CN117757234A - Preparation process of multi-component polyester particles - Google Patents
Preparation process of multi-component polyester particles Download PDFInfo
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- CN117757234A CN117757234A CN202311757797.5A CN202311757797A CN117757234A CN 117757234 A CN117757234 A CN 117757234A CN 202311757797 A CN202311757797 A CN 202311757797A CN 117757234 A CN117757234 A CN 117757234A
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- Prior art keywords
- polyethylene terephthalate
- parts
- waste polyethylene
- chain growth
- antioxidant
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- 229920000728 polyester Polymers 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 58
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 56
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 56
- 239000002699 waste material Substances 0.000 claims abstract description 55
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 33
- 239000008187 granular material Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- ZSSVCEUEVMALRD-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 ZSSVCEUEVMALRD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 235000019359 magnesium stearate Nutrition 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- KPNYFXUDBVQRNK-UHFFFAOYSA-N 1-(4-anilinophenyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1NC1=CC=CC=C1 KPNYFXUDBVQRNK-UHFFFAOYSA-N 0.000 claims description 4
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 2
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical group [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008029 phthalate plasticizer Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000010309 melting process Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 7
- 229960001826 dimethylphthalate Drugs 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention relates to the technical field of high polymer materials, and discloses a preparation process of multi-component polyester particles, which comprises the steps of firstly preprocessing waste polyethylene terephthalate, mixing the waste polyethylene terephthalate with a chain growth modifier, a macromolecular antioxidant, an inorganic additive, a plasticizer, an ultraviolet absorber and a lubricant, and finally extruding and granulating the mixture through double screws to obtain the polyester particles, wherein the chain growth modifier can realize the chain growth of the waste polyethylene terephthalate in the high-temperature melting process, so that the prepared polyester particles can reach a relatively balanced state between rigidity and toughness, further show good strength and toughness, and the addition of the lignin-based macromolecular antioxidant can play a role in synergistic antioxidation, so that the prepared polyester particles can show good ageing resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a manufacturing process of multi-component polyester particles.
Background
Under the background of the time that the environmental pollution is gradually aggravated, plastic resource recycling becomes the mainstream, among a plurality of plastic wastes, the polyester product types are more, the waste accounts for higher, the chemical structure is stable, the waste is not easily degraded by microorganisms in the environment, micro plastics can be formed to enter soil, rivers and the like, and the ecological environment is endangered, so that the method has important significance for recycling the polyester. However, after the polyethylene terephthalate polyester products are discarded, the waste polyethylene terephthalate polyester products are exposed to relatively severe environments such as humidity, heat, light, oxygen and the like for a long time, and inevitably undergo degradation, so that chemical bonds are broken, the molecular weight is reduced, the recycled polyester plastics are further aged, the appearance is affected, and the mechanical properties, the mechanical properties and the like are greatly reduced, the quality cannot be ensured, so that the waste polyethylene terephthalate polyester plastics cannot be recycled, and therefore, the waste polyethylene terephthalate polyester plastics need to be properly improved to meet the recycling requirement.
The invention patent application number CN20111087765. X discloses a high-tensile strength renewable recycled polyester sheet toughening process, which is characterized in that ethylene terephthalate, ethylene isophthalate, polyol ester, polybasic alkyd and stearate are added as tackifiers to perform polymerization reaction in the extrusion plasticizing process, so that the molecular weight of polyester generated in the extrusion plasticizing process is increased, and further the tensile strength and other properties of the polyester are enhanced, therefore, the molecular weight of the waste polyethylene terephthalate can be increased in a chain-extending manner, and the problem of poor mechanical properties of the waste polyethylene terephthalate is solved, but the ageing resistance of the waste polyethylene terephthalate cannot be improved in the manner, and based on the method, the multi-component polyester particles provided by the invention have good mechanical properties and ageing resistance.
Disclosure of Invention
The invention aims to provide a manufacturing process of multi-component polyester particles, which solves the problems of poor mechanical properties and poor ageing resistance of waste polyethylene terephthalate.
The aim of the invention can be achieved by the following technical scheme:
a process for making multicomponent polyester pellets comprising the steps of:
first step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
Putting waste polyethylene terephthalate granules, a chain growth modifier, a macromolecular antioxidant, an inorganic additive, a plasticizer, an ultraviolet absorber and a lubricant into a mixer, starting stirring, and uniformly mixing to form a mixed material;
third step, granulating
Transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to be 260-280 ℃ and the screw rotating speed to be 200-300r/min, extruding and granulating, and naturally cooling the master batch to obtain polyester particles;
the chain growth modifier is a block polymer containing norbornene and ether chain segments in the structure;
the macromolecular antioxidant is lignin containing amine antioxidant in the structure.
Further preferably, the polyester particles comprise the following raw materials in parts by weight: 75-85 parts of waste polyethylene terephthalate granules, 2-6 parts of chain growth modifier, 5-12 parts of macromolecular antioxidant, 5-10 parts of inorganic additive, 1-2 parts of plasticizer, 0.5-1 part of ultraviolet absorber and 1-2 parts of lubricant.
Further preferably, the chain growth modifier is prepared as follows:
dissolving glycerol diglycidyl ether in toluene to form a mixed solution, introducing nitrogen to protect gas, evacuating oxygen, adding 5-norbornene-2, 3-dicarboxylic acid into the mixed solution, starting stirring, starting heating until the 5-norbornene-2, 3-dicarboxylic acid is completely dissolved, adding a phase transfer catalyst into the mixed solution until the temperature is raised to 70-80 ℃, continuously stirring for 6-9h after the adding is finished, cooling, discharging, and collecting materials to obtain the chain growth modifier.
Specifically, the diglycidyl ether contains two equivalents of glycidyl groups, and can be subjected to continuous ring-opening esterification with carboxyl groups in 5-norbornene-2, 3-dicarboxylic acid under the action of a phase transfer catalyst to form a polymerization-state chain growth modifier with a structure containing a flexible ether segment and a rigid norbornene block structure.
Further preferably, the molar ratio of the glycerol diglycidyl ether and the 5-norbornene-2, 3-dicarboxylic acid is 1:1.
Further preferably, the phase transfer catalyst is at least one of tetrabutylammonium bromide or tetrabutylammonium bisulfate.
Further preferably, the preparation method of the macromolecular antioxidant is as follows:
step A, preparing lignin intermediate
Dissolving lignin in tetrahydrofuran, adding a catalyst under ice bath conditions, fully stirring and mixing to form a precursor liquid, adding chloroacetyl chloride into the precursor liquid, stirring for 4-6 hours at room temperature after uniformly mixing, separating out a solid material, washing the material with diethyl ether, and drying to obtain a lignin intermediate;
step B, preparing macromolecular antioxidant
Dissolving lignin intermediate in 1, 4-dioxane, placing in nitrogen atmosphere, adding amine antioxidant under nitrogen protection, starting heating, maintaining the temperature at 70-75deg.C for 6-8 hr, adjusting pH to neutrality with sodium hydroxide aqueous solution, filtering, and separating solid material to obtain macromolecular antioxidant.
Specifically, the lignin structure contains abundant aromatic hydroxyl groups, can be subjected to condensation reaction with chloroacetyl chloride under the action of a catalyst to form a halogenated lignin intermediate, and the halogen groups can be substituted with primary amine or secondary amine groups in the amine antioxidant, so that the amine antioxidant is grafted in the macromolecular lignin structure to form the macromolecular antioxidant.
Further preferably, in the step a, the catalyst is at least one of triethylamine or pyridine.
Further preferably, in step B, the amine antioxidant is at least one of N- (4-anilinophenyl) maleimide, N '-diphenyl-p-phenylenediamine, or N-cyclohexyl-N' -phenyl-p-phenylenediamine.
Further preferably, in the step B, the mass fraction of the sodium hydroxide aqueous solution is 12-15%.
Further preferably, the inorganic additive is at least one of fumed silica, calcium carbonate or diatomaceous earth; the plasticizer is a citrate plasticizer or a phthalate plasticizer; the ultraviolet absorber is at least one of UV-326, UV-1164 or UV-531; the lubricant is at least one of calcium stearate or magnesium stearate.
