CN111234470B - Thermal-aging-resistant PET (polyethylene terephthalate) nano composite material and preparation method thereof - Google Patents
Thermal-aging-resistant PET (polyethylene terephthalate) nano composite material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 39
- 239000005020 polyethylene terephthalate Substances 0.000 title claims description 39
- 238000003878 thermal aging Methods 0.000 title claims description 15
- -1 polyethylene terephthalate Polymers 0.000 title claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 65
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 64
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 28
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 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 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 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 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 150000007970 thio esters Chemical class 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JIGJVROAHDAONK-UHFFFAOYSA-N C(C=C)(=O)OC1C(C=C(C=C1C(C)(C)C)C(C)(C)C)=CC1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O Chemical group C(C=C)(=O)OC1C(C=C(C=C1C(C)(C)C)C(C)(C)C)=CC1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O JIGJVROAHDAONK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a heat-aging-resistant PET nano composite material and a preparation method thereof, wherein the heat-aging-resistant PET nano composite material is prepared from PET, a flame retardant, a load-type antioxidant and an antioxidant in parts by weight, and a cerium oxide load-type antioxidant, a hindered phenol antioxidant and a thioester antioxidant are compounded and combined, so that the heat-aging resistance of the composite material is greatly improved, and meanwhile, the antioxidant loaded on filling particles can effectively avoid extraction loss in the hot processing process of the material and effectively improve the weather-resistant aging of the material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a thermal aging resistant PET nano composite material and a preparation method thereof.
Background
The thermal aging resistance of the material is an important index for testing whether the material can be used and stored for a long time. For PET/magnesium hydroxide/aluminum hydroxide materials, because of their poor resistance to thermal aging, large amounts of antioxidants are required to protect the material from substantial degradation under high temperature processing conditions and harsh use environments. The common antioxidant is usually hindered phenol or thioester antioxidant, which has poor antioxidant effect, is not resistant to extraction and has larger volatility, so that the low molecular weight antioxidant is easy to lose in the processes of processing, storing and using the polymer.
Disclosure of Invention
Based on the above, the invention provides the thermal aging resistant PET nano composite material, wherein the cerium oxide supported reactive antioxidant, the hindered phenol antioxidant and the thioester antioxidant are compounded and combined, so that the thermal aging resistance of the composite material is greatly improved, and meanwhile, the antioxidant loaded on the filling particles can effectively avoid the extraction loss brought in the thermal processing process of the material, and the weather aging resistance of the material is effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the thermal aging resistant PET nano composite material is prepared from the following components in parts by weight:
wherein the load type antioxidant is cerium oxide load reaction type antioxidant.
Further, the melt index of the PET at 230 ℃ and 2.16kg is 10-15 g/kg.
Further, the flame retardant is a mixture of magnesium hydroxide and aluminum hydroxide mixed according to the ratio of 1:1, and the average particle size of the flame retardant is 1500 meshes.
Further, the cerium oxide-loaded reactive antioxidant is prepared by reacting nano cerium oxide, gamma-mercaptopropyltriethoxysilane and the reactive antioxidant, and the reactive antioxidant is 2- [1- (2-hydroxy-3, 5-ditert-butylphenyl) -methylene ] -4, 6-ditert-butylphenyl acrylate (antioxidant GM) or 2- [1- (2-hydroxy-3, 5-ditert-pentylphenyl) ethylene ] -4, 6-ditert-pentylphenyl acrylate (antioxidant GS).
Specifically, the preparation method of the cerium oxide supported reactive antioxidant comprises the following steps: adding dried nano cerium oxide into toluene for uniform dispersion, then adding gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing for 3-5 h at 90-100 ℃, then cooling the reaction system to 55-65 ℃, then adding a reactive antioxidant, continuing stirring for 1.5-2.5 h, separating and drying to obtain the cerium oxide supported reactive antioxidant. The means for adding cerium oxide to toluene to disperse uniformly is not limited, and any conventional dispersing means of those skilled in the art may be used, such as ultrasonic dispersion, stirring dispersion, and the like, and any conventional means of those skilled in the art may be used for said separation and drying, such as centrifugal separation, suction filtration separation, and the like, and therefore, no specific limitation is imposed thereon. It should be understood that the above is only an example, and not a limitation of the technical solution of the present invention.
