CN113845727B - Polypropylene composite material with high rigidity and high thermal aging resistance and preparation method thereof - Google Patents
Polypropylene composite material with high rigidity and high thermal aging resistance and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 125
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 125
- -1 Polypropylene Polymers 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000003878 thermal aging Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 52
- 239000003963 antioxidant agent Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 51
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 150000007970 thio esters Chemical group 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 group 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 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000006250 one-dimensional material Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 241000208181 Pelargonium Species 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- 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
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 application discloses a high-rigidity high-thermal-aging-resistance polypropylene composite material and a preparation method thereof, and belongs to the field of high polymer materials. The polypropylene composite material disclosed by the application has the advantages that the polypropylene with a specific low molecular weight and the polypropylene with a high melt strength are matched to be used as resin matrix components, so that the excellent rigidity and high flow formability of an obtained product can be considered; meanwhile, the filler and various high-performance additives are added, so that the finally obtained product has high heat aging resistance. The application also discloses a preparation method and application of the high-rigidity high-thermal-aging-resistance polypropylene composite material.
Description
Technical Field
The application relates to the field of high polymer materials, in particular to a high-rigidity high-thermal aging-resistance polypropylene composite material and a preparation method thereof.
Background
With the proposal of carbon peak and carbon neutralization concepts, more and more main factories are focusing on the low-carbon environmental protection of materials, wherein one direction is the use of recycled materials in automobile industry parts, and carbon emission is reduced by recycling the recycled materials through the regeneration of carbon-based materials.
The polypropylene (PP) material has the advantages of wide source, low density, excellent mechanical property, fatigue resistance, yield, low price and the like, is widely applied to automobile parts, however, the polypropylene has insufficient heat aging resistance, and the modified polypropylene subjected to the compound collocation modification of the auxiliary components has the risk of reduced formability. On the other hand, the regenerated material sources mainly comprise a washing machine barrel, a washing machine base, a ton package bag and the like, and the regenerated material is subjected to one or more times of melting heat treatment, so that the molecular chain of the regenerated material is relatively shorter, and therefore, the mechanical property, particularly the rigidity and the aging property are poorer, and the regenerated material directly replaces the new material and cannot meet the use requirement of air filtration after the traditional modification (the bending modulus is more than or equal to 3000MPa, and the impact strength is more than or equal to 5 KJ/m) 2 The retention rate of the performance after heat aging at 150 ℃/1000h is more than or equal to 85 percent).
Disclosure of Invention
Based on the defects existing in the prior art, the application aims to provide the high-rigidity high-heat-aging-resistance polypropylene composite material, which has high rigidity high-heat-aging-resistance performance through the synergistic use of low-molecular-weight PP, high-melt-strength PP, inorganic filler and high-performance auxiliary agents (antioxidant and epoxy resin), and can be used for an automobile air filter.
In order to achieve the above purpose, the application adopts the following technical scheme:
the high-rigidity high-heat-aging-resistance polypropylene composite material comprises the following components in parts by weight:
1 to 35 parts of polypropylene, 2 to 54 parts of polypropylene, 20 to 30 parts of inorganic filler, 0.3 to 0.8 part of main antioxidant, 0.3 to 0.8 part of auxiliary antioxidant and 0.4 to 0.8 part of epoxy resin; the number average molecular weight of the polypropylene 1 is 100000 ～ 150000; the melt strength of the polypropylene 2 at 200 ℃ is more than or equal to 20cN.
Preferably, the polypropylene 1 is a polypropylene reclaimed material.
The polypropylene composite material can reduce the total carbon emission in the whole industry due to the adoption of the regenerated PP material with a specific proportion, and provides a solution in the aspects of material realization of carbon peak and carbon neutralization.
Preferably, the primary antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is one of a thio-ester antioxidant or a phosphite antioxidant.
The inventor finds that although the existing polypropylene new material sold on the market has excellent mechanical properties, but insufficient heat aging resistance, and the risk of reduced formability after composite modification is easy to occur, while the physical and chemical properties of the modified resin material obtained by adopting the polypropylene material with molecular weight far lower than that of the new material and the polypropylene material with high melt strength to be compounded are not greatly different from those of the new material, but the formability is obviously improved compared with that of the new material. If the specific number average molecular weight is preferably used, not only the mechanical properties such as flexural modulus, impact strength and the like of the final product can be ensured, but also the problem of difficult injection molding processing of the traditional high melt strength polypropylene can be further solved due to the high fluidity brought by the small molecules in the polypropylene reclaimed material; the polypropylene 2 with high melt strength is originally adopted in the formula, and the molecular long-chain branched chains contained in the polypropylene 2 are introduced, so that the defect of smaller molecules of the polypropylene reclaimed material in the product components can be effectively overcome, and the two polypropylene resins are matched with each other, so that the overall performance of the product can be improved; on the basis, two different antioxidants of main and auxiliary are matched, and epoxy resin is matched, so that a series of aging reactions caused by residual free radicals in the polypropylene reclaimed material can be effectively avoided, and the product has excellent heat aging resistance; meanwhile, the proper adding amount can also avoid the problem that the appearance is affected due to precipitation of products caused by excessive addition of the antioxidant.
According to the high-rigidity high-heat-aging-resistance polypropylene composite material, two polypropylene with different properties are matched to serve as a resin matrix, so that the excellent rigidity and high flow formability of an obtained product can be achieved; simultaneously, filler and various high-performance additives are added, so that the finally obtained product has high heat aging resistance effect; preferably, the components of the polypropylene composite material contain polypropylene reclaimed materials in a specific proportion, so that the overall carbon emission is reduced, and the polypropylene composite material has environmental protection significance.
Preferably, the polypropylene reclaimed material is at least one of washing machine barrel polypropylene reclaimed material and washing machine base polypropylene reclaimed material;
more preferably, the polypropylene reclaimed material has a melt strength of 2 to 5cN at 200 ℃.
The polypropylene reclaimed material under the condition can effectively improve the fluidity of the finally prepared polypropylene composite material.
Preferably, the polypropylene 2 has a number average molecular weight of 600000 ～ 900000.
Preferably, the number average molecular weight of the polypropylene 1 is measured by a membrane osmometry method, and the number average molecular weight of the polypropylene 2 is measured by an ultracentrifuge sedimentation balance method.
The two test methods are all known and commonly used molecular weight test methods, and the number average molecular weight measured by adopting an ideal membrane osmotic pressure test method is more accurate for the low molecular weight polypropylene 1 material; and the polypropylene 2 with higher molecular weight and high melt strength is subjected to number average molecular weight measurement by adopting a general ultracentrifuge sedimentation balance method.
More preferably, the melt strength of the polypropylene 2 at 200 ℃ is 30 to 40cN.
The inventor verifies that the impact strength and the bending modulus of the final prepared product can be further improved by introducing polypropylene with higher melt strength, but the melt strength of polypropylene in the prior art is generally below 40cN, and the higher the melt strength is, the higher the cost is; and selecting the polypropylene 2 component with the optimal melt strength of 30-40 cN through cost performance screening.
Preferably, the inorganic filler is at least one of whisker, wollastonite, talcum powder and mica;
more preferably, the inorganic filler is whisker, and the aspect ratio of the whisker is more than or equal to 15;
more preferably, the inorganic filler is a whisker, and the aspect ratio of the whisker is equal to or more than 20.
The inventor finds that the whisker as a one-dimensional material can show higher rigidity compared with inorganic fillers of other one-dimensional material types when being used for polypropylene materials, and has better heat aging resistance compared with two-dimensional materials such as talcum powder and the like. Meanwhile, the whisker can bring further improvement of mechanical properties along with the increase of the length-diameter ratio.
Preferably, the secondary antioxidant is a thioester antioxidant.
The main antioxidant used in the formula of the application has strong antioxidant effect, but belongs to a chain-termination antioxidant, can provide hydrogen atoms in the process of stabilizing the polymer, and generates inert substances with free radicals in the system to enable the terminated chain to grow so as to achieve the antioxidant effect, but can cause the generation of polymer hydroperoxide, so that the substances have high activity and are very easy to be reconverted into new free radicals so as to generate new degradation and oxidation. When the thioester antioxidant is used as the auxiliary antioxidant, the hydroperoxide generated in the system can be effectively decomposed, so that the side reaction of the main antioxidant after application can be effectively avoided, and the long-acting stable antioxidant effect of the finally prepared polypropylene composite material is provided.