The invention has the beneficial effects that:
1) The chain growth modifier prepared by the invention can realize the chain growth of waste polyethylene terephthalate in the high-temperature melting process, and introduces the flexible ether chain links and the rigid norbornene chain links into the structure of the polyethylene terephthalate at the same time, so that the formed polyethylene terephthalate has the effect of hardness and softness, and the rigidity and toughness of the polyethylene terephthalate reach a relatively balanced state, thereby showing more excellent mechanical properties. In addition, the chain growth modifier contains a plurality of hydroxyl groups, so that the formed polyester particles can generate interpenetrating polymer network structures, show higher crosslinking density and more compact structures, and have higher impact performance.
2) According to the invention, lignin-based macromolecular antioxidants are used for modifying waste polyethylene terephthalate, on one hand, lignin contains a large amount of aromatic hydroxyl groups and quinone groups, an antioxidant effect similar to hindered phenol antioxidants can be generated, synergistic effect is generated between the lignin and amine antioxidants in the macromolecular antioxidants, lignin is used as a main antioxidant, the amine antioxidants are used as auxiliary antioxidants, the ageing resistance of the waste polyethylene terephthalate is enhanced, and the amine antioxidants are grafted and are subjected to a stable structure of chemical bonds, so that volatilization and migration are difficult to carry out, and the waste polyethylene terephthalate can stably exist in polyester particles.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FT-IR chart of a chain growth modifier in example 1 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of chain growth modifiers
Dissolving 1.5g of glycerol diglycidyl ether in toluene to form a mixed solution, introducing nitrogen to protect gas, evacuating oxygen, adding 1.34g of 5-norbornene-2, 3-dicarboxylic acid into the mixed solution, starting stirring, heating until the 5g of 5-norbornene-2, 3-dicarboxylic acid is completely dissolved, adding 0.5g of tetrabutylammonium bromide into the mixed solution when the temperature is raised to 75 ℃, continuously stirring for 8 hours after the adding is finished, cooling, discharging, and collecting materials to obtain the chain growth modifier.
FT-IR characterization of the chain growth modifier was determined using a Vector333 Fourier transform infrared spectrometer, and was prepared using KBr tablets, as shown in FIG. 1, and analyzed to determine 3381cm -1 The characteristic absorption peak at the position is a telescopic vibration peak of-OH, 3022cm -1 The characteristic absorption peak at the position is C-H stretching vibration peak at carbon-carbon double bond in norbornene, 1734cm -1 The characteristic absorption peak at the position is C=O stretching vibration peak generated by ring-opening esterification，1103cm -1 The characteristic absorption peak at the position is a stretching vibration peak of ether bond.
Example 2
Preparation of macromolecular antioxidant
Step A, preparing lignin intermediate
Dissolving 1.2g of lignin in tetrahydrofuran, adding 1.5g of pyridine under ice bath conditions, fully stirring and mixing to form a precursor solution, adding 3.5g of chloroacetyl chloride into the precursor solution, stirring for 6 hours under room temperature conditions after uniformly mixing, separating out solid materials, washing the materials with diethyl ether, and drying to obtain a lignin intermediate;
step B, preparing macromolecular antioxidant
1g of lignin intermediate is dissolved in 1, 4-dioxane, and is placed in a nitrogen atmosphere, under the protection of nitrogen, 0.8g of N- (4-anilinophenyl) maleimide is added, heating is started, the temperature is maintained at 70 ℃, after 8 hours, the pH is adjusted to be neutral by using 15% sodium hydroxide aqueous solution by mass fraction, and the solid material is separated, thus obtaining the macromolecular antioxidant.
The organic element content of the macromolecular antioxidant was analyzed by using a TR-CHN5000 element analyzer, and the carbon element content was 58.61% and the nitrogen element content was 5.85% in the structure, and since lignin contains no nitrogen element, it was presumed that the nitrogen element was provided by N- (4-anilinophenyl) maleimide.
