary antioxidant and a coupling agent are mixed according to the mass ratio of 100: 50-80: 30-50: 5-10 (preferably 100:65-75:35-45:7-9) of the raw materials are added into ethanol with the mass which is 5-10 times that of the raw materials to prepare a solution, and the solution is stirred, sprayed and dried, the temperature of a spray dryer is 150-250 ℃, and the spraying speed is 20-80 ml/min, so that the white carbon black loaded antioxidant is obtained;
(b) In an internal mixer, adding ethylene propylene rubber, a dispersing agent and a white carbon black loaded antioxidant into the internal mixer, wherein the mass ratio of the components is 50-100: 1 to 5: 20-80 (preferably 60-90:2-4:30-70), wherein the temperature of the internal mixer is 50-100 ℃, the rotating speed is 20-120 r/min, and after mixing for 5-10 minutes, rubber is discharged to prepare the white carbon black loaded antioxidant master batch;
(c) Adding the white carbon black loaded antioxidant master batch into a rubber single screw extruder, extruding at 25-100 ℃, extruding at 10-30 rpm, extruding the rubber strips, and then air-cooling and granulating to obtain the composite antioxidant.
2. The method according to claim 1, wherein,
The white carbon black in the step (a) is fumed silica and/or precipitated silica hydrate, the fumed silica grade is A200, and the precipitated silica grade is WL-80.
The main antioxidant in the step (a) is one or more than two of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate (1076), 2, 6-di-tert-butyl-p-methylphenol (264), 2' -methylenebis (4-methyl-6-tert-butylphenol) (2246) and 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (330);
The auxiliary antioxidant in the step (a) is one or more than two of N, N '-1, 6-subunit-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ] (1098), N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (1024), tris (2, 4-di-tert-butylphenyl) phosphite (168) and 2, 2-oxamido-bis [ ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) ] propionate (697);
The coupling agent in the step (a) is one or more of vinyl tri (beta-methoxyethoxy) silane (A172), vinyl trichlorosilane (A150), gamma-aminopropyl triethoxysilane (A-1100), vinyl triethoxysilane (A151), methyl mercaptopropyl dimethoxysilane, bis [ (3-triethoxysilyl) propyl ] tetrasulfide (Si-69), preferably one or more of vinyl triethoxysilane (A151) and bis [ (3-triethoxysilyl) propyl ] tetrasulfide (Si-69).
3. The method according to claim 1, wherein,
The ethylene propylene rubber in step (b) is produced by Ji Zhongjihua corporation and has one or more of the trade marks 4045, 3080 and 3092;
The dispersant in the step (b) comprises one or more of sodium dodecyl benzene sulfonate, stearic acid, sorbitan laurate (SP-20), sorbitan fatty acid ester (SP-80), polyoxyethylene sorbitan monooleate (TWEEN 80) and polyoxyethylene sorbitan tristearate (TWEEN 65).
4. The method according to claim 1, wherein,
The rubber single screw extruder in the step (c) is white carbon black loaded antioxidant master batch extrusion equipment, the screw diameter is 25+/-0.1 mm, the length-diameter ratio is 5-8, and the rotating speed is 20-40 revolutions per minute.
5. A composite antioxidant prepared by the method of any one of claims 1-4.
6. Use of the compound antioxidant of claim 5 in polypropylene.
7. The use according to claim 6, wherein,
Adding a composite antioxidant (accounting for 0.5-2% of the total mass of the polypropylene) after the polymerization process of the polypropylene, then placing the polypropylene into a baking oven at 115-125 ℃ for devolatilization drying, taking out polypropylene powder after drying for 6-12 hours, placing the polypropylene powder into a double screw extruder for pelleting, placing the polypropylene particles into an injection machine for sample preparation, and obtaining the polypropylene sample strip at the temperature of 180-200 ℃.
8. The use according to claim 6, wherein,
The double-screw extruder in the step (d) is special equipment for granulating polypropylene, the diameter of the screw is 35+/-0.1 mm, the length-diameter ratio is 15-20, and the rotating speed is 20-40 revolutions per minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211509106.5A CN118109000A (en) | 2022-11-29 | 2022-11-29 | Composite antioxidant, preparation and application thereof in polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211509106.5A CN118109000A (en) | 2022-11-29 | 2022-11-29 | Composite antioxidant, preparation and application thereof in polypropylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118109000A true CN118109000A (en) | 2024-05-31 |
Family
ID=91212573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211509106.5A Pending CN118109000A (en) | 2022-11-29 | 2022-11-29 | Composite antioxidant, preparation and application thereof in polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118109000A (en) |
-
2022
- 2022-11-29 CN CN202211509106.5A patent/CN118109000A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0069938A1 (en) | Image detection apparatus | |
| CN102643480B (en) | Anti-static alloy composite material and preparation method thereof | |
| WO2010074394A2 (en) | Polypropylene resin compositions having high melt tension and method for preparing the same | |
| CN109251399B (en) | Soft low-smoke halogen-free high-flame-retardant oil-resistant cable material for high-voltage line in vehicle and preparation method thereof | |
| CN108047493B (en) | Antioxidant composition for nylon | |
| CN112778684B (en) | Talcum powder filled polypropylene material with high yield strain and low-temperature impact resistance and preparation method thereof | |
| CN110437538B (en) | Polypropylene consumable for 3D printing and preparation method thereof | |
| CN112375324B (en) | HIPS (high impact polystyrene) composite material as well as preparation method and application thereof | |
| CN110218388A (en) | A kind of antiultraviolet ageing resistance polypropylene master batch and its manufacturing process | |
| CN107513210B (en) | Low-odor electroplatable polypropylene material and preparation method thereof | |
| CN110791031A (en) | Low-hardness brominated butyl rubber polypropylene thermoplastic elastomer | |
| CN1243051C (en) | Coloring agglomerate for polyethylene packing film and its prepn process | |
| JPH0319866B2 (en) | ||
| CN118109000A (en) | Composite antioxidant, preparation and application thereof in polypropylene | |
| CN103289388B (en) | In-situ compatibilized glass fiber reinforced nylon 66 composite material and preparation method thereof | |
| CN109627656B (en) | Transparent permanent antistatic PMMA material and preparation method and application thereof | |
| CN100345673C (en) | Preparing method for embedded expanding piece of car | |
| CN110845796A (en) | Polypropylene antistatic soft master batch and preparation method thereof | |
| CN114736452B (en) | Aging-resistant and antistatic polypropylene composition and preparation method and application thereof | |
| WO2013155961A1 (en) | Ethylene-propylene-diene monomer grafted maleic anhydride and preparation method therefor | |
| CN113861568B (en) | Polypropylene composite material and preparation method thereof | |
| CN113637280B (en) | Silver ion antibacterial compatilizer master batch suitable for inorganic filler modified PP | |
| CN103992630A (en) | Polyphenylether resin alloy material for automobile wheel hub housings and preparation method thereof | |
| CN101768306B (en) | Macromolecule carrier predispersing organosilane accessory ingredient and preparation method thereof | |
| CN111286127A (en) | Polypropylene composite material without tiger stripes at high temperature and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |