CN115873346A - Low-odor polypropylene master batch and preparation method and application thereof - Google Patents
Low-odor polypropylene master batch and preparation method and application thereof Download PDFInfo
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- CN115873346A CN115873346A CN202211663583.7A CN202211663583A CN115873346A CN 115873346 A CN115873346 A CN 115873346A CN 202211663583 A CN202211663583 A CN 202211663583A CN 115873346 A CN115873346 A CN 115873346A
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- -1 polypropylene Polymers 0.000 title claims abstract description 107
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 105
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 105
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 47
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 47
- 229910021485 fumed silica Inorganic materials 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 10
- 150000000703 Cerium Chemical class 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 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 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 2
- 229940063655 aluminum stearate Drugs 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 6
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000003905 indoor air pollution Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 210000002345 respiratory system Anatomy 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- 150000004982 aromatic amines Chemical class 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-odor polypropylene master batch, a preparation method and application thereof. Then, the silicon dioxide composite material and high-melt-index polypropylene are extruded to prepare low-odor polypropylene master batches, so that the dispersity of the fumed silicon dioxide composite material in the polypropylene can be improved, and the removal efficiency of VOCs is improved. According to the invention, by preparing the low-odor polypropylene master batch, the problems of poor dispersion of an inorganic adsorbent, poor stability and processability of an organic adsorbent and the like in the existing low-odor low-volatility polypropylene material are solved, so that the low-odor composite polypropylene material has the characteristics of excellent mechanical property, processability and low odor at the same time.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, and particularly relates to a low-odor polypropylene master batch, and a preparation method and application thereof.
Background
Polypropylene (PP) is a thermoplastic resin formed from propylene by polymerization. The appearance is milky white particles, and the density is usually 0.89-0.91g/cm 3 Low cost, good formability, processing temperature of about 200 ℃, stable performance after forming and excellent performanceGood acid and alkali corrosion resistance, and can be widely used in the fields of household appliance structural parts, shells, automobile bumpers, door panels, interior trims and the like.
However, polypropylene materials are often accompanied by the release of Volatile Organic Compounds (VOCs) during use, causing odor and indoor air pollution. VOCs are the main contributors to indoor air pollution, and the components are complex, and many of the components have irritation and toxicity, thereby posing serious threats to human health and atmospheric environment. Most VOCs have pungent odor, are easy to cause respiratory tract discomfort, and have more influence on young and old people and patients with respiratory tract chronic diseases. Higher concentrations of VOCs can also irritate the eyes and respiratory tract, causing skin irritation, asthma, and other diseases. Some VOCs such as benzene, polycyclic aromatic hydrocarbon, aromatic amine, aldehyde and nitrosamine have carcinogenic and teratogenic effects on organisms.
The sources of indoor VOCs are wide, and the indoor VOCs comprise furniture, paint, plastic shells of household appliances and the like. It is anticipated that with consumer focus on indoor air pollution, low odor, low VOCs release will become an important criteria for measuring plastic properties, which presents new challenges for polypropylene materials used in the home appliance and automotive fields.
The odor in the polypropylene material mainly comes from two aspects: one is that in the polymerization process of propylene monomers, organic solvents, oligomers and the like remained in finished products are generally high in odor threshold; secondly, in the modification process of adding various additives (such as a toughening agent, a reinforcing agent, a plasticizer, a coupling agent, a flame retardant, a lubricant, an antioxidant and the like) into the polypropylene, the main material and the additives are blended, extruded and granulated by a screw, and are subjected to the actions of strong shearing, high temperature, oxygen and the like in the process, tertiary hydrogen atoms in the structure of the polypropylene chain are easily oxidized, polymer chain segments are broken to generate various oxidation products, such as ketone, aldehyde and ester micromolecule compounds, which are volatile, have low odor threshold value, are easily released into the air in the daily use process, and are the main reason of causing peculiar smell. The release action of VOCs is relevant with the temperature in the polypropylene, when polypropylene is in high temperature service environment, like sterilizer, microwave oven, electric kettle, or summer burning sun's automotive interior, causes the release of the inside VOCs of polypropylene more easily, leads to the peculiar smell obvious, greatly reduced consumer's use experience. Therefore, the release amount of VOCs of the polypropylene material is reduced, and the polypropylene material has important practical value in the fields of household appliances and automobiles.
At present, for odor control of modified polypropylene materials, there are several methods as follows:
(1) Resin and auxiliary agents with high thermal stability, low volatility and no peculiar smell are selected as much as possible, and the efficiency of the auxiliary agents is improved as much as possible through the synergistic effect among the auxiliary agents, so that the using amount of the auxiliary agents is reduced. However, the additive with high thermal stability and low volatility is accompanied by the increase of cost, and various additive components are complex and mutually influence under the high temperature condition, and the generation and the escape of the small molecular VOCs are difficult to avoid.
(2) The peculiar smell is removed by adding an adsorbent into polypropylene, and the adsorbent can be divided into a physical adsorbent and a chemical adsorbent according to the type of VOCs adsorption. The physical adsorbent is porous materials such as zeolite, porous carbon and the like; the conventional chemical adsorbents are various chelating agents which have chelation reaction with volatile substances to make them not volatile. Chinese patent CN202111247144.3 uses diatomite and activated carbon as adsorbents to prepare low-volatility automobile polypropylene materials. However, diatomite and activated carbon only have VOCs adsorption capacity, and VOCs adsorbed by diatomite and activated carbon are easy to release under high-temperature conditions, so that the diatomite and the activated carbon are 'temporary solution and permanent solution'.
(3) In the extrusion process of blending modification of the polymer and the auxiliary agent, the small molecular compounds generated in the high-temperature shearing process are extracted by adding an extracting agent with strong volatility, and the deodorizing effect is improved by combining vacuumizing (devolatilization). The currently used extracting agents include water, low molecular alcohol ether, aqueous polymer master batch, surfactant and the like. Chinese patent CN202210647166.7 uses a mode of side feeding of absolute ethyl alcohol in the extrusion process and vacuum-pumping devolatilization to prepare the low-odor and low-emission polypropylene composite material for vehicles. However, since ethanol itself belongs to VOCs molecules with pungent odor, the performance requirement of the vacuum pump is high, and if the vacuum degree is insufficient, the ethanol molecules cannot be completely extracted, which causes the aggravation of the odor of the finished product.
(4) The post-treatment heat drying process can accelerate the motion of the odor micromolecules and remove the odor micromolecules better. Within a certain range, as the temperature of the drying material is increased and the drying time is increased, the odor grade is reduced, but the odor grade basically does not change at a certain temperature and time. The mode has limited removal efficiency of VOCs, and long-time drying can accelerate the aging of polypropylene and influence the mechanical property and oxidation resistance of the material.
In summary, these methods have their own drawbacks, such as high cost, long production cycle, and difficulty in fundamentally improving the odor and VOC of the material. In order to meet the requirement of low odor, a new technical scheme is urgently needed for modifying the polypropylene material.
Disclosure of Invention
Based on the above, the invention aims to provide a low-odor polypropylene master batch, and a preparation method and application thereof, wherein the polypropylene master batch takes fumed silica loaded with cerium oxide as a catalyst and an adsorbent, and can effectively adsorb harmful substances such as micromolecule VOCs and the like by utilizing the high catalytic activity of the cerium oxide and the high specific surface area of the fumed silica, and perform catalytic removal, so as to achieve the purpose of effectively reducing the odor of a polypropylene material.
In order to achieve the purpose, the invention adopts the technical scheme that:
the first purpose of the invention is to provide a preparation method of low-odor polypropylene master batch, which comprises the following steps:
dissolving cerium salt in water to obtain a cerium salt solution; preferably, the cerium salt is at least one of cerium nitrate, cerium acetate and cerium chloride;
soaking the fumed silica in a cerium salt solution, taking out the fumed silica after the soaking is finished, and drying the fumed silica to obtain a yellow solid; calcining the yellow solid at the temperature of 400-600 ℃ for 1-4h to obtain the gas-phase silicon dioxide composite material loaded with cerium oxide; the primary particle size of the fumed silica is 5-100nm, the aggregate particle size is about 100-800nm, and the specific surface area is 20-800m 2 (ii)/g; the loading amount of the cerium oxide in the gas phase silicon dioxide composite material loaded with the cerium oxide is 10-30%;
mixing the fumed silica composite material loaded with cerium oxide with high-melt-index polypropylene, and then processing and granulating by a double-screw extruder to obtain low-odor polypropylene master batches; preferably, the high-melt index polypropylene has a melt index of 30-60g/10min at 230 ℃/2.16 kg; more preferably, the mass fraction of the fumed silica composite material loaded with cerium oxide in the low-odor polypropylene master batch is 10%.
The second object of the present invention is to provide a low-odor polypropylene master batch prepared by the preparation method as described in the first object.