Example 3
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
75 parts of waste polyethylene terephthalate granules, 2 parts of the chain growth modifier prepared in the embodiment 1 of the invention, 5 parts of the macromolecular antioxidant prepared in the embodiment 2 of the invention, 5 parts of fumed silica, 1 part of dimethyl phthalate, 0.5 part of ultraviolet absorbent UV-326 and 1 part of calcium stearate are put into a mixer, and stirring is started and uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 200r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Example 4
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
80 parts of waste polyethylene terephthalate granules, 5 parts of the chain growth modifier prepared in the embodiment 1 of the invention, 8 parts of the macromolecular antioxidant prepared in the embodiment 2 of the invention, 6 parts of calcium carbonate, 1.5 parts of dimethyl phthalate, 0.6 part of ultraviolet absorbent UV-1164 and 1.5 parts of magnesium stearate are put into a mixer, and stirring is started, and the mixture is uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Example 5
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
85 parts of waste polyethylene terephthalate granules, 5 parts of the chain extension modifier prepared in the embodiment 1 of the invention, 6 parts of the chain extension modifier prepared in the embodiment 1 of the invention, 12 parts of the macromolecular antioxidant prepared in the embodiment 2 of the invention, 10 parts of kieselguhr, 2 parts of dimethyl phthalate, 1 part of ultraviolet absorber UV-531 and 2 parts of calcium stearate are put into a mixer, and stirring is started, and the mixture is uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Comparative example 1
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
80 parts of waste polyethylene terephthalate granules, 5 parts of 1, 4-butanediol, 8 parts of macromolecular antioxidant prepared in the embodiment 2 of the invention, 6 parts of calcium carbonate, 1.5 parts of dimethyl phthalate, 0.6 part of ultraviolet absorbent UV-1164 and 1.5 parts of magnesium stearate are put into a mixer, and stirring is started, so that a mixed material can be formed;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Comparative example 2
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
80 parts of waste polyethylene terephthalate granules, 8 parts of macromolecular antioxidant prepared in the embodiment 2 of the invention, 6 parts of calcium carbonate, 1.5 parts of dimethyl phthalate, 0.6 part of ultraviolet absorbent UV-1164 and 1.5 parts of magnesium stearate are put into a mixer, and stirring is started, and the mixture is uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Comparative example 3
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
80 parts of waste polyethylene terephthalate granules, 5 parts of the chain growth modifier prepared in the embodiment 1 of the invention, 8 parts of lignin, 6 parts of calcium carbonate, 1.5 parts of dimethyl phthalate, 0.6 part of ultraviolet absorbent UV-1164 and 1.5 parts of magnesium stearate are put into a mixer, and stirring is started, and the mixture is uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Comparative example 4
Preparation of polyester granules
First step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
80 parts of waste polyethylene terephthalate granules, 5 parts of the chain growth modifier prepared in the embodiment 1 of the invention, 6 parts of calcium carbonate, 1.5 parts of dimethyl phthalate, 0.6 part of ultraviolet absorber UV-1164 and 1.5 parts of magnesium stearate are put into a mixer, and stirring is started, and the mixture is uniformly mixed to form a mixed material;
third step, granulating
And (3) transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to 265 ℃ and the screw speed to 300r/min, extruding and granulating, and naturally cooling the master batch to obtain the polyester granules.
Performance detection
According to national standard GB/T1040.2-2022, testing the tensile strength and elongation at break of the polyester particles; placing the test sample in an accelerated aging box at 120 ℃ for 48 hours, taking out the test sample, and testing the tensile strength and the elongation at break again;
according to national standard GB/T1843-2008, the impact property of the polyester particles is tested;
according to national standard GB/T9341-2008, the bending property of polyester particles is tested;
the results are recorded in the following table:
analysis of the test results shows that the polyester particles prepared by using the chain growth modifier prepared in the embodiment 1 of the invention and the macromolecular antioxidant prepared in the embodiment 2 of the invention as raw materials have high strength, good toughness and good mechanical properties, and the strength and toughness are limited in reduction value after accelerated aging, so that the polyester particles have good ageing resistance.
In comparative example 1, conventional 1, 4-butanediol is used as a chain growth modifier, although toughness of polyester particles can be improved to a certain extent, strength is obviously reduced, and in comparative example 2, the chain growth modifier is not added, so that strength and toughness are extremely poor, and ageing resistance performance is affected to a certain extent.