Preferably, the hindered phenol antioxidant is antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate); the thioester antioxidant is antioxidant 412S (pentaerythritol tetra (3-laurylthiopropionate)); the phosphite antioxidant is antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite).
Preferably, the epoxy resin is bisphenol a type epoxy resin.
The application also aims to provide a preparation method of the high-rigidity high-thermal aging resistance polypropylene composite material, which comprises the following steps:
(1) Uniformly mixing the reclaimed material 1, the polypropylene 2, the inorganic filler, the main antioxidant, the auxiliary antioxidant and the epoxy resin to obtain a premix;
(2) And (3) placing the premix into a double-screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat-aging-resistance polypropylene composite material.
Preferably, the steps in the preparation method of the high-rigidity high-heat aging resistance polypropylene composite material can be replaced by:
(1) Uniformly mixing polypropylene 1, polypropylene 2, a main antioxidant, an auxiliary antioxidant and epoxy resin to obtain premix;
(2) And (3) placing the premix into a main screw feeding port in a double screw extruder, simultaneously placing the inorganic filler into a lateral screw feeding port in the middle of the screw in the double screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat aging-resistant polypropylene composite material.
Preferably, in the process of melt extrusion granulation of the double-screw extruder, the temperature of each zone is as follows: the first area temperature is 80-120 ℃, the second area temperature is 190-210 ℃, the third area temperature is 210-230 ℃, the fourth area temperature is 210-230 ℃, the fifth area temperature is 210-230 ℃, the sixth area temperature is 210-230 ℃, the seventh area temperature is 210-230 ℃, the eighth area temperature is 210-230 ℃, and the ninth area temperature is 210-230 ℃; the rotating speed of the host machine is 200-800 rpm; the length-diameter ratio of the double screw extruder is (36-56): 1.
It is a further object of the present application to provide the use of said high stiffness high thermal ageing resistant polypropylene composite for air filtration in automotive products.
The product obtained by the application completely meets the use requirement of automobile air filtration (the flexural modulus is more than or equal to 3000MPa, and the impact strength is more than or equal to 5 KJ/m) 2 The retention rate of the performance after heat aging at 150 ℃/1000h is more than or equal to 85 percent).
Preferably, when the polypropylene composite material with high rigidity and high heat aging resistance is used for preparing an air filter of an automobile product, the inorganic filler accounts for 18-32% of the components in percentage by mass.
As the industrial air filter material has production regulations, the adding proportion of the inorganic filler component in the components of the polypropylene material needs to reach 18-32%, so the product can meet the requirements in application.
The application has the beneficial effects that the application provides the high-rigidity high-thermal aging resistance polypropylene composite material, and the components of the product are matched with low-molecular-weight polypropylene and high-melt-strength polypropylene to be used as a resin matrix, so that the excellent rigidity and the molding fluidity of the obtained product can be considered; meanwhile, the filler and various high-performance additives are added, so that the finally obtained product has high heat aging resistance. The application also provides a preparation method and application of the high-rigidity high-thermal-aging-resistance polypropylene composite material.
Detailed Description
The present application will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present application, and the object of the present application is to be understood in detail, not to limit the present application. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present application. The experimental reagents and instruments designed in the practice and comparative examples of the present application are common reagents and instruments unless otherwise specified. The melt strength of each example and comparative example was determined and verified using a melt strength tester method (compounding a single screw experimental extruder and a "Gottfertreotens" tester) with a heating temperature of 200℃and an extrusion rate of 40mm/min.