Preferably, the mass ratio of the nano cerium oxide to the gamma-mercaptopropyltriethoxysilane to the reactive antioxidant is 1:1: 3.
Further, the antioxidant is formed by mixing [ beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and tris- (2, 4-di-tert-butylphenyl) phosphite ester (antioxidant 168) according to a mass ratio of 1: 1.
The invention also aims to provide a preparation method of the thermal aging resistant PET nano composite material, which comprises the steps of mixing PET, a flame retardant, a supported antioxidant and an antioxidant at a high speed according to a ratio to obtain a uniform mixed material; and adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the heat-aging-resistant PET nanocomposite.
Further, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-160 ℃, 160-175 ℃, 175-185 ℃, 185-195 ℃, 190-200 ℃, 220-230 ℃, 230-240 ℃, 240-250 ℃ and 240-250 ℃ respectively.
Rare earth oxides are widely used in petrochemical and biomedical industries, usually in the form of catalysts. The nano cerium oxide has the characteristics of small crystal grain size, stability and easy dispersion, and is suitable for ultraviolet separants in sunscreen cosmetics, anti-aging agents in plastics and coatings; the crystal lattice is intact, the specific gravity is large, and pores are not easy to form in the ceramic; the product has good dispersibility and transparency, and is easy to be added into polymers such as plastic, silicon rubber and the like.
In view of the poor long-term aging resistance of the flame retardant system of PET + magnesium hydroxide + aluminum hydroxide, compared with the prior art, the cerium oxide supported reactive antioxidant is prepared by creatively supporting cerium oxide on a high-performance antioxidant and is compounded and combined with hindered phenol antioxidants. Compared with the traditional antioxidant system, the prepared composite material has the advantages that the retention rate of the mechanical properties of the composite material after thermal aging is increased, and the color difference of the composite material after thermal aging is low, which shows that the thermal aging resistance of the composite material is greatly improved; meanwhile, the antioxidant is loaded on the filling particles, so that the pumping loss of the composite material in the hot working process can be effectively avoided, and the weather-resistant aging of the composite material is effectively improved.
Meanwhile, the addition of the nano cerium oxide in the supported oxidant effectively improves the mechanical property of the composite material and enlarges the application range of the composite material.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
It should be noted that the melt index of PET used in the following examples is 10 to 15g/kg at 230 ℃ and 2.16kg, the flame retardant is a mixture of magnesium hydroxide and aluminum hydroxide in a mass ratio of 1:1, and the average particle size of the flame retardant is 1500 meshes.
In the examples, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1.
Example 1
The supported oxidant adopted in the embodiment is prepared by uniformly dispersing 10g of dried nano cerium oxide in 500mL of toluene, then adding 10g of gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing at 95 ℃ for 4h, then cooling the temperature of a reaction system to 60 ℃, adding 30g of antioxidant GM into the reaction system, continuously stirring for 2h, carrying out suction filtration to obtain a solid, and drying the solid to obtain the cerium oxide supported reactive antioxidant.
Mixing 100 parts of PET, 10 parts of flame retardant, 5 parts of load type antioxidant and 0.3 part of antioxidant at a high speed for 10min to obtain a uniform mixed material; adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the heat-aging-resistant PET nanocomposite; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃, 220 ℃, 230 ℃, 240 ℃ and 240 ℃. The results of the relevant property tests are shown in table 1.
Example 2
The supported oxidant adopted in the embodiment is prepared by uniformly dispersing 10g of dried nano cerium oxide in 500mL of toluene, then adding 10g of gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing at 90 ℃ for 5h, cooling the temperature of a reaction system to 55 ℃, adding 30g of antioxidant GM into the reaction system, continuously stirring for 2.5h, performing suction filtration to obtain a solid, and drying the solid to obtain the cerium oxide supported reaction type antioxidant.
Mixing 100 parts of PET, 8 parts of flame retardant, 4 parts of load-type antioxidant and 0.5 part of antioxidant at a high speed for 10min to obtain a uniform mixed material; adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the heat-aging-resistant PET nanocomposite; wherein the extrusion temperature of each extrusion interval in the double-screw extruder is 155 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 225 ℃, 235 ℃, 245 ℃ respectively. The results of the relevant property tests are shown in table 1.