In comparative example 3, lignin was used as an antioxidant only, and although the prepared polyester pellets had a certain aging-resistant effect, they were inferior to those of examples, and in comparative example 4, no antioxidant was added, so that the aging-resistant performance was extremely poor.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A process for making multicomponent polyester pellets comprising the steps of:
first step, pretreatment
Taking waste polyethylene terephthalate, crushing the waste polyethylene terephthalate into particles, and performing cleaning and drying treatment to form waste polyethylene terephthalate particles;
second step, mixing materials
Putting waste polyethylene terephthalate granules, a chain growth modifier, a macromolecular antioxidant, an inorganic additive, a plasticizer, an ultraviolet absorber and a lubricant into a mixer, starting stirring, and uniformly mixing to form a mixed material;
third step, granulating
Transferring the mixed material into a double-screw extruder, controlling the extrusion temperature to be 260-280 ℃ and the screw rotating speed to be 200-300r/min, extruding and granulating, and naturally cooling the master batch to obtain polyester particles;
the chain growth modifier is a block polymer containing norbornene and ether chain segments in the structure;
the macromolecular antioxidant is lignin containing amine antioxidant in the structure.
2. The process for producing multicomponent polyester particles according to claim 1, wherein the polyester particles comprise the following raw materials in parts by weight: 75-85 parts of waste polyethylene terephthalate granules, 2-6 parts of chain growth modifier, 5-12 parts of macromolecular antioxidant, 5-10 parts of inorganic additive, 1-2 parts of plasticizer, 0.5-1 part of ultraviolet absorber and 1-2 parts of lubricant.
3. The process for preparing a multicomponent polyester pellet according to any one of claims 1 to 2, wherein the chain growth modifier is prepared as follows:
dissolving glycerol diglycidyl ether in toluene to form a mixed solution, introducing nitrogen to protect gas, evacuating oxygen, adding 5-norbornene-2, 3-dicarboxylic acid into the mixed solution, starting stirring, starting heating until the 5-norbornene-2, 3-dicarboxylic acid is completely dissolved, adding a phase transfer catalyst into the mixed solution until the temperature is raised to 70-80 ℃, continuously stirring for 6-9h after the adding is finished, cooling, discharging, and collecting materials to obtain the chain growth modifier.
4. A process for making multicomponent polyester pellets according to claim 3 wherein the molar ratio of glycerol diglycidyl ether to 5-norbornene-2, 3-dicarboxylic acid is 1:1.
5. A process for making multicomponent polyester pellets as in claim 3 wherein said phase transfer catalyst is at least one of tetrabutylammonium bromide or tetrabutylammonium bisulfate.
6. The process for preparing multicomponent polyester pellets according to any of claims 1 to 2, wherein the preparation of the macromolecular antioxidant is as follows:
step A, preparing lignin intermediate
Dissolving lignin in tetrahydrofuran, adding a catalyst under ice bath conditions, fully stirring and mixing to form a precursor liquid, adding chloroacetyl chloride into the precursor liquid, stirring for 4-6 hours at room temperature after uniformly mixing, separating out a solid material, washing the material with diethyl ether, and drying to obtain a lignin intermediate;
step B, preparing macromolecular antioxidant
Dissolving lignin intermediate in 1, 4-dioxane, placing in nitrogen atmosphere, adding amine antioxidant under nitrogen protection, starting heating, maintaining the temperature at 70-75deg.C for 6-8 hr, adjusting pH to neutrality with sodium hydroxide aqueous solution, filtering, and separating solid material to obtain macromolecular antioxidant.
7. The process of claim 6, wherein in step a, the catalyst is at least one of triethylamine or pyridine.
8. The process of claim 6, wherein in step B, the amine antioxidant is at least one of N- (4-anilinophenyl) maleimide, N '-diphenyl-p-phenylenediamine, or N-cyclohexyl-N' -phenyl-p-phenylenediamine.
9. The process for producing multicomponent polyester pellets according to claim 6, wherein in step B, the aqueous sodium hydroxide solution is 12 to 15% by mass.
10. The process for preparing a multicomponent polyester pellet according to any one of claims 1 to 2, wherein the inorganic additive is at least one of fumed silica, calcium carbonate or diatomaceous earth; the plasticizer is a citrate plasticizer or a phthalate plasticizer; the ultraviolet absorber is at least one of UV-326, UV-1164 or UV-531; the lubricant is at least one of calcium stearate or magnesium stearate.
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