The information for the raw materials used in each example and comparative example is as follows:
(1) Polypropylene 1:
polypropylene reclaimed material a: barrel polypropylene reclaimed material of washing machine, product produced by the heptyl company, melt strength at 200 ℃ is 5.5cN, and number average molecular weight is 140000;
polypropylene reclaimed material B: polypropylene reclaimed materials for washing machine bases, products produced by the company of the heptyl, have a melt strength of 2.5cN at 200 ℃ and a number average molecular weight of 110000;
(2) Polypropylene 2:
high melt strength polypropylene a: the Nordic chemical company produces WB135HMS model product with a melt strength of 32cN at 200℃and a number average molecular weight of 750000;
high melt strength polypropylene B: montell corporation produces a PF-814 type product having a melt strength of 25cN and a number average molecular weight of 650000 at 200 ℃;
inorganic filler a: whisker, yingkouweisi such as model WS-1S2, length to diameter ratio 30;
inorganic filler B: whisker, NP-CW2 model product produced by Pelargonium, aspect ratio 15;
inorganic filler C: talcum powder, TYT-777A model product produced by additive source company, and mesh number of 3000;
inorganic filler D: whisker, BT-501 product of Shanghai classical Yangzhi Co., ltd, length-diameter ratio is 12;
and (3) a main antioxidant: hindered phenolic antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) produced by basf, usa;
auxiliary antioxidant A: phosphite antioxidant 168 (tris [ 2.4-di-t-butylphenyl ] phosphite) produced by basf corporation;
auxiliary antioxidant B: thioester antioxidant 412S (pentaerythritol tetrakis (3-laurylthiopropionate)) produced by Basoff, USA;
epoxy resin a: KD-213 bisphenol A type epoxy resin produced by Guogu chemical company;
epoxy resin B: YDF-161 bisphenol F type epoxy resin produced by Guogu chemical company.
Examples 1 to 7
In the embodiment of the high-rigidity high-heat-aging-resistance polypropylene composite material, the preparation method of the product comprises the following steps:
(1) Placing polypropylene 1, polypropylene 2, inorganic filler, main antioxidant, auxiliary antioxidant and epoxy resin into a high-speed mixer, and mixing for 1-3 min to uniformity to obtain premix;
(2) Putting the premix into a double-screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat-aging-resistance polypropylene composite material; when the double-screw extruder is used for melt extrusion granulation, the temperatures of all the areas are as follows: the first area temperature is 100 ℃, the second area temperature is 200 ℃, the third area temperature is 220 ℃, the fourth area temperature is 220 ℃, the fifth area temperature is 220 ℃, the sixth area temperature is 220 ℃, the seventh area temperature is 220 ℃, the eighth area temperature is 220 ℃, and the ninth area temperature is 220 ℃; the rotating speed of the host machine is 500rpm; the aspect ratio of the twin-screw extruder was 42:1.
the proportions of the raw materials used in each example are shown in Table 1.
Examples 8 to 12
The only difference between this example and examples 1-7 is the proportions of the raw materials used, as well as the method of preparing the product, comprising the steps of:
(1) Placing polypropylene 1, polypropylene 2, a main antioxidant, an auxiliary antioxidant and epoxy resin into a high-speed mixer, and uniformly mixing for 5-15 min to obtain premix;
(2) Placing the premix into a main screw feeding port in a double screw extruder, simultaneously placing inorganic filler into a lateral screw feeding port in the middle of the screw in the double screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat aging-resistant polypropylene composite material; when the double-screw extruder is used for melt extrusion granulation, the temperatures of all the areas are as follows: the first area temperature is 100 ℃, the second area temperature is 200 ℃, the third area temperature is 220 ℃, the fourth area temperature is 220 ℃, the fifth area temperature is 220 ℃, the sixth area temperature is 220 ℃, the seventh area temperature is 220 ℃, the eighth area temperature is 220 ℃, and the ninth area temperature is 220 ℃; the rotating speed of the host machine is 500rpm; the aspect ratio of the twin-screw extruder was 42:1, a step of;
wherein the polypropylene regrind used in examples 8 and 9 was replaced with a refrigerator base polypropylene regrind, manufactured by Towegian, inc. having a melt strength of 3cN at 200℃and a number average molecular weight of 115000.
Comparative examples 1 to 8
The products of comparative examples 1 to 7 differ from those of examples 1 to 7 only in the formulation or ratio of the component raw materials, the ratio of the raw materials being shown in Table 1.