The third purpose of the invention is to provide a low-odor composite polypropylene material, which is prepared from the following raw materials in parts by weight:
the low-odor polypropylene master batch is the low-odor polypropylene master batch as described in the second purpose;
the polypropylene resin comprises low-melt index polypropylene resin and high-melt index polypropylene powder; the mass fraction of the low-melt-index polypropylene resin in the polypropylene resin is 14-25%; the low melt index polypropylene resin has a melt index of 5-30g/10min at 230 ℃/2.16 kg; the melt index of the high melt index polypropylene powder is 30-60g/10min under the condition of 230 ℃/2.16 kg.
Further preferably, the filler is at least one of talcum powder, calcium carbonate, barium sulfate, glass fiber and montmorillonite; the primary antioxidant is an antioxidant 1010, and the secondary antioxidant is an antioxidant 168; the lubricant is at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate and ethylene bisstearamide.
A fourth object of the present invention is to provide a method for preparing a low-odor composite polypropylene material according to the third object, comprising the steps of:
(1) Weighing the polypropylene resin, the filler, the low-odor polypropylene master batch, the main antioxidant, the auxiliary antioxidant and the lubricant according to the weight percentage, and uniformly mixing to obtain a mixture;
(2) And (2) adding the mixture obtained in the step (1) into a parallel double-screw extruder, carrying out melt extrusion in the parallel double-screw extruder, and granulating to obtain the low-odor composite polypropylene material.
Further preferably, the process parameters of the parallel twin-screw extruder are as follows: the extrusion temperature in each zone was: the temperature of the first zone was 155 ℃, the temperature of the second zone was 195 ℃, the temperature of the third zone was 195 ℃, the temperature of the fourth zone was 205 ℃, the temperature of the fifth zone was 205 ℃, the temperature of the sixth zone was 195 ℃, the temperature of the seventh zone was 195 ℃, the temperature of the eighth zone was 205 ℃, the temperature of the die head was 205 ℃, the rotation speed of the screw was 250rpm, and the vacuum was-0.05 MPa. The ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area.
The low-odor composite polypropylene material provided by the invention has the following effects of raw materials:
cerium oxide is a catalytic material with excellent performance, and is widely applied to a catalytic system. Due to Ce in cerium oxide 3+ And Ce 4+ The ion pairs are easy to convert, so that the ion pairs have unique oxidation-reduction performance and higher catalytic activity on VOCs at normal temperature. However, the nano cerium oxide as a nano material has high surface energy and is easy to agglomerate, so that the contact between the surface of the nano cerium oxide and gas-phase VOCs is influenced. The gas phase silicon dioxide is used as a nano material with a porous structure, has the excellent characteristics of high specific surface area, high temperature resistance, chemical inertness, thickening property, low cost and the like, and is a good catalyst carrier. The method adopts an impregnation method which is convenient and rapid and has lower cost to prepare the gas phase silicon dioxide composite material loaded with cerium oxide. Fumed silica has a large specific surface area and high surface energy, and is easily wetted by a cerium salt solution. In addition, capillary forces ensure that the liquid is drawn into the entire porous structure, which allows for uniform loading and high dispersion of cerium ions. Drying and calcining to form cerium oxide particles. Cerium oxide is loaded on fumed silica by using an impregnation method, so that the dispersion degree of the cerium oxide in resin is improved; then the polypropylene is prepared by extrusion processing with high-melt index polypropyleneThe low-odor polypropylene master batch is obtained, the dispersity of the fumed silica composite material in polypropylene can be improved, and the removal efficiency of VOCs is improved. The cerium oxide nano-particles with high catalytic activity and the fumed silica carrier with high specific surface area are used, so that the aim of reducing the content of the polypropylene VOCs is effectively fulfilled.
The high-melt-index polypropylene is used in the preparation of the low-odor polypropylene master batch, and the polypropylene resin with lower melt index is used in the preparation of the low-odor composite polypropylene material, so that the final product has excellent mechanical properties and processability.
The filler used in the invention plays a role in improving the shape stability of the product and can reduce the cost.
According to the invention, the main antioxidant and the auxiliary antioxidant are compounded, so that the processing stability of the matrix resin is improved in the polypropylene processing process, and the problems of material degradation and the like caused in the high-temperature processing process are avoided, thereby improving the overall performance of the material.
The lubricant used in the invention has good thermal stability and is not easy to decompose in the processing process of polypropylene. In consideration of the existence of polypropylene with low melting index in the formula, in order to improve the processability of the material and reduce the comprehensive energy consumption, the lubricant is introduced, and the lubricant and the polypropylene are matched with each other in a proper proportion, so that the shearing force received by the material in the processing process is obviously reduced, and the local overheating of the material in the processing process is avoided, and the abnormal black spot is avoided.
Compared with the prior art, the invention has the following beneficial effects:
1. the cerium oxide-loaded fumed silica composite material is prepared by combining cerium oxide nanoparticles with high catalytic activity and fumed silica with high specific surface area, can adsorb micromolecule VOCs in a high-temperature extrusion environment and perform catalytic purification, and the products are pollution-free carbon dioxide and water. Meanwhile, cerium oxide has certain catalytic capability at normal temperature, and compared with similar products only introducing an adsorbent, the cerium oxide has low VOCs emission in the daily use process, and can effectively solve the problem of abnormal odor in the use process of polypropylene parts.
2. According to the invention, by preparing the low-odor polypropylene master batch, the problems of poor dispersion of an inorganic adsorbent, poor stability and processability of an organic adsorbent and the like in the existing low-odor low-volatility polypropylene material are solved, so that the low-odor composite polypropylene material has the characteristics of excellent mechanical property, processability and low odor at the same time.
3. The preparation method and the process of the low-odor composite polypropylene material provided by the invention are simple, easy to control and low in equipment requirement, and the used equipment is general processing equipment. The workpiece can be applied to the fields of household appliances and automobiles, is particularly suitable for the fields of household appliances such as household appliance linings, steam valves, air duct components and wading components, can also be expanded to be used in the fields of automobile interior and exterior decorations, other small household appliances and the like, and has wide application prospect.
Detailed Description
To facilitate an understanding of the present invention, the present invention will be described more fully hereinafter with reference to examples and application examples, a preferred embodiment of which is set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. It is to be understood that the experimental procedures in the following examples, where specific conditions are not noted, are generally in accordance with conventional conditions, or with conditions recommended by the manufacturer. The various reagents used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The mechanism of the low-odor composite polypropylene material for degrading VOCs provided by the invention is as follows:
aiming at the problem that VOCs adsorbed by the existing low-odor polypropylene material using an adsorbent is easy to escape at high temperature to cause peculiar smell, the invention introduces the catalytic material cerium oxide, so that the catalytic material can effectively purify micromolecule VOCs released at high temperature in an extrusion molding stage, also has low-temperature adsorption and catalysis functions in a daily use stage, and reduces the release of VOCs.
Meanwhile, the fumed silica is used as a nano material with a porous structure, and has the excellent characteristics of high specific surface area, high temperature resistance, chemical inertness, thickening property, low cost and the like. The gas-phase silicon dioxide has better adsorption of VOCs, high powder purity and good dispersibility, is an excellent catalyst carrier, and can effectively improve the treatment performance of VOCs of the catalyst. The types and suppliers of the reagents used in the following examples and comparative examples are as follows:
the low melt index polypropylene resin has a melt index of 12g/10min at 230 ℃/2.16kg and is purchased from Guangzhou division of petrochemical Co., ltd;
the high melt index polypropylene powder has a melt index of 35g/10min at 230 ℃/2.16kg and is purchased from Michelson division of petrochemical Co., ltd, china;
primary antioxidant 1010: pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], purchased from Tianjin Lianlong New materials, inc.;
auxiliary antioxidant 168: tris (2, 4-di-tert-butylphenyl) phosphite, purchased from Tianjin Lianlong New materials, inc.;
talc powder: talcum powder WX-2 (2500 mesh), available from Changzhou Weixiong chemical Co., ltd;
the lubricant is Ethylene Bis Stearamide (EBS) which is purchased from Yino chemical technology Co., ltd, guangzhou city;
fumed silica: nanoscale, purchased from Henan Tianrema chemical products, inc.;
cerium acetate: purchased from Changsha delity rare earth chemical Limited liability company;
deionized water: self-made by a deionized water machine;
commercial cerium oxide powder: purchased from zibo rui bo kang rare earth materials ltd;
the reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Examples
A preparation method of low-odor polypropylene master batch comprises the following steps:
dissolving cerium acetate in water to obtain a cerium acetate solution;
soaking the fumed silica in a cerium acetate solution for 2 hours, taking out the fumed silica after the soaking is finished, and drying the fumed silica in an oven at the temperature of 80 ℃ overnight to obtain a light yellow solid; placing the light yellow solid in a muffle furnace at 500 ℃ for calcining for 2h to obtain a gas-phase silicon dioxide composite material loaded with cerium oxide; it should be noted that, when the calcination temperature is within the temperature range of 400-600 ℃, and the calcination time is within the time range of 1-4h, the purpose of the invention can be achieved.