Example 3
The supported oxidant adopted in the embodiment is that 10g of dried nano cerium oxide is uniformly dispersed in 500mL of toluene, then 10g of gamma-mercaptopropyltriethoxysilane is added, the mixture is heated, stirred and refluxed for 3h at 100 ℃, the temperature of a reaction system is reduced to 65 ℃, 30g of antioxidant GS is added into the reaction system, the mixture is continuously stirred for 1.5h, and then the mixture is subjected to suction filtration to obtain a solid which is dried to obtain the cerium oxide supported reaction antioxidant.
Mixing 100 parts of PET, 5 parts of flame retardant, 3 parts of load type antioxidant and 0.3 part of antioxidant at a high speed for 10min to obtain a uniform mixed material; adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the heat-aging-resistant PET nanocomposite; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are 160 ℃, 175 ℃, 185 ℃, 195 ℃, 200 ℃, 230 ℃, 240 ℃, 250 ℃ respectively. The results of the relevant property tests are shown in table 1.
Comparative example 1
Mixing 100 parts of PET, 10 parts of flame retardant and 0.3 part of antioxidant A at a high speed for 10min to obtain a uniform mixed material; adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain a PET composite material; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃, 220 ℃, 230 ℃, 240 ℃ and 240 ℃. The results of the relevant property tests are shown in table 1.
Comparative example 2
Mixing 100 parts of PET, 10 parts of flame retardant, 5 parts of nano-silica supported antioxidant and 0.3 part of antioxidant at high speed for 10min to obtain a uniform mixed material; adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain a PET composite material; wherein the extrusion temperatures of the extrusion zones in the twin-screw extruder are respectively 150 ℃, 160 ℃, 175 ℃, 185 ℃, 190 ℃, 220 ℃, 230 ℃, 240 ℃ and 240 ℃. The results of the relevant property tests are shown in table 1.
The PET composite materials prepared in examples 1-3 and comparative examples 1-2 were tested for their relevant properties, and the test items and test results are shown in Table 1.
TABLE 1
Wherein the retention of tensile strength after 2000h of heat aging/%, is 2000h of tensile strength after heat aging/tensile strength.
Notched Izod impact strength retention after 2000h heat aging ═ notched Izod impact strength/notched Izod impact strength after 2000h heat aging.
As can be seen from the data in Table 1, the thermal aging resistance of the PET nanocomposite prepared by the invention is obviously superior to that of the PET composite added with a single component antioxidant; meanwhile, the anti-aging performance of the load type antioxidant system adopting the nano cerium oxide as the carrier is also superior to that of the load type antioxidant system adopting other carriers.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments 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 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 (8)
1. The thermal aging resistant PET nano composite material is characterized by being prepared from the following components in parts by weight:
100 parts of PET (polyethylene terephthalate) (by weight),
5-10 parts of a flame retardant,
3-5 parts of a load-type antioxidant,
0.3 to 0.5 part of antioxidant,
the supported antioxidant is a cerium oxide supported reactive antioxidant, the cerium oxide supported reactive antioxidant is prepared by reacting nano cerium oxide, gamma-mercaptopropyl triethoxysilane and a reactive antioxidant, and the reactive antioxidant is antioxidant GM or antioxidant GS.
2. The heat aging resistant PET nanocomposite as claimed in claim 1, wherein the PET has a melt index of 10 to 15g/10min at 230 ℃ under 2.16 kg.
3. The heat aging resistant PET nanocomposite as claimed in claim 1, wherein the flame retardant is a mixture of magnesium hydroxide and aluminum hydroxide mixed in a mass ratio of 1:1, and the flame retardant has an average particle size of 1500 meshes.
4. The heat aging resistant PET nanocomposite as claimed in claim 1, wherein the cerium oxide supported reactive antioxidant is prepared by the specific steps of: adding dried nano cerium oxide into toluene for uniform dispersion, then adding gamma-mercaptopropyltriethoxysilane, heating, stirring and refluxing for 3-5 h at 90-100 ℃, then cooling the reaction system to 55-65 ℃, then adding a reactive antioxidant, continuing stirring for 1.5-2.5 h, separating and drying to obtain the cerium oxide supported reactive antioxidant.