Comparative example 9
The only difference between this comparative example and example 1 is that the polypropylene regrind was replaced with a polypropylene washing machine drum regrind product produced by gerrun, having a melt strength of 1.5cN at 200 c and a number average molecular weight of 90000.
Comparative example 10
The only difference between this comparative example and example 1 is that the polypropylene reclaimed material was replaced with a polypropylene washing machine base reclaimed material product manufactured by plastic new company, having a melt strength of 7cN at 200 c and a number average molecular weight of 170000.
Comparative example 11
The only difference between this comparative example and example 1 is that the high melt strength polypropylene was replaced with the product of Montell, inc. of model SD-613, having a melt strength of 15cN at 200℃and a number average molecular weight of 400000.
TABLE 1
Effect example 1
To verify the properties of the polypropylene composite materials with high rigidity and high thermal aging resistance obtained in the examples of the present application, the products obtained in examples 1 to 11 and comparative examples 1 to 10 were subjected to flexural modulus test, melt index test, thermal aging property test, the test methods are shown below, and the test results are shown in table 2.
Flexural modulus test: after the products are molded into the same ISO mechanical sample bars and kept stand for 24 hours in a standard environment (23 ℃ and 50% relative humidity), each test sample bar adopts a German ZWICK/Z010 universal material tester to test the flexural modulus according to ISO 178-2010, the sample bar size is 80 x 10 x 4mm, and the test speed is 2mm/min;
melt index: the melt index of the material was tested at 230℃under a load of 2.16kg according to ISO 1133-2011;
thermal aging performance test: according to the GB/T3512-2014 standard method, placing the material at 150 ℃/1000h, wherein the ventilation frequency is 150 times/h, after the treatment is completed, testing the flexural modulus and the cantilever notch impact strength of the material according to the testing method, comparing the flexural modulus and the cantilever notch impact strength with the data before the treatment, and calculating the change rate, wherein the change rate calculation formula is as follows: performance values after heat aging/performance values before heat aging x 100%.
TABLE 2
As can be seen from Table 2, the high-rigidity high-heat-aging-resistance polypropylene composite material obtained by the embodiments of the application has excellent flexural modulus, higher fluidity (the melt mass flow rate is more than or equal to 13g/10 min), better heat aging resistance and good processing and forming effects, and completely meets the use requirements of an automobile air filter (the flexural modulus is more than or equal to 3000MPa, and the flexural modulus and the retention rate of the notch impact strength of a cantilever beam are more than or equal to 85 percent after heat aging is carried out at 150 ℃/1000 h). Compared with the product prepared by modifying the existing polypropylene new materials sold in the same type (APO-2212, produced by gold technology new material Co., ltd., flexural modulus is 3300MPa, and the highest flexural modulus can reach 4460MPa while the formability is ensured by component adjustment according to the embodiments of the application, and the flexural modulus and the cantilever notched impact strength retention rate of the commercial product are 102% after heat aging of 150 ℃/1000 h); in contrast, the comparative example 1 product obtained by using only polypropylene 1 alone as a component, without compounding polypropylene 2 of high melt strength, although significantly increased in flowability, was insufficient in both rigidity and heat aging resistance, and was difficult to use in practical products. As is clear from the comparison of the properties of the products obtained in examples 1 and 2, the washing machine tub polypropylene reclaimed material is more rigid in the preferred range than the washing machine base polypropylene reclaimed material; in contrast, polypropylene 1 in the product of comparative example 8 had a number average molecular weight that was too low, and the resulting product had a poor flexural modulus; the polypropylene 1 used in comparative example 10 has a number average molecular weight of up to 17000, and the resultant product has a melt mass flow rate of only 9.4g/10min, and poor flowability, although the overall properties are not much different from those of the examples, and is difficult to process and shape. The higher melt strength of the high melt strength polypropylene 2 in the example 1 component than in example 3 and comparative example 11, and the higher flexural modulus of the resulting product, means that the higher melt strength of the high melt strength polypropylene in the said component is more advantageous for improving the rigidity of the product; from comparative examples 3 to 6, it is known that when the addition amount of polypropylene 1 or polypropylene 2 in the components is not proper, the resultant product is difficult to achieve the combined effects of high flow moldability, excellent rigidity and high heat aging resistance at the same time, when it is not within the preferred range of the present application; from examples 1, 4 and 5, the components have better mechanical property improvement than the smooth stone powder when the whisker is used as inorganic filling, and the improvement degree is larger as the length-diameter ratio of the whisker is increased; as can be seen from a comparison of example 1 and example 6, the use of the thio-ester antioxidant as an auxiliary antioxidant in combination with the hindered phenol antioxidant as a component results in a final product having more excellent heat aging resistance than when the phosphite antioxidant is used as an auxiliary antioxidant. As can be seen from comparative examples 2 and 8, the single antioxidant in the components of the product can not completely inhibit the aging phenomenon of the product, and only the product can still maintain the original performance after heat aging by being matched with the epoxy resin to perform synergistic effect, but the antioxidant is not used, so that the same principle is realized; as is clear from comparative example 7, the product components also cannot achieve a synergistic effect on the premise of containing only one of the primary antioxidants.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present application.