The gas phase silicon dioxide composite material loaded with cerium oxide is mixed with high melt index polypropylene powder and then is processed and granulated by a double screw extruder, and the process parameters are as follows: the temperature in the first zone was 155 ℃, the temperature in the second zone was 195 ℃, the temperature in the third zone was 195 ℃, the temperature in the fourth zone was 205 ℃, the temperature in the fifth zone was 205 ℃, the temperature in the sixth zone was 195 ℃, the temperature in the seventh zone was 195 ℃, the temperature in the eighth zone was 205 ℃, the temperature in the die head was 205 ℃, the screw speed was 250rpm, and the vacuum was-0.05 MPa. The ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area. Thus obtaining the low-odor polypropylene master batch.
In order to optimize the dispersion and loading of cerium oxide on fumed silica, five kinds of low-odor polypropylene master batches with different cerium oxide contents are prepared by controlling the dosage of cerium acetate, and are respectively named as A-type master batch, B-type master batch, C-type master batch, D-type master batch and E-type master batch, and the information of each type of master batch is as follows:
a type master batch: the mass fraction of the cerium oxide/fumed silica nano composite material in the master batch is fixed to be 10%, and the loading amount of the cerium oxide on the fumed silica is 10%.
B type master batch: the mass fraction of the cerium oxide/fumed silica nano composite material in the master batch is fixed to be 10%, and the loading amount of the cerium oxide on the fumed silica is 20%.
C type master grain: the mass fraction of the cerium oxide/fumed silica nano composite material in the master batch is fixed to be 10%, and the loading capacity of the cerium oxide on the fumed silica is 30%.
D type master batch: the mass fraction of the commercial cerium oxide powder in the master batch is 10%.
E type master batch: the mass fraction of the fumed silica in the master batch is 10%.
Application example and comparative application example
Application examples 1 to 5 and comparative application examples 1 to 5 were designed with reference to the relationship between the amounts of the raw materials in table 1, and the target product was prepared from each raw material in each of the above application examples and comparative application examples by the following method:
(1) After weighing all the raw materials according to the weight fraction, uniformly mixing the raw materials by using a high-speed stirrer of 600 revolutions per minute to obtain a mixture.
(2) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a main feeder, carrying out melt extrusion in the parallel double-screw extruder, and granulating, wherein the process parameters are as follows: the temperature in the first zone was 155 ℃, the temperature in the second zone was 195 ℃, the temperature in the third zone was 195 ℃, the temperature in the fourth zone was 205 ℃, the temperature in the fifth zone was 205 ℃, the temperature in the sixth zone was 195 ℃, the temperature in the seventh zone was 195 ℃, the temperature in the eighth zone was 205 ℃, the temperature in the die head was 205 ℃, the screw speed was 250rpm, and the vacuum was-0.05 MPa. The ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular low-odor composite polypropylene material.
Table 1 raw material composition parts by weight list of each application example and comparative application example
The polypropylene materials prepared in the application examples and the comparative application examples are subjected to performance tests, and the results are shown in the following table 2:
TABLE 2 Properties of the Polypropylene materials prepared in the application examples and comparative application examples
The results of the performance tests of the above application examples 1 to 5 and comparative application examples 1 to 5 can be analyzed to obtain:
(1) From application examples 3, 4 and 5 and comparative application examples 3 and 4, it is clear that the B-type master batch (application example 3) among the five ABCDE master batches was the best in use at the same 5% usage amount, the odor score was high, and the concentration of VOCs was low. The main difference of the five master batches is that the loading amounts of cerium oxide in the master batches are different. When the loading capacity of cerium oxide is low (10%), the catalytic removal efficiency of formaldehyde and toluene is not high, so that the peculiar smell cannot be completely removed; when the loading amount of cerium oxide is too high, cerium oxide particles are easy to agglomerate on the surface of the gas-phase silicon dioxide particles, the dispersity is not high, the adsorption and oxidation processes of gas-phase VOCs on the surface of cerium dioxide are hindered, and the catalytic efficiency is also influenced.