5. The heat aging resistant PET nanocomposite as claimed in claim 1, wherein the mass ratio of the nano cerium oxide, gamma-mercaptopropyltriethoxysilane, and reactive antioxidant is 1:1: 3.
6. The heat aging resistant PET nanocomposite as claimed in claim 1, wherein the antioxidant is a mixture of pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and tris- (2, 4-di-t-butylphenyl) phosphite in a mass ratio of 1: 1.
7. The preparation method of the thermal aging resistant PET nanocomposite material as claimed in any one of claims 1 to 6, characterized by mixing PET, a flame retardant, a supported antioxidant and an antioxidant at a high speed according to a ratio to obtain a uniform mixed material; and adding the uniform mixed material into a double-screw extruder, mixing, extruding, cooling and granulating to obtain the heat-aging-resistant PET nanocomposite.
8. The method according to claim 7, wherein the extrusion temperature in each extrusion zone of the twin-screw extruder is 150 to 160 ℃, 160 to 175 ℃, 175 to 185 ℃, 185 to 195 ℃, 190 to 200 ℃, 220 to 230 ℃, 230 to 240 ℃, 240 to 250 ℃ and 240 to 250 ℃, respectively.
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CN201811433537.1A CN111234470B (en) | 2018-11-28 | 2018-11-28 | Thermal-aging-resistant PET (polyethylene terephthalate) nano composite material and preparation method thereof |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105348583A (en) * | 2015-12-10 | 2016-02-24 | 定远县杰仕达体育用品有限公司 | Ball type inner container flexible anti-wear material |
CN105713293A (en) * | 2014-12-05 | 2016-06-29 | 天津滨浦生产力促进有限公司 | Nano rare earth oxide/polypropylene composite material and preparation method thereof |
CN106349572A (en) * | 2016-08-31 | 2017-01-25 | 宁波市鄞州柯力塑业有限公司 | Transparent ageing-resistant water cup and preparation method thereof |
CN107418186A (en) * | 2017-08-25 | 2017-12-01 | 广州找塑料新材料科技有限公司 | A kind of vinal enhancing PPO/PA6 alloys of high-modulus and preparation method thereof |
CN108587146A (en) * | 2018-04-27 | 2018-09-28 | 黑龙江鑫达企业集团有限公司 | A kind of heat-resisting Long Glass Fiber Reinforced Pa composite material and preparation method |
-
2018
- 2018-11-28 CN CN201811433537.1A patent/CN111234470B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105713293A (en) * | 2014-12-05 | 2016-06-29 | 天津滨浦生产力促进有限公司 | Nano rare earth oxide/polypropylene composite material and preparation method thereof |
CN105348583A (en) * | 2015-12-10 | 2016-02-24 | 定远县杰仕达体育用品有限公司 | Ball type inner container flexible anti-wear material |
CN106349572A (en) * | 2016-08-31 | 2017-01-25 | 宁波市鄞州柯力塑业有限公司 | Transparent ageing-resistant water cup and preparation method thereof |
CN107418186A (en) * | 2017-08-25 | 2017-12-01 | 广州找塑料新材料科技有限公司 | A kind of vinal enhancing PPO/PA6 alloys of high-modulus and preparation method thereof |
CN108587146A (en) * | 2018-04-27 | 2018-09-28 | 黑龙江鑫达企业集团有限公司 | A kind of heat-resisting Long Glass Fiber Reinforced Pa composite material and preparation method |
Non-Patent Citations (3)
Title |
---|
稀土氧化物对提高甲基乙烯基硅橡胶耐热性的作用;张树明等;《特种橡胶制品》;20091215(第06期);第10-13页 * |
纳米CeO_2在聚合物中的应用;刘康强等;《化工新型材料》;20130315(第03期);第163-165页 * |
负载型抗氧剂的制备及应用研究进展;吴文剑等;《高分子材料科学与工程》;20161231(第10期);第170-176、182页 * |
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