Claims (6)
1. The high-rigidity high-heat-aging-resistance polypropylene composite material is characterized by comprising the following components in parts by weight:
1-35 parts of polypropylene, 2-54 parts of polypropylene, 20-30 parts of inorganic filler, 0.3-0.8 part of primary antioxidant, 0.3-0.8 part of auxiliary antioxidant and 0.4-0.8 part of epoxy resin; the polypropylene 1 is a polypropylene reclaimed material, the number average molecular weight is 110000-140000, and the melt strength at 200 ℃ is 2.5-5 cN; the melt strength of the polypropylene 2 at 200 ℃ is 25-32 cN, and the number average molecular weight is 650000-750000; the main antioxidant is hindered phenol antioxidant; the auxiliary antioxidant is a thio ester antioxidant; the inorganic filler is whisker, and the length-diameter ratio of the whisker is 20-30; the epoxy resin is bisphenol A type epoxy resin.
2. The high rigidity, high thermal aging resistant polypropylene composite material according to claim 1, wherein the polypropylene reclaimed material is at least one of a washing machine tub polypropylene reclaimed material and a washing machine base polypropylene reclaimed material.
3. The method for preparing the high-rigidity and high-thermal-aging-resistance polypropylene composite material according to any one of claims 1 to 2, comprising the following steps:
(1) Uniformly mixing polypropylene 1, polypropylene 2, inorganic filler, main antioxidant, auxiliary antioxidant and epoxy resin to obtain premix;
(2) And (3) placing the premix into a double-screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat-aging-resistance polypropylene composite material.
4. A method of preparing a high stiffness, high thermal aging resistant polypropylene composite material according to claim 3, wherein said steps are replaced by:
(1) Uniformly mixing polypropylene 1, polypropylene 2, a main antioxidant, an auxiliary antioxidant and epoxy resin to obtain premix;
(2) And (3) placing the premix into a main screw feeding port in a double screw extruder, simultaneously placing the inorganic filler into a lateral screw feeding port in the middle of the screw in the double screw extruder for melt extrusion granulation, and drying to obtain the high-rigidity high-heat aging-resistant polypropylene composite material.
5. The method for producing a high-rigidity and high-heat-aging-resistance polypropylene composite material according to claim 3 or 4, wherein the twin-screw extruder is melt-extruded and pelletized at the respective zone temperatures of: the first area temperature is 80-120 ℃, the second area temperature is 190-210 ℃, the third area temperature is 210-230 ℃, the fourth area temperature is 210-230 ℃, the fifth area temperature is 210-230 ℃, the sixth area temperature is 210-230 ℃, the seventh area temperature is 210-230 ℃, the eighth area temperature is 210-230 ℃, and the ninth area temperature is 210-230 ℃; the rotating speed of a host machine of the double-screw extruder is 200-800 rpm; the length-diameter ratio of the double-screw extruder is (36-56): 1.
6. Use of the polypropylene composite material with high rigidity and high thermal aging resistance according to any one of claims 1-2 for preparing an air filter in an automotive product.
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