(2) As is clear from application examples 1,2 and 3 and comparative application example 1 and 2, the B-type master batch used was evaluated to be high in odor and low in VOCs concentration at 2 to 10 parts. When the using part of the B-type master batch is less than 2 parts (comparative application example 1), the content of cerium oxide/fumed silica is low, so that small-molecular VOCs cannot be effectively removed, and the odor evaluation is reduced; when the master batch is used at a fraction of 15 parts (comparative application example 2), the concentration of VOCs is not reduced significantly. From the viewpoint of cost saving by reducing the amount of cerium oxide used, the cost performance is relatively high when the B-type master batch is used in an amount of 5 parts.
(3) As can be seen from comparative application example 5, when cerium oxide powder and fumed silica were directly added to granulation without using the cerium oxide/fumed silica master batch, although the cerium oxide content and fumed silica content were consistent with application example 3, since the cerium oxide powder and fumed silica, as nanomaterials having extremely small particle sizes, were difficult to disperse in PP resin, their abilities to adsorb and catalyze VOCs were difficult to exert, resulting in a significant odor, and ultrahigh concentrations of formaldehyde and toluene. Furthermore, the agglomeration of the nanoparticles can also deteriorate the mechanical properties of the polypropylene material, resulting in a substantial decrease in notched impact strength.
The technical features of the above application examples can be arbitrarily combined, and for the sake of simplicity of description, all possible combinations of the technical features in the above application examples are not described, however, as long as there is no contradiction between the combinations of the technical features, the combinations should be considered as the scope of the present description.
The above application examples only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of low-odor polypropylene master batch is characterized by comprising the following steps: the method comprises the following steps:
dissolving cerium salt in water to obtain a cerium salt solution;
soaking the fumed silica in a cerium salt solution, taking out the fumed silica after the soaking is finished, and drying the fumed silica to obtain a yellow solid; calcining the yellow solid at the temperature of 400-600 ℃ for 1-4h to obtain the gas-phase silicon dioxide composite material loaded with cerium oxide;
mixing the gas-phase silicon dioxide composite material loaded with cerium oxide with high-melt-index polypropylene, and processing and granulating by a double-screw extruder to obtain low-odor polypropylene master batch; the melt index of the high melt index polypropylene is 30-60g/10min under the condition of 230 ℃/2.16 kg.
2. The method for preparing the low-odor polypropylene master batch according to claim 1, wherein the method comprises the following steps: the cerium salt is at least one of cerium nitrate, cerium acetate and cerium chloride.
3. The method for preparing the low-odor polypropylene master batch according to claim 1, wherein the method comprises the following steps: the loading amount of the cerium oxide in the gas phase silicon dioxide composite material loaded with the cerium oxide is 10-30%.
4. A low-odor polypropylene master batch is characterized in that: which is prepared by the preparation method of any one of claims 1 to 3.
5. A low-odor composite polypropylene material is characterized in that: the health-care food is prepared from the following raw materials in parts by weight:
the low-odor polypropylene master batch is the low-odor polypropylene master batch of claim 4;
the polypropylene resin comprises low-melt index polypropylene resin and high-melt index polypropylene powder; the mass fraction of the low-melt-index polypropylene resin in the polypropylene resin is 14-25%; the low melt index polypropylene resin has a melt index of 5-30g/10min at 230 ℃/2.16 kg; the melt index of the high melt index polypropylene powder is 30-60g/10min under the condition of 230 ℃/2.16 kg.
6. The low-odor composite polypropylene material according to claim 5, wherein: the filler is at least one of talcum powder, calcium carbonate, barium sulfate, glass fiber and montmorillonite.
7. The low-odor composite polypropylene material according to claim 5, wherein: the primary antioxidant is an antioxidant 1010, and the secondary antioxidant is an antioxidant 168.
8. The low-odor composite polypropylene material according to claim 5, wherein: the lubricant is at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate and ethylene bisstearamide.
9. The method for preparing a low-odor composite polypropylene material as claimed in claims 5 to 8, wherein: the method comprises the following steps:
(1) Weighing the polypropylene resin, the filler, the low-odor polypropylene master batch, the main antioxidant, the auxiliary antioxidant and the lubricant according to the weight percentage, and uniformly mixing to obtain a mixture;
(2) And (2) adding the mixture obtained in the step (1) into a parallel double-screw extruder, carrying out melt extrusion in the parallel double-screw extruder, and granulating to obtain the low-odor composite polypropylene material.
10. The method for preparing the low-odor composite polypropylene material as claimed in claim 9, wherein: the extrusion temperature of the parallel double-screw extruder is 155-205 ℃.
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